CN102850217B - The preparation method of methoxyethyl acrylate and methoxyethyl methacrylate - Google Patents
The preparation method of methoxyethyl acrylate and methoxyethyl methacrylate Download PDFInfo
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Abstract
A kind of preparation method of (methyl) methoxyethyl acrylate is, employing bottom is reactor, top is the integration apparatus of rectifying tower, with (methyl) methyl acrylate and ethylene glycol-methyl ether for raw material, under catalyzer and stopper effect, reacting by heating in a kettle., generates (methyl) methoxyethyl acrylate; Then product is obtained by separating-purifying.The present invention adopts reactive distillation and azeotropic distillation coupling technique, reactive distillation and azeotropic distillation is carried out in same tower, decreases facility investment, reduce energy consumption, reduce material proportion, shorten the reaction times, improve the efficiency of reactor.Adopt ester exchange process not produce waste water, after being separated, obtain highly purified (methyl) methoxyethyl acrylate.The present invention additionally uses composite catalyst, improves reaction efficiency, shortens the reaction times, reduces polymkeric substance growing amount.The present invention also by adopting novel stopper, improves the colourity of product.
Description
Technical field
The present invention relates to the preparation method of Chemicals, particularly relate to the preparation method of a kind of methoxyethyl acrylate and methoxyethyl methacrylate.
Background technology
Methoxyethyl acrylate or methoxyethyl methacrylate have high temperature resistant and oil-proofness, it is made to can be used as the comonomer of polyacrylic elastomer, manufacture low temperature resistant and important monomer that is super low-temperature resistant acrylic elastomer, it is the comonomer manufacturing coating resin, can be used as barrier coat and tackiness agent in addition, PVC impact modifying agent, contact lens.Its multipolymer provides good bounding force, chemical resistance, elasticity, impact, weathering resistance and low-shrinkage, is the reactive thinner that photocuring is good.
Describe the preparation technology of (methyl) methoxyethyl acrylate in Chinese patent 200810053582.4, this patent adopts vinylformic acid and ethylene glycol-methyl ether under the effect of catalyzer and stopper, with benzene as water entrainer.The acid of esterification process technique, as catalyzer, has certain corrosion to equipment, produces more waste water in production process, due to needs solvent bank water, has the residual of benzene equal solvent in product.Also need in this patent through the process such as soda lye wash, desolventizing, technical process is complicated, and is all batch production, is not suitable for large-scale industrial production, and the water-content of the product that esterification process is produced is also higher, and product quality is poor.
The method of esterification process preparation (methyl) methoxyethyl acrylate is described in Chinese patent 200810053581.X, make to wash with water and replace decompression refining, add sorbent material by single aggressiveness of not yet (methyl) methoxyethyl acrylate of inactivation and dimer fractionation by adsorption simultaneously, wherein adsorption process needs the time, efficiency of post treatment is low, is not suitable for scale operation.
Describe post-esterification treatment process in Chinese patent 200810053579.2, have employed three step water washing process, adopted salt solution before this, and then adopted buck, and finally added washing again, not only produce a large amount of waste water, also will consume salt and alkali.
Describe solid catalyst in Chinese patent 201110242202.3, adopt the compound of cyanate, thiocyanate-and the calcium and magnesium oxides that corrodibility is serious, aftertreatment bothers, and contaminate environment.Its stopper introduced is adopted as organic copper salt, 2, 2, 6, 6-tetramethyl--4-hydroxy piperidine-1-oxygen nitroxyl free radical, tetramethyl piperidine nitrogen oxygen free radical tris phosphite, 2, 6-dinitro-p-cresol (hereinafter referred to as DNPC), 2-sec-butyl-4, 6-dinitrophenol(DNP) (hereinafter referred to as DNBP), p-ten.-butylcatechol, the phenols such as Resorcinol, wherein organic copper salt, 2, 2, 6, 6-tetramethyl--4-hydroxy piperidine-1-oxygen nitroxyl free radical, tetramethyl piperidine nitrogen oxygen free radical tris phosphite and 2, 6-dinitro-p-cresol (hereinafter referred to as DNPC), 2-sec-butyl-4, 6-dinitrophenol(DNP) (hereinafter referred to as DNBP), p-ten.-butylcatechol, the composite result of use of Resorcinol is better, though above-mentioned composite polymerization inhibitor polymerization inhibition effect is better, but be easily entrained in still-process in product, have impact on the quality of product.
The esterification process technique of prior art adopts vinylformic acid to do raw material, and require higher to equipment material, esterification process not only produces a large amount of waste water, bring environmental issue, and water-content is high in the product adopting esterification process to produce, residual solvent in product, limits the application in downstream.The present invention adopts ester exchange process technology, with (methyl) methyl acrylate for raw material, corrosion-free to equipment, reaction process methanol, methyl alcohol and (methyl) methyl acrylate form azeotrope, (methyl) methyl acrylate can be reclaimed by azeotropic distillation, be back in reactor, neither produce water in ester-interchange method process and also can not introduce water entrainer, the entrainer boiling point introduced is lower, can not remain in the product, (methyl) methoxyethyl acrylate product purity obtained after being separated is high, colourity is good, very be suitable as coating resin, acrylic elastomer, contact lens, the comonomer of the novel materials such as photocuring.
General transesterify adopts excessive (methyl) methyl acrylate and the formation of methanol azeotrope, so just make the material proportion of (methyl) methyl acrylate and ethylene glycol-methyl ether in reactor too high, ethylene glycol-the methyl ether dropped into is on the low side, in reactor, the content of (methyl) methyl acrylate is high, reduces the service efficiency of reactor.And the present invention adopts reactive distillation and azeotropic distillation coupling technique to reduce material proportion in reactor, add the input amount of ethylene glycol-methyl ether, improve the service efficiency of reactor, in reaction solution, the content of (methyl) methyl acrylate reduces, also mitigate the load of sepn process below, decrease (methyl) methyl acrylate recovery system simultaneously, be conducive to the energy consumption of saving separation and removal process, reduce the cost that (methyl) methyl acrylate reclaims.
The present invention has larger innovation in Technology, catalyzer and stopper three, adopt azeotropic distillation and reactive distillation coupling technique technology, reduce the proportioning of (methyl) methyl acrylate in reactor and ethylene glycol-methyl ether, improve temperature of reaction, improve reactor efficiency, be convenient to Automated condtrol, be beneficial to large-scale industrial production; Adopt the novel catalyst system that can be recycled, reduce the cost that catalyst levels reduces catalyzer; Select the novel stopper of composite high boiling point, avoid product carrying secretly in still-process.The most outstanding consumption innovatively utilizing reactive distillation and azeotropic distillation coupling technique to reduce (methyl) methyl acrylate of the present invention, utilize entrainer that the methyl alcohol produced is removed fast, accelerate reaction to the movement generating product direction, improve the efficiency of reactor.
Compared with prior art, the present invention also has following concrete advantage and disadvantage:
(1) the present invention adopts reactive distillation and azeotropic distillation coupling technique, and creationary reactive distillation and the azeotropic distillation of making completes in a tower, decreases the investment of recovery tower.The present invention uses hexanaphthene or normal hexane etc. as entrainer, and adding of entrainer adds from the refluxing opening of rectifying tower.The present invention reduces facility investment, be conducive to industrialization continuous seepage, be convenient to Automated condtrol, be conducive to the stable of quality product.
(2) catalyzer adopts the organic tin catalyzer such as dibutyl two isocaprylic acid tin, dibutyl tin sulfide, Dibutyltin oxide, tributyltin oxide, dibutyl tin dilaurate, the organic titanium class catalyzer such as poly(tributoxy titanium), titanium ethanolate, isopropyl titanate, tetrabutyl titanate, above-mentioned organic tin catalyzer and organic titanium class catalyzer can be used alone, the two is better with the use of effect, proportioning is 1: 10 ~ 10: 1 is the best, the catalyst activity be compounded to form is high, greatly decline to the susceptibility of water, this catalyst system can be recycled.
(3) stopper is poly-{ [6-[(1,1,3,3-tetramethyl butyl) is amino]]-1,3,5-triazine-2,4-two [(2,2,6,6,-tetramethyl-4-piperidyl) imino-]-1,6-hexanediamine [(2,2,6,6-tetramethyl--4-piperidyl) imino-], or poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) ester or the composite polymerzation inhibitor of the two.Composite polymerzation inhibitor ratio is 20: 1 ~ 1: 20, and be best with 10: 1 ~ 1: 10, composite polymerzation inhibitor can recycle.
Adopt preparation method of the present invention, can reduce material proportion, improve the efficiency of reactor, and technical process simplifies, reaction conditions is gentle, and easy and simple to handle, transformation efficiency is high, and product quality is high and stable.
Summary of the invention
Object of the present invention is exactly to solve above-mentioned prior art Problems existing, provides the preparation method of a kind of methoxyethyl acrylate and methoxyethyl methacrylate.
In order to achieve the above object, present invention employs following technical scheme: a kind of preparation method of methoxyethyl acrylate, comprises the following steps:
(1) generation of methoxyethyl acrylate
Employing bottom is reactor, top is the integration apparatus of rectifying tower, with methyl acrylate and ethylene glycol-methyl ether for raw material, is aided with catalyzer and stopper, is placed in reactor reacting by heating, generates methoxyethyl acrylate and methyl alcohol; Remove the methyl alcohol generated in reaction process in time to move to promote the direction of reacting to generating methoxyethyl acrylate by making the azeotropic of methyl acrylate and methyl alcohol, the methyl alcohol generated is by entering the rectifying tower on reactor with the azeotropic of methyl acrylate, start when rectifying column bottom temperature starts to rise to add entrainer from the refluxing opening of rectifying tower tower top, by adjusting the flow control tower top temperature of entrainer;
(2) separating-purifying of methoxyethyl acrylate
After reaction certain hour, get sample analysis in reactor, after ethylene glycol in reaction solution-methyl ether content is qualified, reaction solution is moved to storage tank, carry out separating-purifying, first remove light constituent and unreacted methyl acrylate and ethylene glycol-methyl ether, then remove heavy constituent and catalyzer and stopper, obtain product methoxyethyl acrylate;
The weight proportion of described methyl acrylate and ethylene glycol-methyl ether is 1.2-2.5: 1;
The consumption of described catalyzer is the 0.5%-3.0% of reaction solution total amount;
The consumption of described stopper is the 0.02%-0.2% of reaction solution total amount;
The consumption of described entrainer is the 20-40% of ethylene glycol-methyl ether consumption.
A generation method for methoxyethyl methacrylate, comprises the following steps:
(1) generation of methoxyethyl methacrylate
Employing bottom is reactor, top is the integration apparatus of rectifying tower, with methyl methacrylate and ethylene glycol-methyl ether for raw material, is aided with catalyzer and stopper, is placed in reactor reacting by heating, generates methoxyethyl methacrylate and methyl alcohol; Remove the methyl alcohol generated in reaction process in time to move to promote the direction of reacting to generating methoxyethyl methacrylate by making the azeotropic of methyl methacrylate and methyl alcohol, the methyl alcohol generated is by entering the rectifying tower on reactor with the azeotropic of methyl methacrylate, start when rectifying column bottom temperature starts to rise to add entrainer from the refluxing opening of rectifying tower tower top, by adjusting the flow control tower top temperature of entrainer;
(2) separating-purifying of methoxyethyl methacrylate
After reaction certain hour, get sample analysis in reactor, after ethylene glycol in reaction solution-methyl ether content is qualified, reaction solution is moved to storage tank, carry out separating-purifying, first remove light constituent and unreacted methyl methacrylate and ethylene glycol-methyl ether, then remove heavy constituent and catalyzer and stopper, obtain product methoxyethyl methacrylate;
The weight proportion of described methyl methacrylate and ethylene glycol-methyl ether is 1.2-2.5: 1;
The consumption of described catalyzer is the 0.5%-3.0% of reaction solution total amount;
The consumption of described stopper is the 0.02%-0.2% of reaction solution total amount;
The consumption of described entrainer is the 20-40% of ethylene glycol-methyl ether consumption.
In above-mentioned two kinds of preparation methods, wherein, described catalyzer is selected from the one in organic tin catalyzer or organic titanium class catalyzer, or the composite catalyst be made up of a kind of organic tin catalyzer and a kind of organic titanium class catalyzer; Organic tin catalyzer comprises dibutyl two isocaprylic acid tin, dibutyl tin sulfide, Dibutyltin oxide, tributyltin oxide or dibutyl tin dilaurate; Organic titanium class catalyzer comprises poly(tributoxy titanium), titanium ethanolate, isopropyl titanate or tetrabutyl titanate; In composite catalyst, the weight proportion of organic tin catalyzer and organic titanium class catalyzer is 20: 1 ~ 1: 20.
In above-mentioned two kinds of preparation methods, wherein, described stopper is poly-{ [6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazine-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1,6-hexanediamine [(2,2,6,6-tetramethyl--4-piperidyl) imino-], or poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) ester, or the two composite polymerzation inhibitor, in composite polymerzation inhibitor, both weight proportions are 20: 1 ~ 1: 20.
In above-mentioned two kinds of preparation methods, wherein, described entrainer is selected from the one in normal hexane, hexanaphthene or methylcyclohexane.
In above-mentioned two kinds of preparation methods, wherein, the reaction described in step (1) is carried out at ambient pressure, and temperature of reaction controls at 80 ~ 130 DEG C, and the tower top temperature of rectifying tower controls, at 49-51 DEG C, to control at temperature 85-105 DEG C at the bottom of tower.
In above-mentioned two kinds of preparation methods, wherein, in the separating-purifying described in step (2), removing light constituent stage control vacuum tightness is 10-30kPa, and tower top temperature is 30-50 DEG C; Removing heavy constituent stage control vacuum tightness is 5-15kPa, and tower top temperature is 50-60 DEG C.
In above-mentioned two kinds of preparation methods, wherein, in the reaction solution described in step (2), ethylene glycol-methyl ether content is qualified refers to that the content of ethylene glycol-methyl ether in reaction solution reaches 1.0-8.0%.
In above-mentioned two kinds of preparation methods, wherein, in described composite catalyst, the weight proportion of organic tin catalyzer and organic titanium class catalyzer is 1: 10 ~ 10: 1.
In above-mentioned two kinds of preparation methods, wherein, in described composite polymerzation inhibitor, both weight proportions are 10: 1 ~ 1: 10.
Embodiment
Embodiment 1
5 liters of reactors, on reactor, rectifying tower is Φ 50 × 2.5mm, tower height 1000mm.
Catalyzer is dibutyl tin sulfide, and stopper is poly-{ [6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazine-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1,6-hexanediamine [(2,2,6,6-tetramethyl--4-piperidyl) imino-], entrainer is normal hexane.
Be add 2451g methyl acrylate and 1444g ethylene glycol-methyl ether at 1.5: 1 according to the weight ratio of material in a kettle., add catalyzer 78g, stopper 7.8g.
Reactor heats up, rectifying column bottom temperature on question response still rises to 50 DEG C, open rectifying tower top reflux pump, according to certain flow backflow entrainer, controlled the tower top temperature 49 DEG C of rectifying tower by the heating of adjustment reactor and trim the top of column, react after 6 hours, temperature of reaction kettle 110 DEG C, sampling analysis, reaction solution is composed as follows:
After cooling, reaction solution is moved to separating unit.First methyl acrylate and ethylene glycol-methyl ether are removed under certain vacuum degree, then Removal of catalyst and stopper under higher vacuum tightness, tower top comes control temperature and product purity by controlling backflow, obtains the methoxyethyl acrylate of 2080g purity 99.9% after being separated.
Embodiment 2
5 liters of reactors, on reactor, rectifying tower is Φ 50 × 2.5mm, tower height 1000mm.
Catalyzer is dibutyl tin sulfide, and stopper is poly-{ [6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-two [(2,2,6,6,-tetramethyl-4-piperidyl) imino-]-1,6-hexanediamine [(2,2,6,6-tetramethyl--4-piperidyl) imino-] and poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) mixture of ester, the two quality proportioning is 1: 3, and entrainer is hexanaphthene.
Be add 2451g methyl acrylate and 1444g ethylene glycol-methyl ether at 1.5: 1 according to the weight ratio of material in a kettle., add catalyzer 78g, stopper 7.8g.
Reactor heats up, rectifying column bottom temperature on question response still rises to 50 DEG C, open rectifying tower top reflux pump, according to certain flow backflow entrainer, the tower top temperature being controlled rectifying tower by the heating of adjustment reactor and trim the top of column is 49 DEG C, reacts after 6 hours, temperature of reaction kettle 110 DEG C, sampling analysis, reaction solution is composed as follows:
After cooling, reaction solution is moved to separating unit.First methyl acrylate and ethylene glycol-methyl ether are removed under certain vacuum degree, then Removal of catalyst and stopper under higher vacuum tightness, tower top comes control temperature and product purity by controlling backflow, obtains the methoxyethyl acrylate of 2100g purity 99.9% after being separated.
Embodiment 3
5 liters of reactors, on reactor, rectifying tower is Φ 50 × 2.5mm, tower height 1000mm.
Catalyzer is the mixture of Dibutyltin oxide and tetrabutyl titanate, and the two quality proportioning is 3: 1, and stopper is poly-{ [6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazine-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1,6-hexanediamine [(2,2,6,6-tetramethyl--4-piperidyl) imino-] and poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) mixture of ester, the two quality proportioning is 1: 3, and entrainer is methylcyclohexane.
Be add 2451g methyl acrylate and 1444g ethylene glycol-methyl ether at 1.5: 1 according to the weight ratio of material in a kettle., add catalyzer 78g, stopper 7.8g.
Reactor heats up, rectifying column bottom temperature on question response still rises to 50 DEG C, open rectifying tower top reflux pump, according to certain flow backflow entrainer, the tower top temperature being controlled rectifying tower by the heating of adjustment reactor and trim the top of column is 49 DEG C, reacts after 6 hours, temperature of reaction kettle 110 DEG C, sampling analysis, reaction solution is composed as follows:
After cooling, reaction solution is moved to separating unit.First methyl acrylate and ethylene glycol-methyl ether are removed under certain vacuum degree, then Removal of catalyst and stopper under higher vacuum tightness, tower top comes control temperature and product purity by controlling backflow, obtains the methoxyethyl acrylate of 2160g purity 99.9% after being separated.
Embodiment 4
5 liters of reactors, on reactor, rectifying tower is Φ 50 × 2.5mm, tower height 1000mm.
Catalyzer is the mixture of Dibutyltin oxide and tetrabutyl titanate, the two quality proportioning 3: 1, and stopper is poly-{ [6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazine-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1,6-hexanediamine [(2,2,6,6-tetramethyl--4-piperidyl) imino-] and poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) mixture of ester, the two quality proportioning is 1: 3, and entrainer is normal hexane.
Be add 2470g methyl methacrylate and 1444g ethylene glycol-methyl ether at 1.3: 1 according to amount of substance ratio in a kettle., add catalyzer 78g, stopper 7.8g.
Reactor heats up, rectifying column bottom temperature on question response still rises to 50 DEG C, open rectifying tower top reflux pump, according to certain flow backflow entrainer, the tower top temperature being controlled rectifying tower by the heating of adjustment reactor and trim the top of column is 50 DEG C, reacts after 6 hours, temperature of reaction kettle 125 DEG C, sampling analysis, reaction solution is composed as follows:
After cooling, reaction solution is moved to separating unit.First methyl methacrylate and ethylene glycol-methyl ether are removed under certain vacuum degree, then Removal of catalyst and stopper under higher vacuum tightness, tower top comes control temperature and product purity by controlling backflow, obtains the methoxyethyl methacrylate of 2350g purity 99.9% after being separated.
Embodiment 5
8000 liters of reactors, on reactor, rectifying tower is Φ 600 × 5mm, tower height 10000mm.
Catalyzer is the mixture of Dibutyltin oxide and tetrabutyl titanate, the two quality proportioning 3: 1, and stopper is poly-{ [6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazine-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1,6-hexanediamine [(2,2,6,6-tetramethyl--4-piperidyl) imino-] and poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) mixture of ester, the two quality proportioning is 1: 3, and entrainer is hexanaphthene.
Be add 3922kg methyl acrylate and 2310kg ethylene glycol-methyl ether at 1.5: 1 according to weight ratio in a kettle., add catalyzer 125kg, stopper 12kg.
Reactor heats up, rectifying column bottom temperature on question response still rises to 50 DEG C, open rectifying tower top reflux pump, according to certain flow backflow entrainer, the tower top temperature being controlled rectifying tower by the heating of adjustment reactor and trim the top of column is 49 DEG C, reacts after 8 hours, temperature of reaction kettle 115 DEG C, sampling analysis, reaction solution is composed as follows:
After cooling, reaction solution is moved to separating unit.First methyl acrylate and ethylene glycol-methyl ether are removed under certain vacuum degree, then Removal of catalyst and stopper under higher vacuum tightness, tower top comes control temperature and product purity by controlling backflow, obtains the methoxyethyl acrylate of 3450kg purity 99.9% after being separated.
Embodiment 6
8000 liters of reactors, on reactor, rectifying tower is Φ 600 × 5mm, tower height 10000mm.
Catalyzer is the mixture of Dibutyltin oxide and tetrabutyl titanate, and the quality proportioning of the two is 3: 1, and stopper is poly-{ [6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazine-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1,6-hexanediamine [(2,2,6,6-tetramethyl--4-piperidyl) imino-] and poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) mixture of ester, the two quality proportioning is 1: 3, and entrainer is methylcyclohexane.
Be add 3951kg methyl methacrylate and 2310kg ethylene glycol-methyl ether at 1.3: 1 according to weight ratio in a kettle., add catalyzer 125kg, stopper 13kg.
Reactor heats up, rectifying column bottom temperature on question response still rises to 50 DEG C, open rectifying tower top reflux pump, according to certain flow backflow entrainer, the tower top temperature being controlled rectifying tower by the heating of adjustment reactor and trim the top of column is 50 DEG C, reacts after 8 hours, temperature of reaction kettle 127 DEG C, sampling analysis, reaction solution is composed as follows:
After cooling, reaction solution is moved to separating unit.First methyl methacrylate and ethylene glycol-methyl ether are removed under certain vacuum degree, then Removal of catalyst and stopper under higher vacuum tightness, tower top comes control temperature and product purity by controlling backflow, obtains the methoxyethyl methacrylate of 3750kg purity 99.9% after being separated.
Claims (8)
1. a preparation method for methoxyethyl acrylate, is characterized in that, comprises the following steps:
(1) generation of methoxyethyl acrylate
Employing bottom is reactor, top is the integration apparatus of rectifying tower, with methyl acrylate and ethylene glycol-methyl ether for raw material, is aided with catalyzer and stopper, is placed in reactor reacting by heating, generates methoxyethyl acrylate and methyl alcohol; Remove the methyl alcohol generated in reaction process in time to move to promote the direction of reacting to generating methoxyethyl acrylate by making the azeotropic of methyl acrylate and methyl alcohol, the methyl alcohol generated is by entering the rectifying tower on reactor with the azeotropic of methyl acrylate, start when rectifying column bottom temperature starts to rise to add entrainer from the refluxing opening of rectifying tower tower top, by adjusting the flow control tower top temperature of entrainer;
(2) separating-purifying of methoxyethyl acrylate
After reaction certain hour, get sample analysis in reactor, after ethylene glycol in reaction solution-methyl ether content is qualified, reaction solution is moved to storage tank, carry out separating-purifying, first remove light constituent and unreacted methyl acrylate and ethylene glycol-methyl ether, then remove heavy constituent and catalyzer and stopper, obtain product methoxyethyl acrylate;
The weight proportion of described methyl acrylate and ethylene glycol-methyl ether is 1.2-2.5:1;
The consumption of described catalyzer is the 0.5%-3.0% of reaction solution total amount;
The consumption of described stopper is the 0.02%-0.2% of reaction solution total amount;
The consumption of described entrainer is the 20-40% of ethylene glycol-methyl ether consumption;
Described catalyzer is selected from the composite catalyst be made up of a kind of organic tin catalyzer and a kind of organic titanium class catalyzer; Organic tin catalyzer is selected from dibutyl two isocaprylic acid tin, dibutyl tin sulfide, Dibutyltin oxide, tributyltin oxide or dibutyl tin dilaurate; Organic titanium class catalyzer is selected from poly(tributoxy titanium), titanium ethanolate, isopropyl titanate or tetrabutyl titanate; The weight proportion of organic tin catalyzer and organic titanium class catalyzer is 20:1-1:20;
Described stopper is poly-{ [6-[(1,1,3,3-tetramethyl butyl) is amino]]-1,3,5-triazine-2,4-two [(2,2,6,6,-tetramethyl-4-piperidyl) imino-]-1,6-hexanediamine [(2,2,6,6-tetramethyl--4-piperidyl) imino-] and poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) composite polymerzation inhibitor of ester, in composite polymerzation inhibitor, both weight proportions are 20:1 ~ 1:20.
2. a preparation method for methoxyethyl methacrylate, is characterized in that: comprise the following steps:
(1) generation of methoxyethyl methacrylate
Employing bottom is reactor, top is the integration apparatus of rectifying tower, with methyl methacrylate and ethylene glycol-methyl ether for raw material, is aided with catalyzer and stopper, is placed in reactor reacting by heating, generates methoxyethyl methacrylate and methyl alcohol; Remove the methyl alcohol generated in reaction process in time to move to promote the direction of reacting to generating methoxyethyl methacrylate by making the azeotropic of methyl methacrylate and methyl alcohol, the methyl alcohol generated is by entering the rectifying tower on reactor with the azeotropic of methyl methacrylate, start when rectifying column bottom temperature starts to rise to add entrainer from the refluxing opening of rectifying tower tower top, by adjusting the flow control tower top temperature of entrainer;
(2) separating-purifying of methoxyethyl methacrylate
After reaction certain hour, get sample analysis in reactor, after ethylene glycol in reaction solution-methyl ether content is qualified, reaction solution is moved to storage tank, carry out separating-purifying, first remove light constituent and unreacted methyl methacrylate and ethylene glycol-methyl ether, then remove heavy constituent and catalyzer and stopper, obtain product methoxyethyl methacrylate;
The weight proportion of described methyl methacrylate and ethylene glycol-methyl ether is 1.2-2.5:1;
The consumption of described catalyzer is the 0.5%-3.0% of reaction solution total amount;
The consumption of described stopper is the 0.02%-0.2% of reaction solution total amount;
The consumption of described entrainer is the 20-40% of ethylene glycol-methyl ether consumption;
Described catalyzer is selected from the composite catalyst be made up of a kind of organic tin catalyzer and a kind of organic titanium class catalyzer; Organic tin catalyzer is selected from dibutyl two isocaprylic acid tin, dibutyl tin sulfide, Dibutyltin oxide, tributyltin oxide or dibutyl tin dilaurate; Organic titanium class catalyzer is selected from poly(tributoxy titanium), titanium ethanolate, isopropyl titanate or tetrabutyl titanate; The weight proportion of organic tin catalyzer and organic titanium class catalyzer is 20:1-1:20;
Described stopper is poly-{ [6-[(1,1,3,3-tetramethyl butyl) is amino]]-1,3,5-triazine-2,4-two [(2,2,6,6,-tetramethyl-4-piperidyl) imino-]-1,6-hexanediamine [(2,2,6,6-tetramethyl--4-piperidyl) imino-] and poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) composite polymerzation inhibitor of ester, in composite polymerzation inhibitor, both weight proportions are 20:1 ~ 1:20.
3. preparation method according to claim 1 and 2, is characterized in that: described entrainer is selected from the one in normal hexane, hexanaphthene or methylcyclohexane.
4. preparation method according to claim 1 and 2, it is characterized in that: the reaction described in step (1) is carried out at ambient pressure, temperature of reaction controls at 80-130 DEG C, and the tower top temperature of rectifying tower controls, at 49-51 DEG C, to control at temperature 85-105 DEG C at the bottom of tower.
5. preparation method according to claim 1 and 2, is characterized in that: in the separating-purifying described in step (2), and removing light constituent stage control vacuum tightness is 10-30kPa, and tower top temperature is 30-50 DEG C; Removing heavy constituent stage control vacuum tightness is 5-15kPa, and tower top temperature is 50-60 DEG C.
6. preparation method according to claim 1 and 2, is characterized in that: in the reaction solution described in step (2), ethylene glycol-methyl ether content is qualified refers to that the content of ethylene glycol-methyl ether in reaction solution reaches 1.0-8.0%.
7. preparation method according to claim 1 and 2, is characterized in that: in described composite catalyst, and the weight proportion of organic tin catalyzer and organic titanium class catalyzer is 1:10-10:1.
8. preparation method according to claim 1 and 2, is characterized in that: in described composite polymerzation inhibitor, and both weight proportions are 10:1-1:10.
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| CN101146761A (en) * | 2005-11-16 | 2008-03-19 | 西巴特殊化学品控股有限公司 | Manufacture of esters |
| CN102351693A (en) * | 2011-08-23 | 2012-02-15 | 里光 | Preparation method for methoxyethyl methacrylate |
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| CN1525953A (en) * | 2001-06-08 | 2004-09-01 | �����ɷ� | Method for producing (meth) acrylic acid esters |
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