CN103131001A - One-step preparation method of polyoxyethylene ether acrylate - Google Patents
One-step preparation method of polyoxyethylene ether acrylate Download PDFInfo
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- CN103131001A CN103131001A CN2011103776044A CN201110377604A CN103131001A CN 103131001 A CN103131001 A CN 103131001A CN 2011103776044 A CN2011103776044 A CN 2011103776044A CN 201110377604 A CN201110377604 A CN 201110377604A CN 103131001 A CN103131001 A CN 103131001A
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Abstract
The invention discloses a one-step preparation method of polyoxyethylene ether acrylate. The one-step preparation method comprises the following steps of 1, preparing acrylate and ethylene oxide as raw materials into polyoxyethylene ether acrylate having a polymerization degree of 1 to 25 according to a mole ratio of ethylene oxide to acrylate of (1: 1) to (25: 1), 2, utilizing a B-series main catalyst and a metal salt cocatalyst, 3, protecting allyl double bonds by a polymerization inhibitor in reaction and storage, and 4, carrying out ethoxylation of acrylate at a certain temperature under pressure in a high pressure autoclave to obtain the polyoxyethylene ether acrylate finished product. The one-step preparation method has the advantages of simple processes, less side reaction, high product yield, low cost, narrow polyether product molecular weight distribution and good applicability.
Description
[technical field]
The present invention relates to the fine chemical technology field, specifically, is a kind of production method of acrylate Soxylat A 25-7.
[background technology]
The acrylate Soxylat A 25-7, it is a kind of novel nonionogenic tenside, have the structure of two keys, ester bond and polyethers key concurrently, good surfactivity is arranged, can give with the reactive hydrogen addition or with the unsaturated compound copolymerization the good lubrication of product, soft effect, good spreadability and stable emulsifying property, by changing the length of its oxyethyl chain, can be widely used in many fields such as water reducer for building, polyurethane flexible or hard foam stabilizer, agricultural organosilicon synergist, low foam washing, lubricating oil, weaving, market capacity and potentiality are very large.
At present, indirect method is adopted in the production of acrylate Soxylat A 25-7, namely first makes poly glycol monomethyl ether and then direct esterification or carries out transesterify, and complex process, low conversion rate, by product are many, the easy polymerization of esterification process, cause quality product relatively poor, far can not satisfy the demand of future market.
US Patent No. 6362364 is than having described esterification reaction process in greater detail, and with methoxy poly (ethylene glycol), methacrylic acid, tosic acid hydrate, thiodiphenylamine and cyclohexane give raw material, esterification yield can reach 99%, and oxyethyl chain reaches 25.But the common by product of this method is more, and the operation of the post-reaction treatment such as the washing that need neutralize is brought difficulty for product separation, catalyst recovery and wastewater treatment etc., thereby makes complex process equipment.And improved the requirement to the equipment anticorrosion performance.
Ester-interchange method generally carries out transesterification reaction with acrylate and poly glycol monomethyl ether, and catalyzer commonly used is generally highly basic and the strong acid such as the vitriol oil, sulfonic acid such as sodium alkoxide, magnesium alkoxide, sodium hydroxide, calcium hydroxide, Tetramethylammonium hydroxide, cetyltrimethylammonium hydroxide.The people such as Guo Baowen count the methoxy poly (ethylene glycol) ether of 6-12 with EO with excessive methyl methacrylate carries out transesterification reaction by transesterification reaction, the acquisition product.This method is in the solvent-free reaction system, and poly glycol monomethyl ether is because relative molecular mass is relatively large, has larger sterically hinderedly, and-OH is wrapped up by polyethoxye, and-OH reduces with-possibility that COOH contacts, is unfavorable for the carrying out that reacts.Therefore should not adopt this method when obtaining the polyethylene glycol monomethyl ethermethacrylic acid esters of high molecular weight.
Aforesaid method fails to solve that by product is many, product purification is difficult, yield is low, complex process, technical problem that cost is high.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, a kind of one-step method for synthesizing of acrylate Soxylat A 25-7 is provided, thereby simplify production technique, reduce production costs, improve the quality of products.
The objective of the invention is to be achieved through the following technical solutions:
Single stage method prepares the acrylate Soxylat A 25-7, and concrete steps are,
(1) use acrylate, oxyethane as the step of raw material, adjustment ring oxidative ethane and acrylate mol ratio 1: 1～25: 1, acrylate Soxylat A 25-7 that can the corresponding preparation polymerization degree 1～25;
(2) use BX
3Be Primary Catalysts, Mg
2+, Al
3+, Fe
2+, Ti
4+, Sn
2+, Cu
2+Be promotor Deng wherein one or more metal-salt; Preferred as such scheme, Primary Catalysts consumption 0.1wt%～0.50wt%, promotor consumption are 0.1wt%～0.5wt%, all in reasonable mass percent by the product gross weight;
(3) use Resorcinol or MEHQ, perhaps both composition is stopper; Preferred as such scheme, the stopper consumption is the 0.01wt%～0.30wt% of theoretical product total mass;
(4) in autoclave, make acrylate and one step of oxyethane ethoxylation under certain temperature, pressure, obtain the acrylate Soxylat A 25-7.Preferred as such scheme, temperature of reaction is between 15～105 ℃, reaction pressure is 0～0.9MPa;
(5) before the reaction, acrylate, catalyzer, stopper once drop into autoclave, and oxyethane is continuously feeding in reaction process, preferred as such scheme, and input speed is 0.2～5g/mim.
This method yield can reach 90%～94%.Single step reaction of the present invention can make esters of acrylic acid polyoxy Vinyl Ether, and greatly simple technical process has that with short production cycle, less energy consumption, cost are low, the product purity advantages of higher.
The reaction formula of methyl methacrylate ethoxylation of the present invention is:
Compared with prior art, positively effect of the present invention is:
(1) technique of the present invention is simple, and side reaction is few, and product yield is high, greatly reduces cost.
(2) polyether product narrow molecular weight distribution of the present invention, applicability is improved.
[embodiment]
The embodiment of the production method of a kind of acrylate Soxylat A 25-7 of the present invention below is provided.
Embodiment 1
Clean autoclave, add methyl methacrylate 100g, catalyzer 2.7g, promotor 0.9g and stopper 1.6g cover kettle cover, and tighten the screws installs thermocouple thermometer, the resistance to air loss of check whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 50r/min, nitrogen is filled with in autoclave to gauge pressure 0.1MPa, then vacuumize, so triplicate.The unlatching middling speed stirs, and opens heating, when being heated to 20 ℃, with the speed importing oxyethane of 2.5g/min, controls reaction stagnation pressure 0.2～0.4MPa, 25 ℃ of temperature in the kettle.Reinforced complete to 880g oxyethane, insulation 1.0h still is pressed constant, is cooled to 30 ℃ of 10min dischargings of finding time.
Filtration obtains the light yellow clarifying liquid body, is 93.1% through liquid chromatography-mass spectrometry methyl methacrylate Soxylat A 25-7 yield, and molecular-weight average is 940, mean polymerisation degree 23.
Embodiment 2
Clean autoclave, add methyl methacrylate 100g, catalyzer 3.8g, promotor 1.3g and stopper 2.3g cover kettle cover, and tighten the screws installs thermocouple thermometer, the resistance to air loss of check whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 50r/min, nitrogen is filled with in autoclave to gauge pressure 0.1MPa, then vacuumize, so triplicate.The unlatching middling speed stirs, and opens heating, when being heated to 60 ℃, with the speed importing oxyethane of 1.5g/min, controls reaction stagnation pressure 0.1～0.4MPa, 65 ℃ of temperature in the kettle.Reinforced complete to 660g oxyethane, insulation 1.0h still is pressed constant, is cooled to 30 ℃ of 10min dischargings of finding time.
Filtration obtains the light yellow clarifying liquid body, is 90.4% through liquid chromatography-mass spectrometry methyl methacrylate Soxylat A 25-7 yield, and molecular-weight average is 760, mean polymerisation degree 17.
Embodiment 3
Clean autoclave, add methyl acrylate 86g, catalyzer 2.6g, promotor 0.9g and stopper 1.6g cover kettle cover, and tighten the screws installs thermocouple thermometer, the resistance to air loss of check whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 150r/min, nitrogen is filled with in autoclave to gauge pressure 0.3MPa, then vacuumize, so triplicate.The unlatching middling speed stirs, and opens heating, when being heated to 90 ℃, with the speed importing oxyethane of 2.5g/min, controls reaction stagnation pressure 0.5～0.7MPa, 95 ℃ of temperature in the kettle.Reinforced complete to 440g oxyethane, insulation 1.0h still is pressed constant, is cooled to 30 ℃ of 10min dischargings of finding time.
Filtration obtains the light yellow clarifying liquid body, is 92.7% through liquid chromatography-mass spectrometry methyl acrylate Soxylat A 25-7 yield, and molecular-weight average is 526, mean polymerisation degree 12.
Embodiment 4
Add methyl acrylate 86g, catalyzer 1.5g in autoclave, promotor 0.5g and stopper 0.9g cover kettle cover, and tighten the screws installs thermocouple thermometer, the resistance to air loss of check whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 250r/min, nitrogen is filled with in autoclave to gauge pressure 0.1MPa, then vacuumize, so triplicate.The unlatching middling speed stirs, and opens heating, when being heated to 60 ℃, with the speed importing oxyethane of 3.5g/min, controls reaction stagnation pressure 0.2～0.4MPa, 75 ℃ of temperature in the kettle.Reinforced complete to 220g oxyethane, insulation 1.0h still is pressed constant, is cooled to 30 ℃ of 10min dischargings of finding time.
Filtration obtains achromaticity and clarification liquid, is 92.3% through liquid chromatography-mass spectrometry methyl acrylate Soxylat A 25-7 yield, and molecular-weight average is 306, mean polymerisation degree 6.
Embodiment 5
Add ethyl propenoate 100g, catalyzer 2.7g in autoclave, promotor 0.9g and stopper 1.6g cover kettle cover, and tighten the screws installs thermocouple thermometer, the resistance to air loss of check whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 250r/min, nitrogen is filled with in autoclave to gauge pressure 0.1MPa, then vacuumize.The unlatching middling speed stirs, and opens heating, when being heated to 60 ℃, with the speed importing oxyethane of 1.5g/min, controls reaction stagnation pressure 0.2～0.4MPa, 75 ℃ of temperature in the kettle.Reinforced complete to 440g oxyethane, insulation 1.0h still is pressed constant, is cooled to 30 ℃ of 10min dischargings of finding time.
Filtration obtains the light yellow clarifying liquid body, is 90.8% through liquid chromatography-mass spectrometry ethyl propenoate Soxylat A 25-7 yield, and molecular-weight average is 540, mean polymerisation degree 10.
Embodiment 6
Clean autoclave, get rid of wherein foreign matter, add ethyl propenoate 100g, catalyst B F32.3g, magnesium pot molecular sieve 0.8g and the MEHQ 1.4g of new system cover kettle cover, and tighten the screws installs thermocouple thermometer, the resistance to air loss of check whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 50r/min, nitrogen is filled with in autoclave to gauge pressure 0.1MPa, then vacuumize, so triplicate.The unlatching middling speed stirs, and opens heating, when being heated to 60 ℃, with the speed importing oxyethane of 2.5g/min, controls reaction stagnation pressure 0.2～0.4MPa, 75 ℃ of temperature in the kettle.Reinforced complete to 352g oxyethane, insulation 1.0h still is pressed constant, is cooled to 30 ℃ of 10min dischargings of finding time.
Filtration obtains the light yellow clarifying liquid body, and ethyl propenoate Soxylat A 25-7 yield 94.2%, molecular-weight average are 452, mean polymerisation degree 8.
Embodiment 7
Clean autoclave, add β-dimethyl-aminoethylmethacrylate 114g, catalyzer 2.8g, promotor 0.9g and stopper 1.7g cover kettle cover, and tighten the screws installs thermocouple thermometer, the resistance to air loss of check whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 250r/min, nitrogen is filled with in autoclave to gauge pressure 0.1MPa, then vacuumize, so triplicate.The unlatching middling speed stirs, and opens heating, when being heated to 60 ℃, with the speed importing oxyethane of 2.5g/min, controls reaction stagnation pressure 0.2～0.4MPa, 75 ℃ of temperature in the kettle.Reinforced complete to 880g oxyethane, insulation 1.0h still is pressed constant, is cooled to 30 ℃ of 10min dischargings of finding time.
Filtration obtains the light yellow clarifying liquid body, is 92.3% through liquid chromatography-mass spectrometry β-dimethyl-aminoethylmethacrylate Soxylat A 25-7 yield, and molecular-weight average is 954, mean polymerisation degree 18.
Advantage of the present invention: technique is simple, and side reaction is few, and product yield is high, greatly reduces cost; The polyether product narrow molecular weight distribution, applicability is improved.
The above is only the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (5)
1. single stage method prepares the acrylate Soxylat A 25-7, it is characterized in that, concrete steps are,
(1) use acrylate, oxyethane as the step of raw material, adjustment ring oxidative ethane and acrylate mol ratio 1: 1～25: 1, the acrylate Soxylat A 25-7 of the corresponding preparation polymerization degree 1～25;
(2) use BX
3Be Primary Catalysts, X is F, Cl, Br, I, Mg
2+, Al
3+, Fe
2+, Ti
4+, Sn
2+, Cu
2+In one or more metal-salt be promotor;
(3) use one or both in Resorcinol, MEHQ to be stopper;
(4) in autoclave, make acrylate and oxyethane step ethoxylation under the temperature, pressure condition, obtain the acrylate Soxylat A 25-7.
2. single stage method as claimed in claim 1 prepares the acrylate Soxylat A 25-7, it is characterized in that, described in step (1), acrylate comprises methyl methacrylate, β-dimethyl-aminoethylmethacrylate, methyl acrylate, ethyl propenoate.Acrylate once drops into autoclave before reacting, oxyethane is continuously feeding in reaction process, and input speed is 0.2～5g/mim.
3. single stage method as claimed in claim 1 prepares the acrylate Soxylat A 25-7, it is characterized in that catalyst B X described in step (2)
3Be Primary Catalysts, Mg
2+, Al
3+, Fe
2+, Ti
4+, Sn
2+, Cu
2+Deng in one or more metal-salt be promotor; Primary Catalysts consumption 0.1wt%～0.50wt%, promotor consumption are 0.1wt%～0.5wt%, all in the per-cent of the matter of reasonable opinion product gross weight.
4. single stage method as claimed in claim 1 prepares the acrylate Soxylat A 25-7, it is characterized in that, described in step (3), the stopper consumption is the 0.01wt%～0.30wt% of theoretical product total mass.
5. single stage method as claimed in claim 1 prepares the acrylate Soxylat A 25-7, it is characterized in that, temperature of reaction is between 15～105 ℃, and reaction pressure is 0～0.9MPa.
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| CN201110377604.4A CN103131001B (en) | 2011-11-23 | 2011-11-23 | One-step preparation method of polyoxyethylene ether acrylate |
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| CN201110377604.4A CN103131001B (en) | 2011-11-23 | 2011-11-23 | One-step preparation method of polyoxyethylene ether acrylate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924706A (en) * | 2012-07-05 | 2013-02-13 | 上海多纶化工有限公司 | Preparation method for polyethylene glycol mono alkyl ether unsaturated carboxylic ester |
| CN104130126A (en) * | 2014-07-26 | 2014-11-05 | 常州大学 | Method for synthesizing ethoxyethyl acrylate through alkoxylation |
| CN104710606A (en) * | 2013-12-12 | 2015-06-17 | 辽宁奥克化学股份有限公司 | Alkenyl terminated polyether ester and preparation method thereof, and water reducing agent prepared by using alkenyl terminated polyether ester and preparation method thereof |
| CN105885028A (en) * | 2016-06-17 | 2016-08-24 | 华东理工大学 | Polyether alcohol ester compound and application thereof |
| CN109913260A (en) * | 2019-02-15 | 2019-06-21 | 广州赫尔普化工有限公司 | A kind of chitosan quasi-oil demulsifier and preparation method thereof |
| CN110862527A (en) * | 2019-11-21 | 2020-03-06 | 联泓(江苏)新材料研究院有限公司 | Preparation method of unsaturated acid polyoxyalkene ester compound |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924706A (en) * | 2012-07-05 | 2013-02-13 | 上海多纶化工有限公司 | Preparation method for polyethylene glycol mono alkyl ether unsaturated carboxylic ester |
| CN104710606A (en) * | 2013-12-12 | 2015-06-17 | 辽宁奥克化学股份有限公司 | Alkenyl terminated polyether ester and preparation method thereof, and water reducing agent prepared by using alkenyl terminated polyether ester and preparation method thereof |
| CN104130126A (en) * | 2014-07-26 | 2014-11-05 | 常州大学 | Method for synthesizing ethoxyethyl acrylate through alkoxylation |
| CN105885028A (en) * | 2016-06-17 | 2016-08-24 | 华东理工大学 | Polyether alcohol ester compound and application thereof |
| CN105885028B (en) * | 2016-06-17 | 2020-09-04 | 华东理工大学 | Polyether alcohol ester compound and application thereof |
| CN109913260A (en) * | 2019-02-15 | 2019-06-21 | 广州赫尔普化工有限公司 | A kind of chitosan quasi-oil demulsifier and preparation method thereof |
| CN110862527A (en) * | 2019-11-21 | 2020-03-06 | 联泓(江苏)新材料研究院有限公司 | Preparation method of unsaturated acid polyoxyalkene ester compound |
| CN110862527B (en) * | 2019-11-21 | 2022-08-16 | 联泓(江苏)新材料研究院有限公司 | Preparation method of unsaturated acid polyoxyalkene ester compound |
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