CN102617849A - Method for preparing alkyl polyoxyethylene ether acrylate or alkyl polyoxyethylene ether methacrylic ester - Google Patents
Method for preparing alkyl polyoxyethylene ether acrylate or alkyl polyoxyethylene ether methacrylic ester Download PDFInfo
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- CN102617849A CN102617849A CN201210041196XA CN201210041196A CN102617849A CN 102617849 A CN102617849 A CN 102617849A CN 201210041196X A CN201210041196X A CN 201210041196XA CN 201210041196 A CN201210041196 A CN 201210041196A CN 102617849 A CN102617849 A CN 102617849A
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Abstract
The invention discloses a method for preparing alkyl polyoxyethylene ether acrylate or alkyl polyoxyethylene ether methacrylic ester. The method includes dehydrating alkyl polyoxyethylene ether by the aid of entrainer at first, adding inhibitor, resin solid acid catalyst and crylic acid or methacrylic ester, heating while controlling reaction temperature to range from 70 DEG C to 120 DEG C, stirring, realizing reaction and removing water generated in the esterification reaction by the aid of azeotropy; and carrying out filtering, and decompressing and distilling filtrate to obtain a target product. During reaction, resin solid acid is used as the catalyst insoluble in a reaction system, is easy to be removed by means of separating solid from liquid after the reaction is completed, and can be reused, accordingly, cost is lowered, and the quality of the product is improved. In addition, the ecologically environment-friendly alkyl polyoxyethylene ether is selectively used as a raw material, and prepared alkyl polyoxyethylene ether acrylic acid (methacrylic acid) ester non-ionic polymerizable surfactant has a fine application prospect.
Description
Technical field
The present invention relates to the preparation method of a kind of alkyl polyoxyethylene ether propenoate or alkyl polyoxyethylene ether methacrylic ester, belong to the preparing technical field of polymerisable surfactant.
Background technology
Alkyl polyoxyethylene ether propenoate or alkyl polyoxyethylene ether methacrylic ester are one type of nonionic polymerisable surfactants.Alkyl polyoxyethylene ether type nonionogenic tenside is to be made by Fatty Alcohol(C12-C14 and C12-C18) with reactive hydrogen (oleophilic group) and oxyethane (hydrophilic group) polymerization, and can adjust the hydrophile-lipophile balance value of self through the ratio of adjustment lipophilic group (fatty alcohol radical) and hydrophilic radical (polyoxyethylene group).Because alkyl polyoxyethylene ether has good emulsifying property, soil release characteristics, water-soluble, salt tolerance, resistance to acids and bases and static resistance; Can make solubilizing agent, dispersion agent, static inhibitor, emulsifying agent; Be widely used in industry cleaning and emulsification and disperse, also can be used as levelling agent in the printing and dyeing industry.
Acrylic or methacrylic acid is introduced in the alkyl polyoxyethylene ether, synthesized nonionogenic tenside with polymerization activity.Gathering the Soxylat A 25-7 propenoate or gather the polyethenoxy ether methyl acid alkyl ester with alkyl is monomer, prepares the coating of different application demand, thickening material, flocculation agent, textile printing and dyeing stablizer, makeup suspension agent through equal polymerization or copolymerization.
Publication number is the preparation method that the Chinese invention patent of CN1316398 discloses a kind of methyl esters polyethenoxy ether metacrylic acid ester, and this method is with the methyl Soxylat A 25-7, and Resorcinol, P-TOLUENE SULFO ACID 99 are put in people's reactor drum; Under 85 ± 3 ℃ temperature; Stirring drips TEB 3K after Resorcinol and tosic acid are dissolved fully in container, the control rate of addition; In 15 ± 5 minutes, drip off; Maintain the temperature at then in 85 ± 3 ℃ of scopes, reacted 8 ± 0.5 hours, reaction generates the methyl esters polyethenoxy ether metacrylic acid ester.But this patent adopts organic acid catalyst, and product separation purification aftertreatment is complicated.
Publication number is the preparation method that the Chinese invention patent of CN101215118 discloses copolymeric polycarboxylic acid water reducing agent and macromonomer thereof; It is a raw material with the methoxyl group list end-blocking Soxylat A 25-7 and the acrylic or methacrylic acid of different molecular weight, adopts solid super-strong acid SO
4 2-/ Fe
2O
3Or SO
4 2-/ TiO
2Be catalyzer,, prepare alkyl polyoxyethylene ether propenoate or alkyl polyoxyethylene ether methacrylic ester through esterification or transesterification reaction through alkyl polyoxyethylene ether and vinylformic acid, methylacrylic acid, propenoate or methylacrylic acid.The solid super-strong acid that this patent adopted separates with product easily, has improved the quality of product, and reusable, but solid super-strong acid preparation trouble, and use cost is also higher.
Summary of the invention
The present invention is directed to the problem that prior art exists; The novel process that a kind of resin solid acid catalyst prepares alkyl polyoxyethylene ether propenoate or alkyl polyoxyethylene ether methacrylic ester has been proposed; This method production cost is low; Environmental protection, alkyl polyoxyethylene ether propenoate or alkyl polyoxyethylene ether methacrylic ester yield and quality are high.
The present invention combines the technological advantage of organic acid and solid superacid as catalyst esterification, adopts resin solid acid as catalyst alkyl polyoxyethylene ether and acrylic or methacrylic acid esters reaction synthesis of alkyl Soxylat A 25-7 propenoate or alkyl polyoxyethylene ether methacrylic ester.The resin solid acid catalyst that is adopted is with low cost, has both had very high catalyzing esterification activity, is insoluble to reaction system; After reaction finishes, be easy to remove through solid-liquid separation, reusable again; Significantly improve the yield and the quality of alkyl polyoxyethylene ether propenoate or alkyl polyoxyethylene ether methacrylic ester; And it has reduced environmental pollution, has reduced production cost, is convenient to industriallization.
The alkyl polyoxyethylene ether propenoate of indication of the present invention or the structural formula of alkyl polyoxyethylene ether methacrylic ester are following:
In the formula, R
1Represent H or CH
3R
2Representing the carbon atom number is the alkyl of 1-30; N is a T 46155 number of repeat unit in the molecule, and n gets 1-80.
Alkyl polyoxyethylene ether propenoate of the present invention or alkyl polyoxyethylene ether methacrylic ester adopt esterification synthetic; Promptly use acrylic or methacrylic acid; Alkyl polyoxyethylene ether is a raw material; Preparation in the presence of resin solid acid catalyst, dewatering agent and entrainer, reaction equation is following:
In the formula, R
1Represent H or CH
3R
2Representing the carbon atom number is the alkyl of 1-30; N is a T 46155 number of repeat unit in the molecule, and n gets 1-80.
The object of the invention realizes through following technical scheme:
The preparation method of a kind of alkyl polyoxyethylene ether propenoate or alkyl polyoxyethylene ether methacrylic ester may further comprise the steps:
(1) raw material dehydration: alkyl polyoxyethylene ether is dewatered through entrainer;
(2) reaction: after thing dehydration to be mixed finished, cooling added stopper, resin solid acid catalyst and acrylic or methacrylic acid, and the heating control reaction temperature is 70-120 ℃, stirs, and reaction, azeotropic is sloughed the water that esterification generates; Follow the tracks of reaction process through tlc point plate, developping agent is a volume ratio 2～10: 1 chloroform and Virahol; The disappearance of the point of alkyl polyoxyethylene is a stopped reaction on silica gel point plate; The consumption of stopper is the 0.01-1% of acrylic or methacrylic acid quality, and stopper is selected one or more in Resorcinol, para benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-ten.-butylcatechol and the methylene blue for use; The consumption of acrylic or methacrylic acid be alkyl polyoxyethylene ether molar mass 1-10 doubly; The consumption of resin solid acid catalyst is the 1%-50% of reactant total mass;
(3) separate purification: reaction system is reduced to room temperature, filters, and collects the resin solid acid catalyst; Filtrating is extracted azeotropic solvent, acrylic or methacrylic acid out through underpressure distillation, obtains title product alkyl polyoxyethylene ether propenoate or alkyl polyoxyethylene ether methacrylic ester.
Further; Described resin solid acid catalyst is the pearl body that under the effect of perforating agent, becomes through suspension copolymerization with vinylbenzene and divinylbenzene; Has a macroporous netlike through what sulfonation reaction obtained again; Mean pore size is 30-55nm, and median size is 0.30-1.40mm, and the quality CEC is greater than 5.00mmol/g [H
+], have the brown spherical high polymer polymer beads of sulfonic acid group.
Described alkyl polyoxyethylene ether is dewatered through entrainer is meant that an alkyl polyoxyethylene ether and entrainer add in the reactor drum; Heating makes the alkyl polyoxyethylene ether dissolving; Stir, reheat makes the reaction mixture azeotropic dehydration, and the temperature of reaction of control azeotropic dehydration is 60-120 ℃; Until the clarification that refluxes, the water liquid level no longer raises; Said entrainer consumption is the 50-150% of alkyl polyoxyethylene ether quality.
Described entrainer is preferentially selected one or more in normal hexane, hexanaphthene, sherwood oil, benzene, toluene and the YLENE for use.
The consumption of described acrylic or methacrylic acid be preferably alkyl polyoxyethylene ether molar mass 2-8 doubly.
With respect to prior art, the present invention has following beneficial effect:
What (1) the present invention adopted is the resin solid acid catalyst, and this catalyzer is insoluble to reaction system, therefore little to equipment corrosion; In addition, reaction finishes the back product easily through Solid-Liquid Separation, need not wash and neutralize; Catalyzer is reusable through handling again; Thereby reduced cost, reduced environmental pollution, improved the quality of product;
(2) the present invention has adopted the organic solvent azeotropic dehydration technique, can effectively remove to reach the water that reaction generates in the reactant, promotes carrying out smoothly of esterification, has shortened the reaction times, has practiced thrift cost.Solvent is reusable, has also reduced cost.
(3) the present invention drops into excessive acrylic or methacrylic acid in reaction, has improved the transformation efficiency of alkyl polyoxyethylene ether, and the transformation efficiency of alkyl polyoxyethylene ether propenoate or methacrylic ester can reach more than 95%.
(4) the alkyl polyoxyethylene ether propenoate or the alkyl polyoxyethylene ether methacrylic ester of the present invention's preparation are one type of nonionic polymerisable surfactants; The emulsifying agent that can be used as letex polymerization; Also can be through preparing coating, thickening material, the flocculation agent of different application demand, textile printing and dyeing stablizer, makeup suspension agent with other monomer copolymerizable.
Description of drawings
Fig. 1 is the ir spectra (FTIR) of ethoxylated dodecyl alcohol (1) and ethoxylated dodecyl alcohol propenoate (2).
Fig. 2 be the ethoxylated dodecyl alcohol propenoate mr hydrogen spectrum (
1HNMR) spectrum.
Fig. 3 is that ethoxylated dodecyl alcohol (1) is schemed with the usefulness dsc (DSC) of ethoxylated dodecyl alcohol propenoate (2).
The practical implementation method
Below in conjunction with accompanying drawing and embodiment the present invention is further described, but the scope that the present invention requires to protect is not limited to the scope that embodiment explains.
The preparation of resin solid acid: in the there-necked flask of 1L, add 500g water and 5g gelatin, start stirring, be warming up to 50 ℃ and make the gelatin dissolving.Add 100g vinylbenzene then, 18g Vinylstyrene (80wt%), 1.2gBPO and 85g whiteruss are warming up to 80 ℃ of reactions 3 hours, are warming up to 95 ℃ of reactions 1 hour again, the cool to room temperature after-filtration, washing obtains white bead after the oven dry.Then use the petroleum ether extraction pore-creating agent, sieve out cross-linked styrene-divinylbenzene resin white bead of diameter 0.20～1.40mm.
Get the above-mentioned cross-linked styrene that makes-divinylbenzene resin white bead 100g and place the 1L there-necked flask; With 100g ethylene dichloride swelling 2 hours, stir and add the 300g vitriol oil down, be warming up to 90 ℃ and refluxed 4.5 hours; Then be warming up to 110 ℃ and boil off ethylene dichloride; Drip again behind the 30% oleum 400g 115 ℃ of insulations 12 hours down, sampling and measuring resins exchange amount, when the resins exchange amount greater than 5.00mmol/g [H
+] back cooling end reaction; Make the resin solid acid catalyst after being neutrality with distilled water washing resin to effluent; Through detecting, the performance of resinous acid catalyzer is: the quality CEC is 5.30mmol/g [H
+], mean pore size is 38nm, median size is 0.5mm, has the brown spherical high polymer polymer beads of sulfonic acid group.
Whisking appliance is housed, temperature is taken into account in the 500ml four-hole boiling flask of water trap, adds laureth 200g, adds toluene 150g, heating for dissolving starts and stirs, and keeps 110 ℃ of temperature, makes the mixture azeotropic, divides water, clarifies until distillate.
Be cooled to 45 ℃, in four-hole boiling flask, add vinylformic acid 20g, stopper phenothiazine 0.5g then; Resin solid acid catalyst 5g, heating keeps the interior temperature of bottle at 110 ℃; Sampling adopts tlc to follow the tracks of the process of reaction; Use developping agent to be chloroform: Virahol=5: 1 (volume ratio), when not observing the alkyl polyoxyethylene invocation point on the silica gel point plate, reaction finishes.
Reaction finishes, cool to room temperature, and filtration under diminished pressure, resin solid acid is subsequent use after collecting processing again.Filtrating then adds in another round-bottomed flask that vacuum distillation apparatus 500ml is housed, and 60 ℃ of decompression rotary distillations obtain laureth propenoate product.The ir spectra of product (FTIR), proton nmr spectra (
1HNMR) and differential scanning calorimetry (DSC) turn out to be title product laureth propenoate, see accompanying drawing 1-3.Through liquid chromatographic detection, alkyl polyoxyethylene ether propenoate transformation efficiency and product purity can reach more than 95%.
Fig. 1 is the ir spectra (FTIR) of ethoxylated dodecyl alcohol 1 and ethoxylated dodecyl alcohol propenoate 2.Ir spectra adopts the Bruker Vector of company 33 tests, pressing potassium bromide troche.Ethoxylated dodecyl alcohol 1 and ethoxylated dodecyl alcohol propenoate 2 are all at 1062～1146cm
-1Triplet occurs, this is ehter bond-CH in the polyoxyethylene glycol segment
2-O-CH
2Characteristic peak.Compare 1635cm in the spectrogram of ethoxylated dodecyl alcohol propenoate 2 with ethoxylated dodecyl alcohol 1
-1Be the stretching vibration peak of vinylformic acid-C=C key, 989cm
-1For-CH=CH
2The outer formation vibration peak of face.1726cm
-1Be the stretching vibration peak of ester carbonyl group, and 3400cm
-1The hydroxyl peak at place disappears, shows that then vinylformic acid and ethoxylated dodecyl alcohol 1 esterification have taken place generated ethoxylated dodecyl alcohol propenoate 2.
Fig. 2 be the ethoxylated dodecyl alcohol propenoate mr hydrogen spectrum (
1HNMR) spectrum.
1HNMR adopts Bruker Avance Digital 400MHz to measure, and solvent is DMSO-d6.The triplet that between δ=5.95～6.34, occurs is CH=CH
2In the chemical shift of 3 hydrogen.The absorption peak at δ=4.20 places is and ester carbonyl group (CH
2-O-C=O) the chemical shift of the hydrogen on the adjacent methylene radical.And the multiplet between δ=3.29～3.65 is peg molecule chain (CH
2-CH
2-O) in the chemical shift of hydrogen in the methylene radical.δ=1.25 places are the chemical shift of long-chain methylene radical hydrogen in the ethoxylated dodecyl alcohol propenoate.δ=0.83 place is the chemical shift of alkyl chain methyl hydrogen in the ethoxylated dodecyl alcohol propenoate.
Fig. 3 is that ethoxylated dodecyl alcohol 1 is schemed with the usefulness dsc (DSC) of ethoxylated dodecyl alcohol propenoate 2.DSC adopts the TA DSC 204C of company to measure, and is the heating curve second time shown in the figure, and heating rate is 5 ℃/min.As can be seen from Figure 3, the fusing point of ethoxylated dodecyl alcohol 1 is 40 ℃, and the fusing point of amphipathic monomer ethoxylated dodecyl alcohol propenoate 2 is lower slightly, is 39 ℃.This is because behind the hydroxyl and vinylformic acid generation esterification in the compound cinnamic alcohol Soxylat A 25-7 1; Interaction of hydrogen bond in the compound ethoxylated dodecyl alcohol propenoate 2 that generates has weakened, and causes the fusing point of ethoxylated dodecyl alcohol propenoate 2 to be lower than nonesterified compound ethoxylated dodecyl alcohol 1.
Whisking appliance is housed, temperature is taken into account in the 500ml four-hole boiling flask of water trap, adds stearyl Soxylat A 25-7 150g, adds hexanaphthene 120g, heating for dissolving starts and stirs, and keeps 80 ℃ of temperature, makes the mixture azeotropic, divides water, clarifies until distillate.
Be cooled to 45 ℃, in four-hole boiling flask, add vinylformic acid 40g, hydroquinone of polymerization retarder 0.2g then; Resin solid acid catalyst (preparation method is with embodiment 1) 50g, heating, temperature is at 80 ℃ in keeping; Tlc test reaction process is adopted in sampling; Developping agent is a chloroform: Virahol=3: 1 (volume ratio), when not observing the alkyl polyoxyethylene invocation point on the TLC point plate, reaction finishes.
Reaction finishes, cool to room temperature, and filtration under diminished pressure, resin solid acid is subsequent use after collecting processing again.Filtrating adds another is equipped with in the round-bottomed flask of vacuum distillation apparatus 500ml, at 50 ℃ of decompression rotary distillations down, obtains stearyl Soxylat A 25-7 propenoate product, through FTIR,
1HNMR turns out to be title product (the similar Fig. 2 of accompanying drawing situation).Through liquid chromatographic detection, product purity is 98.2%.
Embodiment 3
The preparation of resin solid acid: in the there-necked flask of 1L, add 500g water and 5g gelatin, start stirring, be warming up to 50 ℃ and make the gelatin dissolving.Add 120g vinylbenzene then, 14g Vinylstyrene (80wt%), 1.4gBPO and 95g whiteruss are warming up to 80 ℃ of reactions 3 hours, are warming up to 95 ℃ of reactions 1 hour again, the cool to room temperature after-filtration, washing obtains white bead after the oven dry.Then use the petroleum ether extraction pore-creating agent, sieve out cross-linked styrene-divinylbenzene resin white bead of diameter 0.20～1.40mm.
The above-mentioned cross-linked styrene that makes-divinylbenzene resin white bead is according to the method sulfonation of instance 1, and the performance of the resinous acid catalyzer that obtains at last is: the quality CEC is 5.35mmol/g [H
+], mean pore size is 46nm, median size is 0.8mm, has the brown spherical high polymer polymer beads of sulfonic acid group.
Whisking appliance is housed, temperature is taken into account in the 500ml four-hole boiling flask of water trap, adds octyl group Soxylat A 25-7 120g, adds toluene 180g, heating for dissolving starts and stirs, and keeps 110 ℃ of temperature, makes the mixture azeotropic, divides water, clarifies until distillate.
Be cooled to 45 ℃, add vinylformic acid 45g, stopper phenothiazine 0.3g in then in flask; Resin solid acid catalyst 8g, heating, temperature is at 110 ℃ in keeping; Tlc test reaction process is adopted in sampling; Developping agent is a chloroform: Virahol=6: 1 (volume ratio), when not observing the alkyl polyoxyethylene invocation point on the silica gel point plate, reaction finishes.
Reaction finishes, cool to room temperature, and filtration under diminished pressure, resin solid acid is subsequent use after collecting processing again.Filtrating adds another is equipped with in the round-bottomed flask of vacuum distillation apparatus 500ml, and 50 ℃ of decompression rotary distillations obtain octyl group Soxylat A 25-7 propenoate product, through FTIR,
1HNMR turns out to be title product (the similar Fig. 2 of accompanying drawing situation).Through liquid chromatographic detection, product purity 95.4%.
Whisking appliance is housed, temperature is taken into account in the 500ml four-hole boiling flask of water trap, adds mountain Yu base Soxylat A 25-7 150g, adds normal hexane 150g, heating for dissolving starts and stirs, and keeps 70 ℃ of temperature, makes the mixture azeotropic, divides water, clarifies until distillate.
Be cooled to 45 ℃, in reaction flask, add methylacrylic acid 30g, stopper para benzoquinone 0.8g then; Resin solid acid catalyst (preparation method is with embodiment 3) 40g, heating, temperature is at 70 ℃ in keeping; Tlc test reaction process is adopted in sampling; Developping agent is a chloroform: Virahol=3: 1 (volume ratio), when not observing the alkyl polyoxyethylene invocation point on the silica gel point plate, reaction finishes.
Reaction finishes, cool to room temperature, and filtration under diminished pressure, resin solid acid is subsequent use after collecting processing again.Filtrating adds another is equipped with in the round-bottomed flask of vacuum distillation apparatus 500ml, and 70 ℃ of decompression rotary distillations obtain mountain Yu base polyethenoxy ether metacrylic acid ester product, through FTIR,
1HNMR turns out to be title product (the similar Fig. 2 of accompanying drawing situation).The liquid chromatogram measuring product purity is 97.3%.
Embodiment 5
Whisking appliance is housed, temperature is taken into account in the 500ml four-hole boiling flask of water trap, adds methyl Soxylat A 25-7 150g, adds toluene 40g, hexanaphthene 80g, heating for dissolving starts and stirs, and keeps 90 ℃ of temperature, makes the mixture azeotropic, divides water, clarifies until distillate.
Be cooled to 45 ℃, in flask, add methylacrylic acid 25, stopper para benzoquinone 0.5g then; Resin solid acid catalyst (preparation method is with embodiment 3) 15g, heating, temperature is at 90 ℃ in keeping; The sampling and testing reaction process adopts the tlc test, and developping agent is a chloroform: Virahol=2: 1 (volume ratio); When not observing the alkyl polyoxyethylene invocation point on the silica gel point plate, reaction finishes.
Reaction finishes, cool to room temperature, and filtration under diminished pressure, resin solid acid is subsequent use after collecting processing again.Filtrating adds another is equipped with in the round-bottomed flask of vacuum distillation apparatus 500ml, and underpressure distillation obtains methyl polyethenoxy ether metacrylic acid ester product, through FTIR,
1HNMR turns out to be title product (the similar Fig. 2 of accompanying drawing situation).Its purity of liquid chromatogram measuring is 96.1%.
Claims (5)
1. the preparation method of alkyl polyoxyethylene ether propenoate or alkyl polyoxyethylene ether methacrylic ester is characterized in that may further comprise the steps:
(1) raw material dehydration: alkyl polyoxyethylene ether is dewatered through entrainer;
(2) reaction: after thing dehydration to be mixed finished, cooling added stopper, resin solid acid catalyst and acrylic or methacrylic acid, and the heating control reaction temperature is 70-120 ℃, stirs, and reaction, azeotropic is sloughed the water that esterification generates; Follow the tracks of reaction process through tlc point plate, developping agent is a volume ratio 2～10: 1 chloroform and Virahol; The disappearance of the point of alkyl polyoxyethylene is a stopped reaction on silica gel point plate; The consumption of stopper is the 0.01-1% of acrylic or methacrylic acid quality, and stopper is selected one or more in Resorcinol, para benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-ten.-butylcatechol and the methylene blue for use; The consumption of acrylic or methacrylic acid be alkyl polyoxyethylene ether molar mass 1-10 doubly; The consumption of resin solid acid catalyst is the 1%-50% of reactant total mass;
(3) separate purification: reaction system is reduced to room temperature, filters, and collects the resin solid acid catalyst; Filtrating is extracted azeotropic solvent, acrylic or methacrylic acid out through underpressure distillation, obtains title product alkyl polyoxyethylene ether propenoate or alkyl polyoxyethylene ether methacrylic ester.
2. method according to claim 1; It is characterized in that: described resin solid acid catalyst is the pearl body that under the effect of perforating agent, becomes through suspension copolymerization with vinylbenzene and divinylbenzene; Has a macroporous netlike through what sulfonation reaction obtained again; Mean pore size is 30-55nm, and median size is 0.30-1.40mm, and the quality CEC is greater than 5.00mmol/g [H
+], have the brown spherical high polymer polymer beads of sulfonic acid group.
3. method according to claim 1; It is characterized in that: described alkyl polyoxyethylene ether is dewatered through entrainer is meant that an alkyl polyoxyethylene ether and entrainer add in the reactor drum, and heating makes the alkyl polyoxyethylene ether dissolving, stirs; Reheat makes the reaction mixture azeotropic dehydration; The temperature of reaction of control azeotropic dehydration is 60-120 ℃, and until the clarification that refluxes, the water liquid level no longer raises; Said entrainer consumption is the 50-150% of alkyl polyoxyethylene ether quality.
4. according to claim 1 or 3 described methods, it is characterized in that: described entrainer is selected one or more in normal hexane, hexanaphthene, sherwood oil, benzene, toluene and the YLENE for use.
5. method according to claim 1 is characterized in that: the consumption of described acrylic or methacrylic acid be alkyl polyoxyethylene ether molar mass 2-8 doubly.
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| CN104693436A (en) * | 2014-11-24 | 2015-06-10 | 上海保立佳化工有限公司 | Synthesis method of alkyl polyethyleneoxide ether acrylate |
| CN110538610A (en) * | 2019-07-18 | 2019-12-06 | 中国石油天然气股份有限公司 | Polymerizable surfactant containing long-chain isomeric alkyl, and preparation and application thereof |
| CN114195300A (en) * | 2021-12-08 | 2022-03-18 | 珠海谦信新材料有限公司 | Processing system of acetic acid ester esterification cauldron waste residue liquid |
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