CN103131001B - One-step preparation method of polyoxyethylene ether acrylate - Google Patents
One-step preparation method of polyoxyethylene ether acrylate Download PDFInfo
- Publication number
- CN103131001B CN103131001B CN201110377604.4A CN201110377604A CN103131001B CN 103131001 B CN103131001 B CN 103131001B CN 201110377604 A CN201110377604 A CN 201110377604A CN 103131001 B CN103131001 B CN 103131001B
- Authority
- CN
- China
- Prior art keywords
- acrylate
- polyoxyethylene ether
- ether acrylate
- reaction
- oxyethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 *[N+]([N-]C=N)[N+]([O-])ON Chemical compound *[N+]([N-]C=N)[N+]([O-])ON 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 technical field of fine, specifically, is a kind of production method of polyoxyethylene ether acrylate.
[background technology]
Polyoxyethylene ether acrylate, it is a kind of novel nonionogenic tenside, have the structure of double bond, ester bond and polyethers key concurrently, there is good surfactivity, the good lubrication of product, soft effect, good spreadability and stable emulsifying property can be given with reactive hydrogen addition or with unsaturated compound copolymerization, 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, polyoxyethylene ether acrylate is produced and is adopted indirect method, i.e. first obtained poly glycol monomethyl ether and then direct esterification or carry out transesterify, and complex process, low conversion rate, by product are many, esterification process is easily polymerized, cause quality product poor, far can not meet the demand of future market.
US Patent No. 6362364 compares and describe in detail esterification reaction process, 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 usual by product of this method is more, the post-reaction treatment operations such as neutralization &washing need be carried out, bring difficulty to product separation, catalyst recovery and wastewater treatment etc., thus make complex process equipment.And the requirement that improve equipment anticorrosion performance.
Ester-interchange method generally carries out transesterification reaction with acrylate and poly glycol monomethyl ether, and conventional catalyzer 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 methoxy poly (ethylene glycol) ether of EO number 6-12 and excessive methyl methacrylate, by transesterification reaction, are carried out transesterification reaction by the people such as Guo Baowen, obtain product.This method in solvent-free reaction system, poly glycol monomethyl ether due to relative molecular mass relatively large, have larger sterically hindered ,-OH is wrapped up by polyethoxye, and the possibility that-OH contacts with-COOH reduces, and is unfavorable for the carrying out reacted.This method should not be adopted when therefore obtaining the polyethylene glycol monomethyl ethermethacrylic acid esters of high molecular weight.
Aforesaid method fails to solve the technical problem that by product is many, product purification is difficult, yield is low, complex process, cost are 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 polyoxyethylene ether acrylate is provided, thus simplify production technique, reduction production cost, improve the quality of products.
The object of the invention is to be achieved through the following technical solutions:
Single stage method prepares polyoxyethylene ether acrylate, 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, can the polyoxyethylene ether acrylate of the corresponding preparation polymerization degree 1 ~ 25;
(2) BX is used
3be Primary Catalysts, Mg
2+, Al
3+, Fe
2+, Ti
4+, Sn
2+, Cu
2+metal-salt Deng wherein one or more is promotor; Preferred as such scheme, Primary Catalysts consumption 0.1wt% ~ 0.50wt%, promotor consumption is 0.1wt% ~ 0.5wt%, all to account for the mass percent of theoretical product gross weight;
(3) use Resorcinol or MEHQ, or the composition of the two is stopper; Preferred as such scheme, stopper consumption is the 0.01wt% ~ 0.30wt% of theoretical product total mass;
(4) in autoclave, under certain temperature, pressure, make acrylate and oxyethane one step ethoxylation, obtain polyoxyethylene ether acrylate.Preferred as such scheme, temperature of reaction is between 15 ~ 105 DEG C, and reaction pressure is 0 ~ 0.9MPa;
(5) before 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 obtain esters of acrylic acid polyoxy Vinyl Ether, greatly simple technical process, have with short production cycle, less energy consumption, cost are low, 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 polyoxyethylene ether acrylate of the present invention is below provided.
Embodiment 1
Cleaning autoclave, add methyl methacrylate 100g, catalyzer 2.7g, promotor 0.9g and stopper 1.6g, covers kettle cover, tighten the screws, installs thermocouple thermometer, the resistance to air loss of inspection whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 50r/min, nitrogen is filled with to gauge pressure 0.1MPa in autoclave, then vacuumizes, so in triplicate.Opening moderate-speed mixer, and open heating, when being heated to 20 DEG C, importing oxyethane with the speed of 2.5g/min, control reaction stagnation pressure 0.2 ~ 0.4MPa, temperature in the kettle 25 DEG C.Feed in raw material complete to 880g oxyethane, insulation 1.0h still pressure is constant, is cooled to 30 DEG C of 10min dischargings of finding time.
Filtration obtains light yellow clarifying liquid body, and be 93.1% through liquid chromatography-mass spectrometry methyl methacrylate Soxylat A 25-7 yield, molecular-weight average is 940, mean polymerisation degree 23.
Embodiment 2
Cleaning autoclave, add methyl methacrylate 100g, catalyzer 3.8g, promotor 1.3g and stopper 2.3g, covers kettle cover, tighten the screws, installs thermocouple thermometer, the resistance to air loss of inspection whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 50r/min, nitrogen is filled with to gauge pressure 0.1MPa in autoclave, then vacuumizes, so in triplicate.Opening moderate-speed mixer, and open heating, when being heated to 60 DEG C, importing oxyethane with the speed of 1.5g/min, control reaction stagnation pressure 0.1 ~ 0.4MPa, temperature in the kettle 65 DEG C.Feed in raw material complete to 660g oxyethane, insulation 1.0h still pressure is constant, is cooled to 30 DEG C of 10min dischargings of finding time.
Filtration obtains light yellow clarifying liquid body, and be 90.4% through liquid chromatography-mass spectrometry methyl methacrylate Soxylat A 25-7 yield, molecular-weight average is 760, mean polymerisation degree 17.
Embodiment 3
Cleaning autoclave, add methyl acrylate 86g, catalyzer 2.6g, promotor 0.9g and stopper 1.6g, covers kettle cover, tighten the screws, installs thermocouple thermometer, the resistance to air loss of inspection whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 150r/min, nitrogen is filled with to gauge pressure 0.3MPa in autoclave, then vacuumizes, so in triplicate.Opening moderate-speed mixer, and open heating, when being heated to 90 DEG C, importing oxyethane with the speed of 2.5g/min, control reaction stagnation pressure 0.5 ~ 0.7MPa, temperature in the kettle 95 DEG C.Feed in raw material complete to 440g oxyethane, insulation 1.0h still pressure is constant, is cooled to 30 DEG C of 10min dischargings of finding time.
Filtration obtains light yellow clarifying liquid body, and be 92.7% through liquid chromatography-mass spectrometry methyl acrylate Soxylat A 25-7 yield, molecular-weight average is 526, mean polymerisation degree 12.
Embodiment 4
In autoclave, add methyl acrylate 86g, catalyzer 1.5g, promotor 0.5g and stopper 0.9g, covers kettle cover, tighten the screws, installs thermocouple thermometer, the resistance to air loss of inspection whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 250r/min, nitrogen is filled with to gauge pressure 0.1MPa in autoclave, then vacuumizes, so in triplicate.Opening moderate-speed mixer, and open heating, when being heated to 60 DEG C, importing oxyethane with the speed of 3.5g/min, control reaction stagnation pressure 0.2 ~ 0.4MPa, temperature in the kettle 75 DEG C.Feed in raw material complete to 220g oxyethane, insulation 1.0h still pressure is constant, is cooled to 30 DEG C of 10min dischargings of finding time.
Filtration obtains achromaticity and clarification liquid, and be 92.3% through liquid chromatography-mass spectrometry methyl acrylate Soxylat A 25-7 yield, molecular-weight average is 306, mean polymerisation degree 6.
Embodiment 5
In autoclave, add ethyl propenoate 100g, catalyzer 2.7g, promotor 0.9g and stopper 1.6g, covers kettle cover, tighten the screws, installs thermocouple thermometer, the resistance to air loss of inspection whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 250r/min, nitrogen is filled with to gauge pressure 0.1MPa in autoclave, then vacuumizes.Opening moderate-speed mixer, and open heating, when being heated to 60 DEG C, importing oxyethane with the speed of 1.5g/min, control reaction stagnation pressure 0.2 ~ 0.4MPa, temperature in the kettle 75 DEG C.Feed in raw material complete to 440g oxyethane, insulation 1.0h still pressure is constant, is cooled to 30 DEG C of 10min dischargings of finding time.
Filtration obtains light yellow clarifying liquid body, and be 90.8% through liquid chromatography-mass spectrometry ethyl propenoate Soxylat A 25-7 yield, molecular-weight average is 540, mean polymerisation degree 10.
Embodiment 6
Cleaning autoclave, get rid of wherein foreign matter, add ethyl propenoate 100g, catalyst B F32.3g, the magnesium pot molecular sieve 0.8g and MEHQ 1.4g of brand-new, covers kettle cover, tighten the screws, installs thermocouple thermometer, the resistance to air loss of inspection whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 50r/min, nitrogen is filled with to gauge pressure 0.1MPa in autoclave, then vacuumizes, so in triplicate.Opening moderate-speed mixer, and open heating, when being heated to 60 DEG C, importing oxyethane with the speed of 2.5g/min, control reaction stagnation pressure 0.2 ~ 0.4MPa, temperature in the kettle 75 DEG C.Feed in raw material complete to 352g oxyethane, insulation 1.0h still pressure is constant, is cooled to 30 DEG C of 10min dischargings of finding time.
Filtration obtains light yellow clarifying liquid body, ethyl propenoate Soxylat A 25-7 yield 94.2%, and molecular-weight average is 452, mean polymerisation degree 8.
Embodiment 7
Cleaning autoclave, add β-dimethyl-aminoethylmethacrylate 114g, catalyzer 2.8g, promotor 0.9g and stopper 1.7g, covers kettle cover, tighten the screws, installs thermocouple thermometer, the resistance to air loss of inspection whole system.Nitrogen purge autoclave 3 times.Open low rate mixing 250r/min, nitrogen is filled with to gauge pressure 0.1MPa in autoclave, then vacuumizes, so in triplicate.Opening moderate-speed mixer, and open heating, when being heated to 60 DEG C, importing oxyethane with the speed of 2.5g/min, control reaction stagnation pressure 0.2 ~ 0.4MPa, temperature in the kettle 75 DEG C.Feed in raw material complete to 880g oxyethane, insulation 1.0h still pressure is constant, is cooled to 30 DEG C of 10min dischargings of finding time.
Filtration obtains light yellow clarifying liquid body, and be 92.3% through liquid chromatography-mass spectrometry β-dimethyl-aminoethylmethacrylate Soxylat A 25-7 yield, 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; Polyether product narrow molecular weight distribution, applicability is improved.
The above is only the preferred embodiment of the present invention; it 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 (4)
1. single stage method prepares polyoxyethylene ether acrylate, 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 polyoxyethylene ether acrylate of the corresponding preparation polymerization degree 1 ~ 25;
Described acrylate is selected from methyl methacrylate, β-dimethyl-aminoethylmethacrylate, methyl acrylate, ethyl propenoate; Acrylate is for once dropping into autoclave before reaction, and oxyethane is continuously feeding in reaction process, and input speed is 0.2 ~ 5g/min;
(2) BX is used
3be Primary Catalysts, X is F, Cl, Br, I, Mg
2+, Al
3+, Fe
2+, Ti
4+, Sn
2+, Cu
2+in the metal-salt of one or more be promotor;
(3) one or both in use Resorcinol, MEHQ are stopper;
(4) in autoclave, under temperature, pressure condition, make acrylate and oxyethane one step ethoxylation, obtain polyoxyethylene ether acrylate.
2. single stage method as claimed in claim 1 prepares polyoxyethylene ether acrylate, 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+in the metal-salt of one or more be promotor; Primary Catalysts consumption 0.1wt% ~ 0.50wt%, promotor consumption is 0.1wt% ~ 0.5wt%, all to account for the mass percent of theoretical product gross weight.
3. single stage method as claimed in claim 1 prepares polyoxyethylene ether acrylate, and it is characterized in that, stopper consumption described in step (3) is the 0.01wt% ~ 0.30wt% of theoretical product total mass.
4. single stage method as claimed in claim 1 prepares polyoxyethylene ether acrylate, and it is characterized in that, temperature of reaction is between 15 ~ 105 DEG C, and reaction pressure is 0.1 ~ 0.9MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110377604.4A CN103131001B (en) | 2011-11-23 | 2011-11-23 | One-step preparation method of polyoxyethylene ether acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110377604.4A CN103131001B (en) | 2011-11-23 | 2011-11-23 | One-step preparation method of polyoxyethylene ether acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103131001A CN103131001A (en) | 2013-06-05 |
| CN103131001B true CN103131001B (en) | 2015-04-22 |
Family
ID=48491492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110377604.4A Expired - Fee Related CN103131001B (en) | 2011-11-23 | 2011-11-23 | One-step preparation method of polyoxyethylene ether acrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103131001B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924706B (en) * | 2012-07-05 | 2015-06-17 | 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 |
| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1378875A (en) * | 2001-04-06 | 2002-11-13 | 盐城冬阳合成润滑油有限公司 | C13 isomerol polyoxyvinether emulsifier and its preparing process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006057040A (en) * | 2004-08-23 | 2006-03-02 | Sanyo Chem Ind Ltd | Vinyl monomer |
-
2011
- 2011-11-23 CN CN201110377604.4A patent/CN103131001B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1378875A (en) * | 2001-04-06 | 2002-11-13 | 盐城冬阳合成润滑油有限公司 | C13 isomerol polyoxyvinether emulsifier and its preparing process |
Non-Patent Citations (2)
| Title |
|---|
| 甲基丙烯酸聚乙二醇单甲醚酯大单体的合成与表征;杨勇等;《高分子材料科学与工程》;20111115;第27卷(第11期);第29-31页，第35页 * |
| 甲基丙烯酸聚氧乙烯酯的合成;邢凤兰等;《齐齐哈尔轻工学院学报》;19931231;第9卷(第4期);第43-48页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103131001A (en) | 2013-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103131001B (en) | One-step preparation method of polyoxyethylene ether acrylate | |
| CN106631699B (en) | A method of preparing sec-butyl alcohol | |
| CN106631684A (en) | Method for preparing SBA(sec-butyl alcohol) through hydrolysis with sec-butyl acetate | |
| CN102015615A (en) | Method for preparing fatty acid alkyl ester using fatty acid | |
| CN101906209B (en) | Method for synthesizing polyethylene glycol monomethacrylate from solid superacid by catalytic esterification | |
| CN112250662A (en) | Preparation method of cyclic sulfate | |
| CN101445453B (en) | Synthetic method of trimethylolpropane tricaprylate | |
| CN113278143A (en) | Efficient unsaturated carbon dioxide-based polyol and preparation method thereof | |
| CN103881082B (en) | The preparation method of polycarboxylic acid water reducer macromer methyl allyl alcohol polyoxyethylene ether | |
| CN102363645A (en) | Method for synthesizing tetramethylolmethane polyoxyethylene ether | |
| CN109020849B (en) | Preparation method of deuterated dimethyl sulfoxide | |
| CN102050700B (en) | Method for preparing alkoxy aluminum | |
| CN101445507B (en) | Method for preparing praziquantel | |
| CN107652163B (en) | Production method of high-purity methyl allyl alcohol | |
| CN103755520A (en) | Method for producing substituted benzyl alcohol, substituted benzaldehyde and substituted benzyl acid through oxidizing substituted methylbenzene with air based on gas-liquid-solid heterogeneous reaction separation synchronization reactor | |
| CN102344563A (en) | Solid superacid catalyzed esterification synthesis of methoxy polyethylene glycol methacrylic acid ester | |
| CN108689839A (en) | A method of utilizing formic acid, acetate mixture production cyclohexyl formate and cyclohexyl acetate | |
| CN104945255B (en) | Preparation method of cyclohexyl methacrylate | |
| CN101486648A (en) | Preparation of allyl methacrylate | |
| CN109160880B (en) | Preparation method of ethyl benzoate | |
| CN102126966A (en) | Method for synthesizing N,N-diethyl ethanolamine | |
| CN105481691B (en) | The synthetic method of double cyclopentenyl oxygen ethylmethyl acrylate | |
| CN102746180B (en) | Preparation method for hydroxyethyl dual fatty acid amide | |
| CN108033872B (en) | Method and equipment for clean and environment-friendly production of 1,1',2, 3-tetrachloropropene | |
| CN105837448A (en) | Method for synthesis of (meth)acrylate diluent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150422 Termination date: 20171123 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |