CN101497569A - Method for synthesizing allyl alcohol polyethenoxy ether metacrylic acid ester - Google Patents
Method for synthesizing allyl alcohol polyethenoxy ether metacrylic acid ester Download PDFInfo
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- CN101497569A CN101497569A CNA2008101639905A CN200810163990A CN101497569A CN 101497569 A CN101497569 A CN 101497569A CN A2008101639905 A CNA2008101639905 A CN A2008101639905A CN 200810163990 A CN200810163990 A CN 200810163990A CN 101497569 A CN101497569 A CN 101497569A
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- allyl alcohol
- polyethenoxy ether
- alcohol polyethenoxy
- acid ester
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Abstract
The invention provides a method for synthesizing an allyl alcohol polyethenoxy ether metacrylic acid ester, and belongs to the technical field of synthesizing ester compounds in the organic chemistry. The method comprises that: an allyl alcohol polyethenoxy ether and a methacrylic acid are used as raw materials, a phosphotungstic acid immobilized on active carbon is used as a catalyst, phenothiazine or hydroquinone or a mixture of the phenothiazine and the hydroquinone is used as a polymerization inhibitor, and in the presence of a water-carrying agent and under the condition of continuously filling with nitrogen, the esterification reaction is carried out, after the reaction, the obtained products are refined to obtain the allyl alcohol polyethenoxy ether metacrylic acid ester; and the degree of polymerization of a chain segment of the allyl alcohol polyethenoxy ether is between 1 and 10, and a mol ratio of the allyl alcohol polyethenoxy ether to the methacrylic acid is 1.0:1.0-1.5. According to test comparisons, the method has the advantages of reasonable use of the phosphotungstic acid immobilized on active carbon with good catalytic activity and stability as the catalyst, more advanced and reasonable process, mild reaction conditions and safe and easy operation, and solves the problem of the equipment corrosion.
Description
Technical field
The present invention relates to a kind of synthetic method of allyl alcohol polyethenoxy ether metacrylic acid ester, belong to technical field of synthesis of ester compounds in the organic chemistry.
Background technology
Allyl alcohol polyethenoxy ether metacrylic acid ester is the difunctionality monomer, contain two polymerisable double bonds, Raolical polymerizable no matter wherein, anionic polymerisation, the polymerization of the two keys in α position is much better than allyl double bonds, not only have simultaneously lipophilic group (alkyl) and hydrophilic radical (polyoxyethylene group), and molecular polarity is with ethylene oxide group number increase and decrease in the molecule, the HLB value can be adjusted as required, therefore has purposes widely, be applicable to silicon oil modified, and optical lens, reinforced plastics, tackiness agent, coating, rubber, fields such as the linking agent of printing ink, at present, allyl alcohol polyethenoxy ether metacrylic acid ester the rarely seen report of synthesis technique.
Summary of the invention
It is reasonable to the purpose of this invention is to provide a kind of technology, product yield and purity height, has the synthetic method of the allyl alcohol polyethenoxy ether metacrylic acid ester of better use properties.
The expression formula of allyl alcohol polyethenoxy ether metacrylic acid ester is:
In the formula: n=1～10;
The present invention is the synthetic method of allyl alcohol polyethenoxy ether metacrylic acid ester, with allyl alcohol polyethenoxy ether and methacrylic acid is raw material, it is characterized in that with the gac immobilized phosphotungstic acid be catalyzer, thiodiphenylamine or Resorcinol or both mixtures are stopper, the band aqua exists, continues to feed under the condition of nitrogen gas and carry out esterification, makes with extra care to make allyl alcohol polyethenoxy ether metacrylic acid ester after reaction finishes.
The described allyl alcohol polyethenoxy ether segmental polymerization degree can be 1～10.
The mol ratio of described allyl alcohol polyethenoxy ether and methacrylic acid can be 1.0:1.0～1.5, can adjust accordingly according to the different polymerization degree of allyl alcohol polyethenoxy ether.
Described band aqua can be made up of toluene and hexanaphthene, and both volume ratios are 20:80～80:20, and the add-on of band aqua is 30～60% of allyl alcohol polyethenoxy ether and a methacrylic acid gross weight.The add-on of described gac immobilized phosphotungstic acid can be 1.0～5.0% of allyl alcohol polyethenoxy ether, methacrylic acid, band aqua gross weight.
The add-on of described thiodiphenylamine or Resorcinol or both mixtures can be 0.025～0.2% of allyl alcohol polyethenoxy ether and methacrylic acid gross weight.
Described esterification reaction temperature can be 100～120 ℃.
Described reaction time of esterification can be 5.0～7.0 hours.
After described process for refining can be filtering catalyst, add 0.2～0.4% diatomite of allyl alcohol polyethenoxy ether and methacrylic acid gross weight, filter once more, solvent is deviate from underpressure distillation.
The present invention through test relatively, rationally selecting the gac immobilized phosphotungstic acid with good catalytic activity and stability for use is catalyzer, and by optimized choice to reasonable adjustment, esterification reaction temperature and the time of the add-on of allyl alcohol polyethenoxy ether, methacrylic acid, band aqua, catalyzer, stopper and proportioning, make technology of the present invention more become rationally advanced, reaction process mild condition, simple and safe operation have been avoided the etching problem of equipment.Reclaiming the catalyzer that obtains with preparation method of the present invention can reuse, and can improve esterification efficient, shorten the reaction times by solvent bank water and combining of nitrogen band water mode in addition.The allyl alcohol polyethenoxy ether metacrylic acid ester that is made by the present invention has characteristics such as constant product quality, reactive behavior are good, be applicable to silicon oil modified, and the linking agent of optical lens, reinforced plastics, tackiness agent, coating, rubber, printing ink etc.
Embodiment
Embodiment 1: reflux exchanger is being housed, water trap, thermometer, add allyl alcohol polyethenoxy ether 174.2g (polymerization degree is 5) in the reactor of agitator unit respectively, methacrylic acid 72.6g, gac immobilized phosphotungstic acid 13.5g, hydroquinone of polymerization retarder 0.25g, band aqua 201g (volume ratio of toluene: hexanaphthene=35:65), be warming up to 100～105 ℃ under the whipped state, feed nitrogen, reacted 5.5 hours, the reactionless generation water of band aqua is reaction end when taking out of, close nitrogen, be cooled to 60～70 ℃, filter and remove phosphate-tungstic acid (recovery re-uses), in filtrate, add diatomite 0.49g then, stir about 30 minutes, filter, underpressure distillation goes out solvent, obtains allyl alcohol polyethenoxy ether metacrylic acid ester, acid number is less than 0.5mgKOH/g, esterification yield 98.5%.
Embodiment 2: reflux exchanger is being housed, water trap, thermometer, add allyl alcohol polyethenoxy ether 177.6g (polymerization degree is 9) in the reactor of agitator unit respectively, methacrylic acid 48.2g, gac immobilized phosphotungstic acid 18.0g, stopper thiodiphenylamine 0.18g, band aqua 225.8g (volume ratio of toluene: hexanaphthene=45:55), be warming up to 110～115 ℃ under the whipped state, feed nitrogen, reacted 6.0 hours, the reactionless generation water of band aqua is reaction end when taking out of, close nitrogen, be cooled to 60～70 ℃, filter and remove phosphate-tungstic acid (recovery re-uses), in filtrate, add diatomite 0.68g then, stir about 30 minutes, filter, underpressure distillation goes out solvent, obtains allyl alcohol polyethenoxy ether metacrylic acid ester, acid number is less than 0.5mgKOH/g, esterification yield 98.0%.
Reaction equation is in the foregoing description:
Annotate: in the formula: n=1～10.
Claims (9)
1, a kind of synthetic method of allyl alcohol polyethenoxy ether metacrylic acid ester, with allyl alcohol polyethenoxy ether and methacrylic acid is raw material, it is characterized in that with the gac immobilized phosphotungstic acid be catalyzer, thiodiphenylamine or Resorcinol or both mixtures are stopper, the band aqua exists, continues to feed under the condition of nitrogen gas and carry out esterification, makes with extra care to make allyl alcohol polyethenoxy ether metacrylic acid ester after reaction finishes.
2, by the synthetic method of the described allyl alcohol polyethenoxy ether metacrylic acid ester of claim 1, it is characterized in that the described allyl alcohol polyethenoxy ether segmental polymerization degree is 1～10.
3, by the synthetic method of the described allyl alcohol polyethenoxy ether metacrylic acid ester of claim 1, the mol ratio that it is characterized in that described allyl alcohol polyethenoxy ether and methacrylic acid is 1.0:1.0～1.5.
4, press the synthetic method of the described allyl alcohol polyethenoxy ether metacrylic acid ester of claim 1, it is characterized in that described band aqua is made up of toluene and hexanaphthene, both volume ratios are 20:80～80:20, and the add-on of band aqua is 30～60% of allyl alcohol polyethenoxy ether and a methacrylic acid gross weight.
5, by the synthetic method of the described allyl alcohol polyethenoxy ether metacrylic acid ester of claim 1, the add-on that it is characterized in that described gac immobilized phosphotungstic acid is 1.0～5.0% of allyl alcohol polyethenoxy ether, methacrylic acid, a band aqua gross weight.
6, by the synthetic method of the described allyl alcohol polyethenoxy ether metacrylic acid ester of claim 1, the add-on that it is characterized in that described thiodiphenylamine or Resorcinol or both mixtures is 0.025～0.2% of allyl alcohol polyethenoxy ether and a methacrylic acid gross weight.
7, by the synthetic method of the described allyl alcohol polyethenoxy ether metacrylic acid ester of claim 1, it is characterized in that described esterification reaction temperature is 100～120 ℃.
8, by the synthetic method of the described allyl alcohol polyethenoxy ether metacrylic acid ester of claim 1, it is characterized in that described reaction time of esterification is 5.0～7.0 hours.
9, press the synthetic method of the described allyl alcohol polyethenoxy ether metacrylic acid ester of claim 1, after it is characterized in that described process for refining is filtering catalyst, 0.2～0.4% the diatomite that adds allyl alcohol polyethenoxy ether and methacrylic acid gross weight, filter once more, solvent is deviate from underpressure distillation.
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| Application Number | Priority Date | Filing Date | Title |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857654A (en) * | 2010-06-13 | 2010-10-13 | 苏州博纳化学科技有限公司 | Synthetic method of reactive emulsifier |
| CN101648868B (en) * | 2009-09-07 | 2012-07-11 | 太仓中化环保化工有限公司 | Production method of fluorine-containing (methyl) acrylate monomer |
| 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 |
| CN113583194A (en) * | 2021-08-27 | 2021-11-02 | 中铁建设集团建筑发展有限公司 | Concrete performance regulator and preparation method thereof |
-
2008
- 2008-12-30 CN CNA2008101639905A patent/CN101497569A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648868B (en) * | 2009-09-07 | 2012-07-11 | 太仓中化环保化工有限公司 | Production method of fluorine-containing (methyl) acrylate monomer |
| CN101857654A (en) * | 2010-06-13 | 2010-10-13 | 苏州博纳化学科技有限公司 | Synthetic method of reactive emulsifier |
| CN101857654B (en) * | 2010-06-13 | 2012-05-23 | 苏州博纳化学科技有限公司 | Synthetic method of reactive emulsifier |
| 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 |
| CN113583194A (en) * | 2021-08-27 | 2021-11-02 | 中铁建设集团建筑发展有限公司 | Concrete performance regulator and preparation method thereof |
| CN113583194B (en) * | 2021-08-27 | 2024-01-16 | 中铁建设集团建筑发展有限公司 | Concrete performance regulator and preparation method thereof |
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Application publication date: 20090805 |