CN101270046A - Technique for preparing octadecyl acrylate with fusion esterification method - Google Patents
Technique for preparing octadecyl acrylate with fusion esterification method Download PDFInfo
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- CN101270046A CN101270046A CNA200810018016XA CN200810018016A CN101270046A CN 101270046 A CN101270046 A CN 101270046A CN A200810018016X A CNA200810018016X A CN A200810018016XA CN 200810018016 A CN200810018016 A CN 200810018016A CN 101270046 A CN101270046 A CN 101270046A
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- octadecyl acrylate
- stearyl alcohol
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Abstract
The present invention provides a method used for preparing octadecyl acrylate through melt esterification. In the method, inhibitor with 0.3 to 0.8 percent of the weight of the octadecanol is added into the octadecanol and is heated so as to be completely melted; acrylic acid with 1.2 to 1.5 times of the molar weight of the octadecanol and a catalyst with 0.5 to 1.2 percent of the weight of the octadecyl are added orderly and mixed; the mixture is heated to be at the temperature between 60 DEG C and 120 DEG C for 2 to 3 hours for reflux reaction; water generated in the reaction is separated; the mixture is continuously heated to be at the temperature between 130 DEG C and 140 DEG C, and reacts for 2 to 4 hours at the constant temperature; the acrylic acid that can not completely react and the residual water are removed through vacuum distillation; the reaction products are washed by caustic alkali aqueous solution and then by water to be neutral; finally the products are treated through vacuum drying for 6 to 8 hours at the temperature of 40 DEG C; thus the waxy solid octadecyl acrylate can be prepared. The method has the advantages of high reaction rate, high reaction selectivity, short reaction time, high yield of the ester, easy separation of the water that is generated in the reaction, and so on. No azeotropic agent is used in the reaction. Thus the method avoids the serious pollution caused by toxic solvents and belongs to the clean production process.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to a kind of higher hydrocarbyl acrylate---the synthetic method of octadecyl acrylate is specifically related to a kind of technology that adopts preparing octadecyl acrylate with fusion esterification method.
Background technology
Octadecyl acrylate is a kind of important Organic Chemicals.Octadecyl acrylate is that vinylformic acid and stearyl alcohol react the trifunctional acrylate monomer that obtains under an acidic catalyst effect, and its zero pour is 24 ℃, has hypotoxicity, low viscous characteristic, and is water insoluble, dissolves in characteristics such as common organic solvents.The main application of octadecyl acrylate is to make softening agent, tackiness agent, fibre finish, paper finishing agent, lubricating oil additive, flow agent etc.
At present, the method for preparing octadecyl acrylate mainly contains ester-interchange method and solvent esterification process.Ester-interchange method is to utilize transesterification reaction (alcoholysis reaction) to be prepared the classical method for making of senior ester by lower member ester.Proposed at first by Neher as far back as 1936 and perfect, usefulness ester exchange methods such as nineteen forty-four Rehberg have prepared the senior acrylate of a series of positive structures by methyl acrylate, and the variation that has studied normal paraffin length in great detail aligns Effect on Performance such as the density of the senior acrylate of structure, relative molecular mass, fusing point, boiling point, productive rate.Lower member ester uses methyl acrylate mostly when preparing higher hydrocarbyl acrylate with transesterification reaction, because its boiling point lower (about 80 ℃) so reaction can only be carried out at a lower temperature, makes the reaction times lengthening; The boiling point of product methyl alcohol and azeotrope that methyl acrylate forms is 62～63 ℃, easily reactant taken away, thus the yield of the senior mixed ester of reduction vinylformic acid.In addition, the copolymerization of methyl acrylate and higher hydrocarbyl acrylate or homopolymerization also can make the productive rate of higher hydrocarbyl acrylate reduce, and the therefore general stopper that uses is more, considers that from cost and aftertreatment difficulty this method is at industrial potassium hydroxide.
The solvent esterification process is directly to carry out the synthetic method that esterification prepares the senior mixed ester of vinylformic acid, preparation technology is simple relatively, but in order in time the water that generates in the building-up process to be discharged, as azeotropic agent, wherein the most frequently used azeotropic agent is a toluene generally must to use organic solvent (forming azeotrope with water).But use toluene to make solvent, when post-reaction treatment, it must be removed on the one hand, on the other hand in process of production,, bring serious pollution, must be reclaimed because toluene toxicity is very big.In addition, the solvent esterification process need at high temperature return time be longer, causes polymerization easily.Moreover the consumption of solvent esterification process catalyzer and stopper is higher, synthetic cost height.Catalyst levels is generally 2.0～3.0%, and the stopper consumption is 1.0～1.5%.
Summary of the invention
The purpose of this invention is to provide a kind of technology that adopts preparing octadecyl acrylate with fusion esterification method, this technology is not used entrainer, have that speed of reaction is fast, reaction preference is high, reaction times is short, the yield height of ester, advantages such as resultant water is easy to have been avoided problems such as the complexity of the aftertreatment technology that with an organic solvent brings in the existing production technique and difficult treatment, have realized the production that cleans of higher hydrocarbyl acrylate.
The present invention adopts the technology of preparing octadecyl acrylate with fusion esterification method, and is specific as follows:
Be the stopper that in stearyl alcohol, adds stearyl alcohol quality 0.3～0.8% earlier, after heating makes its off-bottom, add the vinylformic acid of 1.2～1.5 times of stearyl alcohol molar weights and the catalyzer of stearyl alcohol quality 0.5～1.2% more successively, mix; With mixture heating up to 60～120 ℃, back flow reaction 2～3 hours, tell the moisture that reaction generates, continue to be warming up to 130 ℃～140 ℃, insulation reaction 2～4 hours; Treat that esterification finishes substantially, unreacted intact vinylformic acid and residual water are removed in underpressure distillation, then with reaction product earlier with the caustic-alkali aqueous solution washing to remove remaining catalyzer, stopper and vinylformic acid, be washed with water to neutrality again; In 40 ℃ of vacuum-dryings, promptly get the waxy solid octadecyl acrylate at last.
The stearyl alcohol that the present invention adopts is positive stearyl alcohol or various isomery stearyl alcohol.
The stopper that is adopted is Resorcinol or thiodiphenylamine.
The catalyzer that is adopted is a tosic acid.
The caustic-alkali aqueous solution that is adopted is the aqueous solution of potassium hydroxide or sodium hydroxide.
Process characteristic of the present invention is temperature reaction 5～6h progressively under refluxad; Total reaction time was finished with interior at 8 hours; The yield of octadecyl acrylate can reach more than 93%.
The physical properties of the octadecyl acrylate of the present invention's preparation and infared spectrum, nuclear magnetic spectrum see Table 1,2,3.
Table 1 adopts the composition and the characteristic of fusion esterification method synthetic octadecyl acrylate
Table 2 adopts the ft-ir characteristic absorption peak of fusion esterification method synthetic octadecyl acrylate
The H-NMR spectrum signature chemical shift of table 3 acrylate
From table 1,2,3 data as can be seen, the constitutional features no significant difference that the physical properties of the octadecyl acrylate of the present invention's preparation and infared spectrum, nuclear magnetic spectrum show shows that the method with preparing octadecyl acrylate with fusion esterification method is reliable.
The present invention compared with prior art has the following advantages:
1, the present invention adopts preparing octadecyl acrylate with fusion esterification method, has that speed of reaction is fast, reaction preference is high, and resultant water is easy to, and the reaction times is short, the yield advantages of higher of ester.
2, the present invention does not use entrainer, does not need solvent recuperation, and the serious pollution problem of having avoided toxic solvents to bring belongs to and cleans production technique.
3, the present invention adopts progressively that temperature-raising method carries out, and reaction is easy to control, and reflux temperature is lower, and the side reaction polyreaction is less.
4, the present invention has reduced the consumption (being 0.5%) of catalyst levels (generally 0.3%～0.8%) and stopper, can guarantee to obtain purer higher hydrocarbyl acrylate with higher yields, has reduced the aftertreatment cost.
Embodiment
Embodiment 1
In being housed, the 500ml four-hole boiling flask of thermometer, agitator and reflux condensing tube adds positive stearyl alcohol of 74.7g and 0.81g hydroquinone of polymerization retarder, be heated to 60 ℃ make its off-bottom after, add 24.5 vinylformic acid and 1g catalyzer tosic acid more successively, mix; With the about 2.5h of heating reflux reaction under the condition about 90～110 ℃ of mixture elder generation, load onto water trap then and dewater, after waiting to tell more water, be warming up to 135 ℃ and continue insulation reaction 2.5h, when observing the water yield of deviating from when suitable, think that then esterification finishes substantially with theoretical value.Stop heating this moment, unreacted intact vinylformic acid and residual water are removed in underpressure distillation; Pour product into beaker then, remove residual tosic acid and Resorcinol and a small amount of vinylformic acid, wash with water more for several times, until neutrality with the aqueous sodium hydroxide washes of mass concentration 5%.In 40 ℃ of dry 7.5h of vacuum, promptly get the waxy solid octadecyl acrylate.Total reaction time 6 hours.The yield of octadecyl acrylate is 94.2%.
Embodiment 2
In being housed, the 500ml four-hole boiling flask of thermometer, agitator and reflux condensing tube adds different hard ester alcohol of 76.8g (isomery stearyl alcohol) and 0.72g stopper thiodiphenylamine, be heated to 60 ℃ make its off-bottom after, add 26.5 vinylformic acid and 1g catalyzer tosic acid more successively, mix.With the heating reflux reaction 3h under 80～120 ℃ of conditions of mixture elder generation, load onto water trap then and dewater; After waiting to tell more water, be warming up to 140 ℃ and continue insulation reaction 2h,, think that then esterification finishes substantially when observing the water yield of deviating from when suitable with theoretical value.Stop heating, unreacted intact vinylformic acid and residual water are removed in underpressure distillation.Pour product into beaker then,, wash with water more for several times, until neutrality with the potassium hydroxide aqueous solution flush away of mass concentration 5% residual tosic acid and Resorcinol and a small amount of vinylformic acid.40 ℃ of dry 7h of vacuum promptly get the waxy solid octadecyl acrylate.Total reaction time 6.5 hours.The yield of octadecyl acrylate is 93.5%.
Embodiment 3
In being housed, the 500ml four-hole boiling flask of thermometer, agitator and reflux condensing tube adds different hard ester alcohol of 78.2g (isomery stearyl alcohol) and 0.90g hydroquinone of polymerization retarder, be heated to 60 ℃ make its off-bottom after, add 25.5 vinylformic acid and 1g catalyzer tosic acid more successively.Mixture is the about 2h of heating reflux reaction under 90～120 ℃ of conditions earlier, loads onto water trap then and dewaters, and after waiting to tell more water, is warming up to 140 ℃ and continues insulation reaction 3h; When observing the water yield of deviating from when suitable, think that then esterification finishes substantially with theoretical value.Stop heating, unreacted intact vinylformic acid and residual water are removed in underpressure distillation.Pour product into beaker then, remove residual tosic acid and Resorcinol and a small amount of vinylformic acid, wash with water more for several times, until neutrality with the aqueous sodium hydroxide washes of mass concentration 5%.40 ℃ of dry 8h of vacuum promptly get the waxy solid octadecyl acrylate.Total reaction time 5.5 hours.The yield of octadecyl acrylate is 93.8%.
Embodiment 4
In the 500ml four-hole boiling flask of thermometer, agitator and reflux condensing tube is housed, add positive stearyl alcohol of 76.0g and 0.9g stopper thiodiphenylamine, be heated to 60 ℃ make its off-bottom after, add 25.0 vinylformic acid and 1g catalyzer tosic acid more successively.Mixture is the about 2.5h of heating reflux reaction under 100～120 ℃ of conditions earlier, loads onto water trap then and dewaters, and after waiting to tell more water, is warming up to 140 ℃ and continues insulation reaction 3.5h; When observing the water yield of deviating from when suitable, think that then esterification finishes substantially with theoretical value.Stop heating, unreacted intact vinylformic acid and residual water are removed in underpressure distillation.Pour product into beaker then, remove residual tosic acid and Resorcinol and a small amount of vinylformic acid, wash with water more for several times, until neutrality with the aqueous sodium hydroxide washes of mass concentration 5%.40 ℃ of dry 8h of vacuum promptly get the waxy solid octadecyl acrylate.Total reaction time 6 hours.The yield of octadecyl acrylate is 94.3%.
Claims (6)
1, the technology of preparing octadecyl acrylate with fusion esterification method, it is the stopper that in stearyl alcohol, adds stearyl alcohol quality 0.3～0.8% earlier, after heating makes its off-bottom, add the vinylformic acid of 1.2～1.5 times of stearyl alcohol molar weights and the catalyzer of stearyl alcohol quality 0.5～1.2% more successively, mix; With mixture heating up to 60～120 ℃, back flow reaction 2～3 hours, tell the moisture that reaction generates, continue to be warming up to 130 ℃～140 ℃, insulation reaction 2～4 hours, underpressure distillation are removed unreacted intact vinylformic acid and residual water, then reaction product are washed with caustic-alkali aqueous solution earlier, be washed with water to neutrality again, be drying to obtain the waxy solid octadecyl acrylate.
2, the technology of preparing octadecyl acrylate with fusion esterification method according to claim 1, it is characterized in that: described stearyl alcohol is positive stearyl alcohol or isomery stearyl alcohol.
3, the technology of preparing octadecyl acrylate with fusion esterification method according to claim 1, it is characterized in that: described stopper is Resorcinol or thiodiphenylamine.
4, the technology of preparing octadecyl acrylate with fusion esterification method according to claim 1, it is characterized in that: described catalyzer is a tosic acid.
5, the technology of preparing octadecyl acrylate with fusion esterification method according to claim 1, it is characterized in that: described caustic-alkali aqueous solution is the aqueous solution of potassium hydroxide or sodium hydroxide.
6, the technology of preparing octadecyl acrylate with fusion esterification method according to claim 1 is characterized in that: described drying is in 40 ℃ of vacuum-drying 6～8h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381971A (en) * | 2011-09-06 | 2012-03-21 | 南通惠康国际企业有限公司 | Preparation method of light stabilizer intermediate acrylic acid (2'-chloroethyl) ester |
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- 2008-04-18 CN CNA200810018016XA patent/CN101270046A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381971A (en) * | 2011-09-06 | 2012-03-21 | 南通惠康国际企业有限公司 | Preparation method of light stabilizer intermediate acrylic acid (2'-chloroethyl) ester |
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Open date: 20080924 |