CN103936696A - Production method of epoxy fatty acid methyl ester plasticizer - Google Patents
Production method of epoxy fatty acid methyl ester plasticizer Download PDFInfo
- Publication number
- CN103936696A CN103936696A CN201410183332.8A CN201410183332A CN103936696A CN 103936696 A CN103936696 A CN 103936696A CN 201410183332 A CN201410183332 A CN 201410183332A CN 103936696 A CN103936696 A CN 103936696A
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- CN
- China
- Prior art keywords
- methyl ester
- acid methyl
- softening agent
- production method
- epoxy aliphatic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
Abstract
The invention discloses a production method of an epoxy fatty acid methyl ester plasticizer. The production method comprises the following steps in sequence: (1) arranging a cooling water inner coil in a reaction kettle, wherein the cooling water inner coil and an outer spacer bush circulation cooling pipe at the outer side of the reaction kettle form a double-circulation cooling system; (2) putting fatty acid methyl ester and organic acid in the reaction kettle, heating, stirring and running the double-circulation cooling system, and stopping heating when the temperature is increased to 45-55 DEG C; (3) switching on a cooling water valve and dropwise adding hydrogen peroxide at a speed of 50-65g/s, wherein the reaction temperature is controlled to be 45-55 DEG C and the dropwise adding time is 2-3 hours; (4) after dropwise adding is finished, performing heat-preservation refluxing for 2-3 hours to obtain a crude plasticizer product; (5) sequentially performing hot-water washing, neutralization and reduced pressure distillation on the crude plasticizer product, stopping stirring and switching off the double-circulation cooling system, thereby obtaining the epoxy fatty acid methyl ester plasticizer. The preparation method is safe, stable, energy-saving and environment-friendly, and the production cycle is short.
Description
Technical field
The present invention relates to softening agent preparation field, particularly the production method of a kind of epoxy aliphatic acid methyl ester softening agent (being biological softening agent).
Background technology
Softening agent is one of auxiliary agent common in plastics industry, and common kind has DOP, DBP etc., and its Main Function is the melt viscosity when the second-order transition temperature of reduction material and plastics processing, but, many softening agent be take oil as raw material, containing toxic, do not utilize environmental requirement.
Along with the raising of plastics industry to environmental requirement, often adopt in recent years epoxy aliphatic acid methyl ester to use as new plasticizer.Epoxy aliphatic acid methyl ester claims again biological softening agent, being that crude vegetal and alcohols esterification are made by epoxidation, is a kind of use nontoxic polyvinyl chloride softening agent widely, and volatility is low, can replace traditional toxicity softening agent that oil makes as raw material of take, meet the environmental requirement of softening agent.Existing epoxy aliphatic acid methyl ester production method, that to take lass lining or stainless steel be reaction vessel, raw material is: fatty acid methyl ester, formic acid, hydrogen peroxide, catalyzer, under the existence of catalyzer, formic acid reacts with hydrogen peroxide and generates peroxyformic acid, peroxyformic acid reacts with the unsaturated double-bond in fatty acid methyl ester immediately, generates epoxy aliphatic acid methyl ester.Epoxidation reaction is generally used the vitriol oil for catalyzer, hydrogen peroxide need to slowly drip under stirring state, after dropwising, also will carry out insulation for a long time refluxes, whole process approximately continues 18-20 hour, and the production cycle is long, and the vitriol oil and formic acid are middle strong acid in addition, finished product acid number is difficult to control, institute's water amount of blowdown is large, production cost is high, in addition because epoxidation reaction is quick thermopositive reaction, once reacting liquid temperature is controlled the improper beyond the region of objective existence that also can easily induce reaction, overflows.
Generally speaking, there is following defect in the production of epoxy aliphatic acid methyl ester softening agent of the prior art: (1) reaction rise time is long, and production cost is higher; (2) generation by product is many, and quality is unstable; (3) technique is wayward, has unsafe factor; (4) when adding catalyzer, oxirane value reduces, and affects the plasticization effect of product, and complex process, and waste water is many.
Summary of the invention
For the defect in solving the problems of the technologies described above, a kind of safety and stability, with short production cycle, energy-conserving and environment-protective, the production method of epoxy aliphatic acid methyl ester softening agent are cheaply provided.
The production method of a kind of epoxy aliphatic acid methyl ester softening agent provided by the invention, carry out as follows successively:
(1) water coolant inner coil pipe is set in reactor, makes the outer separator circulating cooling pipe in water coolant inner coil pipe and reactor outside form dual cycle cooling system;
(2) fatty acid methyl ester and organic acid are dropped in reactor, heat temperature raising, opens and stirs and move described dual cycle cooling system, stops heating after being warmed up to 45-55 ℃;
(3) open cooling water valve, with the speed dropping hydrogen peroxide of 50-65g/s, reacting liquid temperature is controlled at 45-55 ℃, and time for adding is 2-3 hour;
(4), after hydrogen peroxide drips and finishes, insulation backflow 2-3 hour, obtains the thick product of softening agent;
(5) the thick product of softening agent is carried out to hot water cleaning, neutralization, underpressure distillation dehydration successively, stop stirring and close described dual cycle cooling system, obtain epoxy aliphatic acid methyl ester softening agent.
Described " outer separator circulating cooling pipe " fingerstall is located at the cooling tube in reactor kettle outside, in kettle outside, plays hydronic effect.Due to " outer separator circulating cooling pipe " and " water coolant inner coil pipe " can from outside, interiorly play circulating cooling effect, therefore its composition is called to " dual cycle cooling system " simultaneously.
Described organic acid add-on accounts for the 10%-12% of fatty acid methyl ester quality
The add-on of described hydrogen peroxide accounts for the 36%-40% of fatty acid methyl ester quality.
Preferably, described organic acid is formic acid, but is not limited to this, such as adopting the organic acids such as Glacial acetic acid.
Described water coolant inner coil pipe and outer separator circulating cooling pipe are connected to same cooling water pipeline, and water coolant inner coil pipe and outer separator circulating cooling pipe are supplied with water coolant by same cooling water pipeline, make equipment operation more efficient.
The hot water of the cooling rear formation of described dual cycle cooling system cleans the hot water of the thick product of softening agent for described step (5).
Neutralization in described (5) is that the pH value in the thick product of softening agent is adjusted to 6.5-6.8.
The neutralizing agent that described neutralization adopts is soda ash or calcium carbonate.
The production method of a kind of epoxy aliphatic acid methyl ester softening agent provided by the invention, has following beneficial effect:
(1) due to the dual cycle cooling system that has adopted inner coil pipe and outer separator cooling tube to form, significantly shorten the production time, improved production efficiency, saved cost.
(2) dual cycle cooling system has shortened the production time, also just avoided the phenomenon of a large amount of byproducts of generation that cause because of technical process process length, products obtained therefrom byproduct is few, steady quality, also guaranteed to a certain extent that Production Flow Chart is easy to control, improved the safety and stability of producing simultaneously.
(3) owing to not adding acid base catalysator, reduced processing wastewater, and the oxirane value of product raises to some extent, quality is good.
(4) epoxy plasticizer head product washing, is used and reclaims the discarded hot water of recirculated cooling water, reduces sewage disposal burden, has also reduced production cost simultaneously.
Embodiment
In order to make those skilled in the art person understand better technical scheme of the present invention, below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1.
In 3000L reactor, fatty acid methyl ester and formic acid (account for fatty acid methyl ester quality 10%) are dropped in reactor, heat up, open and stir and move dual cycle cooling system, be warmed up to 45 ℃ and stop heating, open cooling water valve, with the speed of 50g/s, drip hydrogen peroxide (account for fatty acid methyl ester quality 36%), reacting liquid temperature is controlled at 45-55 ℃, time for adding is 2 hours, hydrogen peroxide drips and finishes rear insulation backflow 2 hours, guarantee that epoxidation reaction is abundant, obtain the thick product of softening agent, the thick product of softening agent is washed, neutralization, underpressure distillation dehydration 1.5 hours, stop stirring and closing dual cycle cooling system, obtain epoxy aliphatic acid methyl ester softening agent.
Above-mentioned dual cycle cooling system refers to add in reactor stainless steel water coolant inner coil pipe, the cooling system forming with the outer separator circulating cooling pipe in reactor outside." dual cycle cooling system " in all the other embodiment is identical with above-mentioned explanation, no longer repeat specification.
The hot water of cooling rear formation is for the thick product water washing process of softening agent.
Wherein N-process, is that use soda ash or calcium carbonate are acid acceptor, and pH value is transferred to 6.5-6.8.
Embodiment 2.
In 3000L reactor, fatty acid methyl ester and Glacial acetic acid (account for fatty acid methyl ester quality 11%) are dropped in reactor, heat up, open and stir and move dual cycle cooling system, be warmed up to 50 ℃ and stop heating, open cooling water valve, with the speed of 55g/s, drip hydrogen peroxide (account for fatty acid methyl ester quality 38%), reacting liquid temperature is controlled at 45-55 ℃, time for adding is 2.5 hours, hydrogen peroxide drips and finishes rear insulation backflow 2.5 hours, guarantee that epoxidation reaction is abundant, obtain the thick product of softening agent, the thick product of softening agent is washed, neutralization, underpressure distillation dehydration 1.5 hours, stop stirring and closing dual cycle cooling system, obtain epoxy aliphatic acid methyl ester softening agent.
The hot water of cooling rear formation is for the thick product water washing process of softening agent.
Wherein N-process, is that use soda ash or calcium carbonate are acid acceptor, and pH value is transferred to 6.5-6.8.
Embodiment 3.
In 3000L reactor, fatty acid methyl ester and Glacial acetic acid (account for fatty acid methyl ester quality 12%) are dropped in reactor, heat up and open and stir and move dual cycle cooling system, be warmed up to 55 ℃ and stop heating, open cooling water valve, with the speed of 60g/s, drip hydrogen peroxide (account for methyl-formiate quality 40%), reacting liquid temperature is controlled at 45-55 ℃, time for adding is 3 hours, hydrogen peroxide drips and finishes rear insulation backflow 3 hours, guarantee that epoxidation reaction is abundant, obtain the thick product of softening agent, the thick product of softening agent is washed, neutralization, underpressure distillation dehydration 2.5 hours, stop stirring and closing dual cycle cooling system, obtain epoxy aliphatic acid methyl ester softening agent.
The hot water of cooling rear formation is for the thick product water washing process of softening agent.
Wherein N-process, is that use soda ash or calcium carbonate are acid acceptor, and pH value is transferred to 6.5-6.8.
Embodiment 4.
In 3000L reactor, fatty acid methyl ester and Glacial acetic acid (account for fatty acid methyl ester quality 11%) are dropped in reactor, heat up and open and stir and move dual cycle cooling system, be warmed up to 52 ℃ and stop heating, open cooling water valve, with the speed of 65g/s, drip hydrogen peroxide (account for methyl-formiate quality 37%), reacting liquid temperature is controlled at 45-55 ℃, time for adding is 2 hours, hydrogen peroxide drips and finishes rear insulation backflow 3 hours, guarantee that epoxidation reaction is abundant, obtain the thick product of softening agent, the thick product of softening agent is washed, neutralization, underpressure distillation dehydration 2 hours, stop stirring and closing dual cycle cooling system, obtain epoxy aliphatic acid methyl ester softening agent.
The hot water of cooling rear formation is for the thick product water washing process of softening agent.
Wherein N-process, is that use soda ash or calcium carbonate are acid acceptor, and pH value is transferred to 6.5-6.8.
Experimental example 1
To the epoxy aliphatic acid methyl ester softening agent of embodiment 1-4 gained and tradition, add the oxirane value of the epoxy aliphatic acid methyl ester softening agent of catalyzer (vitriol oil) gained to test, standard is the mensuration > > of < < GBT1677-2008 softening agent oxirane value, the results are shown in following table, " comparative example 1 " in table refers to the epoxy aliphatic acid methyl ester softening agent that adds catalyzer (vitriol oil) gained.
By upper table contrast, can be found out, the present invention, owing to not needing to add catalyzer, makes the oxirane value of gained epoxy aliphatic acid methyl ester softening agent have obvious lifting compared with traditional technology.
Above the production method of a kind of epoxy aliphatic acid methyl ester softening agent provided by the present invention is described in detail.Applied specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment is just for helping to understand core concept of the present invention.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention.These improvement and modification also should fall in the protection domain of the claims in the present invention.
Claims (8)
1. a production method for epoxy aliphatic acid methyl ester softening agent, is characterized in that, carries out as follows successively:
(1) water coolant inner coil pipe is set in reactor, makes the outer separator circulating cooling pipe in water coolant inner coil pipe and reactor outside form dual cycle cooling system;
(2) fatty acid methyl ester and organic acid are dropped in reactor, heat temperature raising, opens and stirs and move described dual cycle cooling system, stops heating after being warmed up to 45-55 ℃;
(3) open cooling water valve, with the speed dropping hydrogen peroxide of 50-65g/s, reacting liquid temperature is controlled at 45-55 ℃, and time for adding is 2-3 hour;
(4), after hydrogen peroxide drips and finishes, insulation backflow 2-3 hour, obtains the thick product of softening agent;
(5) the thick product of softening agent is carried out to hot water cleaning, neutralization, underpressure distillation dehydration successively, stop stirring and close described dual cycle cooling system, obtain epoxy aliphatic acid methyl ester softening agent.
2. the production method of a kind of epoxy aliphatic acid methyl ester softening agent according to claim 1, is characterized in that, described organic acid add-on accounts for the 10%-12% of fatty acid methyl ester quality.
3. the production method of a kind of epoxy aliphatic acid methyl ester softening agent according to claim 1, is characterized in that, the add-on of described hydrogen peroxide accounts for the 36%-40% of fatty acid methyl ester quality.
4. the production method of a kind of epoxy aliphatic acid methyl ester softening agent according to claim 1, is characterized in that, described organic acid is formic acid.
5. the production method of a kind of epoxy aliphatic acid methyl ester softening agent according to claim 1, is characterized in that, described water coolant inner coil pipe and outer separator circulating cooling pipe are connected to same cooling water pipeline.
6. the production method of a kind of epoxy aliphatic acid methyl ester softening agent according to claim 1, is characterized in that, the hot water of the cooling rear formation of described dual cycle cooling system cleans the hot water of the thick product of softening agent for described (5).
7. the production method of a kind of epoxy aliphatic acid methyl ester softening agent according to claim 1, is characterized in that, the neutralization in described (5) is that the pH value in the thick product of softening agent is adjusted to 6.5-6.8.
8. the production method of a kind of epoxy aliphatic acid methyl ester softening agent according to claim 7, is characterized in that, the neutralizing agent that described neutralization adopts is soda ash or calcium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410183332.8A CN103936696A (en) | 2014-04-30 | 2014-04-30 | Production method of epoxy fatty acid methyl ester plasticizer |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410183332.8A CN103936696A (en) | 2014-04-30 | 2014-04-30 | Production method of epoxy fatty acid methyl ester plasticizer |
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| CN103936696A true CN103936696A (en) | 2014-07-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104560407A (en) * | 2015-01-06 | 2015-04-29 | 中山联成化学工业有限公司 | Method for preparing epoxy plasticizer |
| CN104592169A (en) * | 2015-01-21 | 2015-05-06 | 吴俊荣 | Method for preparing epoxy fatty acid methyl ester by taking illegal cooking oil as raw material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664835A (en) * | 2012-09-18 | 2014-03-26 | 江阴市向阳科技有限公司 | Preparation method of biological plasticizing agent epoxidized fatty acid methyl ester |
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2014
- 2014-04-30 CN CN201410183332.8A patent/CN103936696A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664835A (en) * | 2012-09-18 | 2014-03-26 | 江阴市向阳科技有限公司 | Preparation method of biological plasticizing agent epoxidized fatty acid methyl ester |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104560407A (en) * | 2015-01-06 | 2015-04-29 | 中山联成化学工业有限公司 | Method for preparing epoxy plasticizer |
| CN104560407B (en) * | 2015-01-06 | 2017-08-25 | 中山联成化学工业有限公司 | A kind of preparation method of epoxy plasticiser |
| CN104592169A (en) * | 2015-01-21 | 2015-05-06 | 吴俊荣 | Method for preparing epoxy fatty acid methyl ester by taking illegal cooking oil as raw material |
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Application publication date: 20140723 |