CN103833497B - By the method for the thick cyclic ethers of ethanolamine treatment with by its obtained smart cyclic ethers - Google Patents
By the method for the thick cyclic ethers of ethanolamine treatment with by its obtained smart cyclic ethers Download PDFInfo
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- CN103833497B CN103833497B CN201210492787.9A CN201210492787A CN103833497B CN 103833497 B CN103833497 B CN 103833497B CN 201210492787 A CN201210492787 A CN 201210492787A CN 103833497 B CN103833497 B CN 103833497B
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Abstract
The present invention relates to the method for the thick cyclic ethers of a kind of ethanolamine treatment, described thick cyclic ethers comprises 2-20 carbon atom, and the method comprises: 1) in thick cyclic ethers, add thanomin, carries out reflux condensation mode after being heated above the boiling point of thick cyclic ethers; 2) by step 1) mixture that obtains carries out layering; 3) in step 2) add thanomin in lower coarse cyclic ethers after layering, carry out reflux condensation mode after being heated above the boiling point of thick cyclic ethers; With 4) by step 3) mixture that obtains carries out layering, obtains the cyclic ethers after lower floor's process.Technological process of the present invention is not too fierce, easily controls, and yield is improved further.The invention still further relates to the smart cyclic ethers obtained by aforesaid method, the ultraviolet reductibility of this smart cyclic ethers is little, and total yield is high, and without obvious irritating smell.
Description
Technical field
The present invention relates to the method thick cyclic ethers being processed to (such as removing acidic substance wherein), particularly relate to the method for the thick cyclic ethers of a kind of ethanolamine treatment.The invention still further relates to and smart cyclic ethers obtained by this method.
Background technology
Thick cyclic ethers is a kind of mixture, and it material comprised includes but not limited to, such as, and the fluothane containing 7 carbon atoms, fluorine ether containing 7 carbon atoms and with fluorine, the equiatomic 5 and 6 yuan of rings of oxygen.
In general factory floor, have employed sodium hydroxide to process thick cyclic ethers (hereinafter referred to " workshop treatment process "), its technological process is, gets m gram of thick cyclic ethers, adds the sodium hydroxide solution (wherein, the thick cyclic ethers of mNaOH=0.32m) of 45%; Heated and stirred, to backflow, is incubated; Continue stirring 15 hours; Add tap water (wherein the thick cyclic ethers of m water=0.6m): heated and stirred to 80 DEG C; Leave standstill separatory after 2 hours; Tap water (wherein the thick cyclic ethers of m water=0.6m) is added in the thick cyclic ethers of then lower floor after separation; Heated and stirred to 70 DEG C; Leave standstill separatory after 2 hours.Repeat above-mentioned technological operation, then wash once, the pH value of upper solution should be 7, otherwise continues to press water-washing step, until pH is washed till 7.The thick cyclic ethers processed is weighed, rectifying (generally will wash 2 times).
But above-mentioned workshop treatment process exists following problem, first, because the alkalescence of the sodium hydroxide adopted is comparatively strong, its corrodibility is also comparatively strong, therefore technological process is wayward; Secondly, owing to adding tap water thereafter, it is fiercer with the reaction of sodium hydroxide, therefore technological process is also wayward.
Thanomin, chemical, it is mainly shock absorption and the preparation for emulsion in pharmaceutical preparation.In addition, the prevailing therepic use of thanomin is as Monoethanolamine Oleate injection, as sclerosant.Thanomin has hydroxyl and amino, and thus alcohols and the specific reaction of amine can occur.
Therefore, this area still seek one can overcome the thick cyclic ethers of process that defect that above-mentioned " workshop treatment process " exist makes the various aspects of performance of the smart cyclic ethers of acquisition all excellent simultaneously method and by its obtained smart cyclic ethers.
Summary of the invention
In in first, the present invention relates to the method for the thick cyclic ethers of a kind of ethanolamine treatment, described thick cyclic ethers comprises 2-20 carbon atom, and the method comprises: 1) in thick cyclic ethers, add thanomin, carries out reflux condensation mode after being heated above the boiling point of thick cyclic ethers; 2) by step 1) mixture that obtains carries out layering; 3) in step 2) add thanomin in lower coarse cyclic ethers after layering, carry out reflux condensation mode after being heated above the boiling point of thick cyclic ethers; With 4) by step 3) mixture that obtains carries out layering, obtain the cyclic ethers after lower floor's process, wherein, in step 1) in thick cyclic ethers and step 1) and step 3) in the weight ratio of whole thanomins that adds be 1:1, and in step 1) in the thanomin that adds be step 1) and step 3) in add 2/3 of whole thanomins, in step 3) in the thanomin that adds be step 1) and step 3) in add 1/3 of whole thanomins.
In aforesaid method of the present invention, described thick cyclic ethers comprises 5-10 carbon atom.
In the present invention's specific embodiment, the reflux condensation mode temperature in step 1) is 80-120 DEG C, in step 3) in reflux condensation mode temperature be 80-120 DEG C.In step 1) in the reflux condensation mode time be 10-20 hour, in step 3) in the reflux condensation mode time be 6-10 hour.In step 2) in separation time be 1-4 hour, in step 4) in separation time be 0.5-2 hour.
In the present invention one embodiment particularly, in step 1) in reflux condensation mode temperature be 90 DEG C, in step 3) in reflux condensation mode temperature be 90 DEG C.In step 1) in the reflux condensation mode time be 15 hours, in step 3) in the reflux condensation mode time be 8 hours.In step 2) in separation time be 2 hours, in step 4) in separation time be 1 hour.
Aforesaid method of the present invention also comprises the cyclic ethers after by process and weighs, rectifying.
In a second aspect, the invention still further relates to the smart cyclic ethers obtained by aforesaid method, the ultraviolet reductibility of this smart cyclic ethers between 215-225nm, total yield between 75-80%, and without obvious irritating smell.
Embodiment
First, as follows to the term definition that some in this specification sheets is concrete.
" scope " disclosed herein represents with the form of lower limit and the upper limit.Described scope can represent by one or more lower limit and one or more upper limit.Given range is limited by a selected lower limit and a upper limit.Selected lower limit and the upper limit define the border of special scope.All scopes that can carry out by this way limiting are reconfigurable, and namely any lower limit can be combined to form a scope with any upper limit.
In this article, unless otherwise indicated, all ratios all refer to weight ratio.
In this article, unless otherwise indicated, numerical range " a-b " represents any number between a to b, comprises end points a and b.
If do not particularly not pointed out, this specification sheets term " one " used refers to " at least one ".
In this article, except as otherwise noted, the ratio of each component or weight all refer to dry weight.
If do not illustrated especially, " comprising " mentioned in this article represents open, namely can also comprise other steps do not listed.
If do not illustrated especially, the concrete numerical value herein in embodiment and concrete material can with other integrate features describing part herein.
Specifically, the invention provides the method for the thick cyclic ethers of a kind of ethanolamine treatment, described thick cyclic ethers comprises 2-20 carbon atom, better comprises 5-10 carbon atom, better comprises 7-9 carbon atom.
Method of the present invention adopts thanomin through twice reflux condensation mode to process thick cyclic ethers, to remove acidic substance wherein.Specifically, described method comprises following step successively:
1) in thick cyclic ethers, add thanomin, after being heated above the boiling point of thick cyclic ethers, carry out reflux condensation mode;
2) by step 1) mixture that obtains carries out layering;
3) in step 2) add thanomin in lower coarse cyclic ethers after layering, carry out reflux condensation mode after being heated above the boiling point of thick cyclic ethers; With
4) by step 3) mixture that obtains carries out layering, obtains the cyclic ethers after lower floor's process,
Wherein, in step 1) in thick cyclic ethers and step 1) and step 3) in the weight ratio of whole thanomins that adds be 1:1(namely, step 1) in thick cyclic ethers/step 1) and step 3) in the weight ratio of whole thanomins that adds be 1:1), and in step 1) in the thanomin that adds be step 1) and step 3) in add 2/3 of whole thanomins, in step 3) in the thanomin that adds be step 1) and step 3) in the 1/3(ratio herein of whole thanomins that adds be all benchmark in weight).
In above-mentioned steps 1) in, after the boiling point being heated above thick cyclic ethers, carry out reflux condensation mode, that is, at this reflux condensation mode temperature, be incubated for some time.
In above-mentioned steps 2) in, by step 1) mixture that obtains carries out layering.In a concrete embodiment, described layering at room temperature makes described mixture leave standstill.In another particular embodiment of the invention, described layering also can be at room temperature adopt the devices such as such as separating funnel to carry out.In the embodiment that another is concrete, described layering also can be at room temperature carry out centrifugation.Layering of the present invention also can be the combination of two or three in above-mentioned three kinds of modes.
In above-mentioned steps 3) in, in step 2) add thanomin in lower coarse cyclic ethers after layering, carry out reflux condensation mode after being heated above the boiling point of thick cyclic ethers, that is, at this reflux condensation mode temperature, be incubated for some time.
In above-mentioned steps 4) in, by step 3) mixture that obtains carries out layering.In a concrete embodiment, described layering at room temperature makes described mixture leave standstill.In another particular embodiment of the invention, described layering also can be at room temperature adopt the devices such as such as separating funnel to carry out.In the embodiment that another is concrete, described layering can be at room temperature carry out centrifugation.Layering of the present invention also can be the combination of two or three in above-mentioned three kinds of modes.
Finally, the cyclic ethers after lower floor's process is obtained.
To above-mentioned steps 1) and 3) in the temperature and time of reflux condensation mode and above-mentioned steps 2) and 4) time of middle layering is not particularly limited, as long as described method at twice reflux condensation mode carry out just can.
In step 1) in, following processing condition can be selected: reflux condensation mode temperature is 80-120 DEG C, preferably 85-100 DEG C, be preferably 90 DEG C; Soaking time (i.e. reflux condensation mode time) is 10-20 hour, preferably 12-18 hour, is preferably 15 hours.
In step 2) in, can select following processing condition: under room temperature, time of repose (i.e. separation time) is 1-4 hour, preferably 2-3 hour, is preferably 2 hours.
For reflux condensation mode temperature be 90 DEG C, soaking time to be 15 hours and time of repose the be processing condition of 2 hours, described step 1) and 2) be performed such, get m gram of thick cyclic ethers, add 2/3m gram of thanomin, under agitation be heated to 90 DEG C and carry out reflux condensation mode, 90 DEG C time, be incubated 15 hours (90 DEG C time reflux condensation mode 15 hours), then remove heating unit, make it leave standstill to room temperature, whole time of repose is 2 hours.
In step 3) in, following processing condition can be selected: reflux condensation mode temperature is 80-120 DEG C, preferably 85-100 DEG C, be preferably 90 DEG C; Soaking time (i.e. reflux condensation mode time) is 6-10 hour, preferably 7-9 hour, is preferably 8 hours.
In step 4) in, can select following processing condition: under room temperature, time of repose (i.e. separation time) is 0.5-2 hour, preferably 1-1.5 hour, is preferably 1 hour.
For reflux condensation mode temperature be 90 DEG C, soaking time to be 8 hours and time of repose the be processing condition of 1 hour, described step 3) and 4) be performed such, in step 2) add 1/3m gram of thanomin in lower coarse cyclic ethers after layering, under agitation be heated to 90 DEG C and carry out reflux condensation mode, 8 hours are incubated (90 DEG C time reflux condensation mode 8 hours) 90 DEG C time, then remove heating unit, make it leave standstill to room temperature, whole time of repose is 1 hour.
In step 4) after, the cyclic ethers after lower floor can being processed is weighed, further rectifying.
The present invention also provides a kind of smart cyclic ethers obtained by aforesaid method, the ultraviolet reductibility of described smart cyclic ethers between 215-225nm, total yield between 75-80%, and without obvious irritating smell.
Compared with the treatment process of workshop, the advantage of the inventive method is embodied in following several aspect:
First, the present invention adopts the alkaline thanomin less than sodium hydroxide to process thick cyclic ethers, and technological process is not too fierce, easily controls.
Secondly, method of the present invention adopts twice reflux condensation mode to process thick cyclic ethers, and yield is improved further.
Further, the ultraviolet reductibility of the smart cyclic ethers obtained by the inventive method is little, total yield improves, and without obvious irritating smell.
Embodiment
Below, use embodiment that the present invention is described, but it is to be understood that the subject area the present invention is not limited to this.
In the following embodiments, described " ultraviolet reductibility " can adopt reference substance relative method to measure.Specifically, in all solution, test substance absorbs and meets Law of Lambert-Beer, then prepare need testing solution and reference substance solution respectively, in reference substance solution, the amount of contained tested composition should be 100% ± 10% of tested composition labelled amount in need testing solution, solvent for use also should be completely the same, measure the absorbancy of need testing solution and reference substance solution under the maximum wavelength of this material after, calculate the concentration of detected solution in trial-product by formula 3-3:
Cx=(Ax/AR) CR formula (3-2)
Content=(Cx × D)/W × 100 formula (3-3)
In formula, Cx is the concentration of need testing solution; Ax is the absorbancy of need testing solution; CR is the concentration of reference substance solution; AR is the absorbancy of reference substance solution; D is extension rate; W is trial-product sampling amount.(doing blank with pure water)
In the following embodiments, the yield of following formulae discovery cyclic ethers is adopted:
Calculating=(weight of the cyclic ethers after rectifying)/(the starting the weight of the thick cyclic ethers dropped into) * 100% of cyclic ethers yield.
Embodiment 1
The thick cyclic ethers that lot number is 090619 is processed with thanomin
In flask, be weighed into the thick cyclic ethers of 1080g, add 720g hydramine, ensure that thanomin can cover thick cyclic ethers completely.Carry out first time reflux condensation mode, its process temperature is controlled at 90 DEG C, carries out back flow reaction 15 hours, and now color changes rapidly (colourless → yellow-green colour → brown → black), and the color of upper strata reactant is black, very thickness.Then 2 hours are left standstill.Get lower coarse cyclic ethers, measuring its ultraviolet reductibility (T% → 0) is 251.3nm, irritant smell.
Then, with separating funnel, the thick cyclic ethers of above-mentioned acquisition is carried out layering.
Again then, in lower coarse cyclic ethers after separating the layers, add 360g hydramine, ensure that thanomin can cover thick cyclic ethers completely.Carry out second time reflux condensation mode, its process temperature is controlled at 90 DEG C, carries out back flow reaction 8 hours, and now color slowly changes (colourless → yellow-green colour → burgundy → brown), and the color of upper strata reactant is brown, without thickness.Then 1 hour is left standstill.Take off a layer cyclic ethers, measuring its ultraviolet reductibility (T% → 0) is 218.3nm, without obvious irritation smell.
Comparative example 1
" the workshop treatment process " described in " background technology " is adopted to process the thick cyclic ethers (below referred to as " the thick cyclic ethers 090410 of alkaline-heating method ") that lot number is 090410.
Be that the property indices of the thick cyclic ethers 090410 of the alkaline-heating method of thick cyclic ethers and the comparative example 1 processed in two steps in the thick cyclic ethers of 090619, embodiment 1 is listed in the table below in 1 by lot number.
Table 1
As can be seen from the above table, the ultraviolet reductibility of the cyclic ethers that the present invention obtains in two steps afterwards obviously reduces, and total yield significantly improves, and without obvious irritating smell.
Comparative example 2-4
By the step that comparative example 1 is identical, adopt " the workshop treatment process " described in " background technology " to process three batches of thick cyclic ethers, obtain 300kg, 600kg and 800kg tri-batches of smart cyclic ethers.Test the performance of these three batches of smart cyclic ethers, its ultraviolet reductibility (T% → 0) is respectively 217.5nm, 216.5nm and 224.1nm; Total yield after rectifying is respectively 78.6%, 79.2% and 78.4%.
In addition, the indices of the treatment process of thick to the treatment process of thick for comparative example 2-4 cyclic ethers and embodiment 1 cyclic ethers is listed in the table below in 2.
Table 2
As can be seen from the above table, compared with the treatment process of workshop, the ultraviolet reductibility through the smart cyclic ethers of present invention process acquisition obviously reduces, and total yield significantly improves, and without obvious irritating smell, and stability significantly improves.
Although the present invention is described in detail by above example, this description is only for illustrative purposes and should be interpreted as is the restriction to the spirit and scope of the present invention that the claims of enclosing require.In addition, above-described embodiment is only the object exemplified, and it can have various distortion, and those skilled in the art can understand these distortion and also belong to scope of the present invention.
Claims (9)
1., by a method for the thick cyclic ethers of ethanolamine treatment, described thick cyclic ethers comprises 2-20 carbon atom, and the method comprises:
1) in thick cyclic ethers, add thanomin, after being heated above the boiling point of thick cyclic ethers, carry out reflux condensation mode;
2) by step 1) mixture that obtains carries out layering;
3) in step 2) add thanomin in lower coarse cyclic ethers after layering, carry out reflux condensation mode after being heated above the boiling point of thick cyclic ethers; With
4) by step 3) mixture that obtains carries out layering, obtains the cyclic ethers after lower floor's process,
Wherein, in step 1) in thick cyclic ethers and step 1) and step 3) in the weight ratio of whole thanomins that adds be 1:1, and in step 1) in the thanomin that adds be step 1) and step 3) in add 2/3 of whole thanomins, in step 3) in the thanomin that adds be step 1) and step 3) in add 1/3 of whole thanomins.
2. the method for claim 1, is characterized in that, described thick cyclic ethers comprises 5-10 carbon atom.
3. method as claimed in claim 1 or 2, is characterized in that, in step 1) in reflux condensation mode temperature be 80-120 DEG C, in step 3) in reflux condensation mode temperature be 80-120 DEG C.
4. method as claimed in claim 1 or 2, is characterized in that, in step 1) in the reflux condensation mode time be 10-20 hour, in step 3) in the reflux condensation mode time be 6-10 hour.
5. method as claimed in claim 1 or 2, is characterized in that, in step 2) in separation time be 1-4 hour, in step 4) in separation time be 0.5-2 hour.
6. method as claimed in claim 3, is characterized in that, in step 1) in reflux condensation mode temperature be 90 DEG C, in step 3) in reflux condensation mode temperature be 90 DEG C.
7. method as claimed in claim 4, is characterized in that, in step 1) in the reflux condensation mode time be 15 hours, in step 3) in the reflux condensation mode time be 8 hours.
8. method as claimed in claim 5, is characterized in that, in step 2) in separation time be 2 hours, in step 4) in separation time be 1 hour.
9. method as claimed in claim 1 or 2, is characterized in that, described method also comprises the cyclic ethers after by process and weighs, rectifying.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208410A (en) * | 1996-01-16 | 1999-02-17 | 林德股份公司 | Process and device for the preparation of tetrahydrofuran |
| CN101153029A (en) * | 2006-09-26 | 2008-04-02 | 上海富诺林精细化工有限公司 | Method for purifying fluorocarbon solvent |
| CN102596926A (en) * | 2009-10-30 | 2012-07-18 | 株式会社日立工业设备技术 | Process and system for purification of tetrahydrofuran |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208410A (en) * | 1996-01-16 | 1999-02-17 | 林德股份公司 | Process and device for the preparation of tetrahydrofuran |
| CN101153029A (en) * | 2006-09-26 | 2008-04-02 | 上海富诺林精细化工有限公司 | Method for purifying fluorocarbon solvent |
| CN102596926A (en) * | 2009-10-30 | 2012-07-18 | 株式会社日立工业设备技术 | Process and system for purification of tetrahydrofuran |
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