CN103073517A - Method for recovering reaction solvent and residual products in process of preparing N-substituted isothiazolinone derivant - Google Patents
Method for recovering reaction solvent and residual products in process of preparing N-substituted isothiazolinone derivant Download PDFInfo
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- CN103073517A CN103073517A CN2013100401290A CN201310040129A CN103073517A CN 103073517 A CN103073517 A CN 103073517A CN 2013100401290 A CN2013100401290 A CN 2013100401290A CN 201310040129 A CN201310040129 A CN 201310040129A CN 103073517 A CN103073517 A CN 103073517A
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- reaction solvent
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Abstract
The invention provides a method for recovering reaction solvent and residual products in the process of preparing N-substituted isothiazolinone derivant. The method comprises the following steps of: adding solubilizer into used reaction solvent when the N-substituted isothiazolinone derivant is prepared; and recovering the reaction solvent and the residual N-substituted isothiazolinone derivant dissolved or suspended in the reaction solvent by a distillation method, wherein the dissolving of the residual N-substituted isothiazolinone derivant in the reaction solvent can be remained due to the solubilizer, the boiling point of the solubilizer is higher than that of the reaction solvent, so the solubilizer and the reaction solvent do not form an azeotrope or have a chemical reaction. After the method provided by the invention is adopted, the reaction solvent and the residual products dissolved or suspended in the reaction solvent when the N-substituted isothiazolinone derivant is prepared can be effectively recovered, so that the product yield can be improved, the environment pollution can be reduced, and a distillation container is free from scaling.
Description
Technical field
The present invention relates to the preparation technology that N-replaces isothiazolinone derivatives, more specifically, relate to the recovery method that N-replaces reaction solvent and bottom product in the isothiazolinone derivatives preparation process.
Background technology
It is a class wide-spectrum bactericide that N-shown in the general formula I replaces isothiazolinone derivatives, and bacterium, fungi are had preferably inhibition.They have efficiently, low toxicity, can natural degradation in environment etc. advantage.Therefore be widely used in the fields such as Treatment of Industrial Water, makeup, material of construction, weaving, papermaking.
Wherein, R is alkyl, cycloalkyl or aryl, and further R can be the group of alkyl, aryl, alkoxyl group or aryloxy; R1, R2 are H or Cl independently.
This type of N-replaces isothiazolinone derivatives a kind of production method commonly used and comprises sulfuration, aminolysis and three large steps of chlorine cyclisation, as shown in Figure 1: the compound of general formula I V obtains the compound of general formula III through sulfuration, the compound of general formula III obtains the compound of general formula I I through aminolysis, the compound of general formula I I obtains the product shown in the general formula I through the chlorine cyclisation, and flow sequence is shown in the arrow among the figure.Wherein, the structural formula of the compound of the compound of the compound of general formula I V, general formula III, general formula I I is respectively:
Wherein, the chlorine cyclisation step normally, in reactor, add ethyl acetate as reaction solvent, the control temperature of reaction, the pressed powder that in batches adds general formula I I passes into a certain amount of chlorine simultaneously, reinforced complete after, reaction for some time, pass into nitrogen and remove hydrochloride solid product and the reaction solvent that the hydrogenchloride of generation, solid-liquid separation obtain general formula I.In order to reduce production costs, use the method for distillation to reclaim ethyl acetate.In the operating process of reality, can run into a problem, namely the product of a small amount of general formula I of dissolving or suspension is constantly concentrated in distillation in the reaction solvent, causes at last the distil container fouling; If keep the distil container non-scaling, just must remain a certain amount of ethyl acetate, not only cause waste but also contaminate environment.
Therefore, need a more effective method reclaim reaction solvent and bottom product, and so that distil container non-scaling, free from environmental pollution and improve product yield.
Summary of the invention
In order one of to solve the problems of the technologies described above at least, the invention provides the recovery method that a kind of N-replaces reaction solvent and bottom product in the isothiazolinone derivatives preparation process, both can improve the rate of recovery of reaction solvent, can reclaim again the bottom product that dissolves or suspend in the reaction solvent, and so that the distil container non-scaling, improve yield and free from environmental pollution, solved the technical problem that exists in the prior art, realized goal of the invention of the present invention.
The recovery method of reaction solvent and bottom product in the N-replacement isothiazolinone derivatives preparation process provided by the invention may further comprise the steps:
Add solubilizing agent in the reaction solvent that when the described N-of preparation replaces isothiazolinone derivatives, uses;
Then reclaim the described reaction solvent in the N-replacement isothiazolinone derivatives preparation process and reclaim the residual N-that dissolves or be suspended in the described reaction solvent by the method for distilling and replace isothiazolinone derivatives;
Wherein, N-residual in the described reaction solvent of described solubilizing agent solubilized replaces isothiazolinone derivatives, and the boiling point of described solubilizing agent is higher than described reaction solvent with described reaction solvent formation azeotrope or chemical reaction occurs.
Adopt aforesaid method of the present invention, replace in the isothiazolinone derivatives preparation process at N-, both can reclaim most reaction solvent, can reclaim again the bottom product that dissolves or suspend in the reaction solvent, so that distill rear container non-scaling, raising product yield, and reduced environmental pollution.
Preferably, described reaction solvent is ethyl acetate.
Certainly, also methylene dichloride or toluene etc. of described reaction solvent.But because methylene dichloride has high volatile volatile, and toluene has toxicity, and therefore, normally used solvent is ethyl acetate.Certainly, method for recovering solvents of the present invention, the recovery that also is applicable to prepare other reaction solvents that use when N-replaces isothiazolinone derivatives.
Preferably, described solubilizing agent is that boiling point is higher than 110 ℃ alcohol, polyvalent alcohol, polyhydric alcohol polymer or their mixture.Most of alcohol, polyvalent alcohol and polyhydric alcohol polymer all have good mutual solubility with ethyl acetate, and chemical reaction does not occur, and it is better that N-is replaced the isothiazolinone solvability.Because the boiling point of ethyl acetate is 77 ℃, to consider by distillation and it can be separated well with solubilizing agent, the boiling point of selected solubilizing agent should be higher than 110 ℃.
Further, preferably, described solubilizing agent is propyl carbinol, ethylene glycol, glycol ether, Triethylene glycol or their mixture.The boiling point of propyl carbinol is 116～118 ℃, and the boiling point of ethylene glycol is 196～198 ℃, and the boiling point of glycol ether and Triethylene glycol is more taller than the boiling point of ethylene glycol.These materials and ethyl acetate be miscible, chemical reaction does not occur and can pass through fractionation by distillation.Glycol ether also can be used as the stablizer that N-replaces the isothiazolinone compounds, often uses in different formula for a product.
In above-mentioned arbitrary technical scheme, preferably, the consumption of described solubilizing agent and the volume percent of described reaction solvent are 0.1%～10%.The concrete consumption of solubilizing agent can specifically be determined according to the residual content that N-in the amount of distillation reaction solvent and the reaction solvent replaces isothiazolinone, those of ordinary skill in the art just can come to determine the concrete consumption of solubilizing agent as the case may be according to this principle, repeat no more.
In sum, recovery method according to reaction solvent provided by the invention, in the situation that solubilizing agent exists, distill, can reclaim most reaction solvent, a small amount of bottom product of dissolving or suspension finally is concentrated in solubilizing agent in the reaction solvent, be convenient to recycle, both can improve the rate of recovery of reaction solvent, can reclaim again the bottom product that dissolves or suspend in the reaction solvent, so that container non-scaling after the distillation, and reduced environmental pollution, have good technique effect and practicality.
Description of drawings
Fig. 1 is that N-replaces isothiazolinone derivatives preparation process schematic flow sheet in the prior art;
Fig. 2 shows the FB(flow block) that N-of the present invention replaces recovery method one embodiment of reaction solvent and bottom product in the isothiazolinone derivatives preparation process.
Embodiment
Describe the present invention in detail below in conjunction with the drawings and specific embodiments.Need to prove, in the situation that do not conflict, the application's embodiment and the feature among the embodiment can make up mutually.
A lot of details have been set forth in the following description so that fully understand the present invention; but; the present invention can also adopt other to be different from other modes described here and implement, and therefore, protection scope of the present invention is not subjected to the restriction of following public specific embodiment.
As shown in Figure 2, the recovery method of reaction solvent and bottom product in the N-replacement isothiazolinone derivatives preparation process provided by the invention may further comprise the steps:
Wherein, described solubilizing agent can be kept the dissolving that N-residual in the described reaction solvent replaces isothiazolinone derivatives, and the boiling point of described solubilizing agent is higher than described reaction solvent and does not form azeotrope and chemical reaction occurs with described reaction solvent.
Adopt aforesaid method of the present invention, replace in the isothiazolinone derivatives preparation process at N-, both can reclaim most reaction solvent, can reclaim again the bottom product that dissolves or suspend in the reaction solvent, so that container non-scaling after the distillation, and reduced environmental pollution.
Preferably, described reaction solvent is ethyl acetate.N-replaces the reaction solvent that uses in the isothiazolinone derivatives preparation process and is generally ethyl acetate, and certainly, described reaction solvent is methylene dichloride or toluene etc. also.But because methylene dichloride has high volatile volatile, and toluene has toxicity, and therefore, normally used solvent is ethyl acetate.It will be understood by those of skill in the art that method for recovering solvents of the present invention, also be applicable to prepare the recovery of other reaction solvents that use when N-replaces isothiazolinone derivatives.
Preferably, described solubilizing agent is that boiling point is higher than 110 ℃ alcohol, polyvalent alcohol, polyhydric alcohol polymer or their mixture.Most of alcohol, polyvalent alcohol and polyhydric alcohol polymer all have good mutual solubility with ethyl acetate, and chemical reaction does not occur, and it is better that N-is replaced the isothiazolinone solvability.Because the boiling point of ethyl acetate is 77 ℃, to consider by distillation and it can be separated well with solubilizing agent, the boiling point of selected solubilizing agent should be higher than 110 ℃.
Preferably, described solubilizing agent is propyl carbinol, ethylene glycol, glycol ether, Triethylene glycol or their mixture.The boiling point of propyl carbinol is 116～118 ℃, and the boiling point of ethylene glycol is 196～198 ℃, and the boiling point of glycol ether and Triethylene glycol is more taller than the boiling point of ethylene glycol.These materials and ethyl acetate be miscible, chemical reaction does not occur and can pass through fractionation by distillation.Glycol ether also can be used as the stablizer that N-replaces the isothiazolinone compounds, often uses in different formula for a product.
In above-mentioned arbitrary technical scheme, preferably, the consumption of described solubilizing agent and the volume percent of described reaction solvent are: 0.1%～10%.The concrete consumption of solubilizing agent can specifically be determined according to the residual content that N-in the amount of distillation reaction solvent and the reaction solvent replaces isothiazolinone.In principle, when the amount of distillation reaction solvent is large, the corresponding increase of the amount of solubilizing agent; When N-replacement isothiazolinone content was high in the solvent, the amount of solubilizing agent is corresponding increase also.
Aforesaid method provided by the invention both can improve the rate of recovery of ethyl acetate, and the bottom product that can reclaim again dissolving in the reaction solvent or suspend is so that non-scaling in the container after the distillation, reduced environmental pollution.
Particularly, in the preferred embodiment, described reaction solvent is ethyl acetate, when the distillation ethyl acetate, the solubilizing agent that adds described ethyl acetate cumulative volume 0.1%～10%, this solubilizing agent should have following characteristic: (1) replaces isothiazolinone derivatives to N-good solubility, and (2) can be miscible with ethyl acetate, (3) its boiling point be higher than ethyl acetate and not with ethyl acetate form azeotrope, not with ethyl acetate generation chemical reaction.In the situation that solubilizing agent exists, distill, can reclaim most ethyl acetate, a small amount of bottom product of solvent or suspension finally is concentrated in solubilizing agent in the reaction solvent, be convenient to recycle, and so that container non-scaling after the distillation, reduced environmental pollution.
Below verify inventing described method with specific embodiment:
Embodiment 1
The N-that adds 1000ml in matrass replaces the used ethyl acetate of reaction in the isothiazolinone derivatives preparation process, and the glycol ether of 10ml carries out air distillation, obtains at last ethyl acetate 930ml, and the rate of recovery is 93.0%.
Embodiment 2
Add the used ethyl acetate of reaction of 1000ml in matrass, the ethylene glycol of 50ml carries out air distillation, obtains at last ethyl acetate 950ml, and the rate of recovery is 95.0%.
Embodiment 3
Add the used ethyl acetate of reaction of 1000ml in matrass, the propyl carbinol of 100ml carries out air distillation, obtains at last ethyl acetate 955ml, and the rate of recovery is 95.5%.
From above embodiment, can find out method provided by the invention, but efficient recovery N-replaces the reaction solvent in the isothiazolinone derivatives preparation process, and reclaim dissolving or be suspended in bottom product in the reaction solvent, yield and the container non-scaling of product have been improved, thereby the reduction cost, and reduced environmental pollution, have good economic and social benefit.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1.N-the recovery method of reaction solvent and bottom product is characterized in that in the replacement isothiazolinone derivatives preparation process, may further comprise the steps:
Add solubilizing agent in the reaction solvent that when preparation N-replaces isothiazolinone derivatives, uses;
Then reclaim described reaction solvent by the method for distilling and reclaim the residual N-that dissolves or be suspended in the described reaction solvent and replace isothiazolinone derivatives;
Wherein, described solubilizing agent can be kept the dissolving that N-residual in the described reaction solvent replaces isothiazolinone derivatives, and the boiling point of described solubilizing agent is higher than described reaction solvent with described reaction solvent formation azeotrope or chemical reaction occurs.
2. the recovery method of reaction solvent and bottom product in the N-replacement isothiazolinone derivatives preparation process according to claim 1 is characterized in that, described reaction solvent is ethyl acetate.
3. N-according to claim 2 replaces the recovery method of reaction solvent and bottom product in the isothiazolinone derivatives preparation process, it is characterized in that, described solubilizing agent is that boiling point is higher than 110 ℃ alcohol, polyvalent alcohol, polyhydric alcohol polymer or their mixture.
4. N-according to claim 3 replaces the recovery method of reaction solvent and bottom product in the isothiazolinone derivatives preparation process, it is characterized in that, described solubilizing agent is propyl carbinol, ethylene glycol, glycol ether, Triethylene glycol or their mixture.
5. each described N-replaces the recovery method of reaction solvent and bottom product in isothiazolinone derivatives preparation process according to claim 1-4, it is characterized in that, the consumption of described solubilizing agent and the volume percent of described reaction solvent are 0.1%～10%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4325201A (en) * | 1967-03-09 | 1982-04-20 | Rohm And Haas Company | Seed treatment with 3-isothiazolones |
| WO1993011168A1 (en) * | 1991-12-06 | 1993-06-10 | Shell Oil Company | Separation process |
| US6511946B1 (en) * | 1998-07-28 | 2003-01-28 | Fuchs Petrolub Ag | Water-miscible cooling lubricant concentrate |
| CN1440426A (en) * | 2000-07-11 | 2003-09-03 | 联合碳化化学及塑料技术公司 | Method of reducing formation of precipitates in solvent recovery system |
| CN102786492A (en) * | 2011-05-19 | 2012-11-21 | 大连百傲化学有限公司 | Preparation method of 3-isothiazolinone compound |
-
2013
- 2013-02-01 CN CN2013100401290A patent/CN103073517A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4325201A (en) * | 1967-03-09 | 1982-04-20 | Rohm And Haas Company | Seed treatment with 3-isothiazolones |
| WO1993011168A1 (en) * | 1991-12-06 | 1993-06-10 | Shell Oil Company | Separation process |
| US6511946B1 (en) * | 1998-07-28 | 2003-01-28 | Fuchs Petrolub Ag | Water-miscible cooling lubricant concentrate |
| CN1440426A (en) * | 2000-07-11 | 2003-09-03 | 联合碳化化学及塑料技术公司 | Method of reducing formation of precipitates in solvent recovery system |
| CN102786492A (en) * | 2011-05-19 | 2012-11-21 | 大连百傲化学有限公司 | Preparation method of 3-isothiazolinone compound |
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Application publication date: 20130501 |