CN103102298A - Method for producing n-vinyl pyrrolidone - Google Patents
Method for producing n-vinyl pyrrolidone Download PDFInfo
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- CN103102298A CN103102298A CN2013100479793A CN201310047979A CN103102298A CN 103102298 A CN103102298 A CN 103102298A CN 2013100479793 A CN2013100479793 A CN 2013100479793A CN 201310047979 A CN201310047979 A CN 201310047979A CN 103102298 A CN103102298 A CN 103102298A
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- sylvite
- pyrrolidone
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- vinyl pyrrolidone
- diethylene glycol
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Abstract
The invention discloses a method for producing n-vinyl pyrrolidone (NVP). With the adoption of diethylene glycol dimethyl ether as a catalyst, not only are the effects of a convectional catalyst of reducing the reaction temperature, shortening the reaction time, improving the conversion rate, inhibiting the side reaction and improving the product yield achieved, but also the cost for producing NVP is effectively lowered because the price of diethylene glycol dimethyl ether is lower than the conventional catalyst, so that the method is more beneficial for industrial production.
Description
Technical field
The present invention relates to a kind of method of producing vinyl pyrrolidone, belong to fine chemistry industry and chemical pharmacy field.
Background technology
Continuous progress and development along with science and technology, every new industry has larger promoter action to the relevant kind in the PVP series product in recent years, following PVP series product will be more widely used in frontier, as the application of medical product innovation field, environment-protective water process field, biosensor, new special paint field, wine brewing and field of beverage, energy extraction field, printing industry and cultivation field etc., to there be larger demand to support to the PVP product, the coming years, the market requirement will be with 10% speed increment, and market outlook are wide.And also just constantly significantly increase progressively accordingly as the consumption of the monomer vinyl pyrrolidone (NVP) that synthesizes the PVP product.
In recent years, many producers successively produce the fine chemical product of this high added value of NVP, and its synthetic method has several, due to the restriction that is subjected to raw materials cost, mainly still take the acetylene synthesis method, i.e. acetylene gas and a-p synthetic NVP under catalyst action; During the synthetic NVP of general Reppe method, mostly adopt highly basic such as KOH to do the vinylation reaction of catalyst a-pyrrolidone and acetylene, the defective of the method is fairly obvious, the amount that is the non-volatility polymeric by-products produced in reaction process is larger, not only cause target product NVP yield to reduce, and make the separation of NVP and purify complicated.Therefore, generally all take comparatively gentle reaction conditions in industrial production, control the generation of polymerization side reactions by the mode that reduces a-pyrrolidone transformation efficiency, but in a lot of situations, produce little effect, in order to improve the yield of NVP, add one or more promotors to tend to bring about tangible results.The years of researches result shows BDO, and the effect of polyethylene kind promotor, terminal hydroxy group polyethers and linear diols class promotor is apparent in view, not only can reduce temperature of reaction, make reaction process relatively gentle, and can fast reaction speed, improve transformation efficiency, and can suppress the generation of polymerization side reactions, increase selectivity, improve yield, but these promotor prices are too high, and consumption is 2%～4%, large usage quantity, fringe cost is too high, is not suitable for suitability for industrialized production.
Summary of the invention
The present invention is directed in traditional mode of production vinyl pyrrolidone (NVP) process, the promotor that uses, because of price high, consumption is large, the problem that whole production process cost is raise, the present invention efficiently solves present promotor high because of price by using diethylene glycol dimethyl ether as promotor, consumption is large, the problem that whole production process cost is raise.
To achieve these goals, the present invention adopts following technical scheme:
The method of a kind of production vinyl pyrrolidone (NVP), described production method comprises the following steps:
A, prepare sylvite catalyzer a-pyrrolidone sylvite in reactor, and make the a-pyrrolidone excessive, put into the sylvite storage tank after a-pyrrolidone sylvite is fully dewatered;
B, add the diethylene glycol dimethyl ether of a-pyrrolidone sylvite weight 1 ± 0.05% in step a in the sylvite storage tank, and it is mixed;
C, be that the acetylene of 8:2 and the mixed gas of nitrogen pass into autoclave with volume ratio, sent into simultaneously the mixed solution of a-p sylvite, a-p and diethylene glycol dimethyl ether by volume pump, control temperature at 130 ℃～150 ℃, pressure-controlling is reacted 3h under 12 atmospheric pressure, unreacted a-p and NVP are told respectively in reacted mixed solution distillation, and the NVP that collection distills out rectifying again obtains target product vinyl pyrrolidone (NVP).
The beneficial effect that the invention provides technical scheme is: the method that the invention provides a kind of production vinyl pyrrolidone (NVP), by using diethylene glycol dimethyl ether as promotor, both reach traditional promotor and reduced temperature of reaction, Reaction time shorten, improve transformation efficiency, suppressing side reaction produces, improve the effect of product yield, simultaneously low because of the more traditional promotor of diethylene glycol dimethyl ether price again, consumption is less, effectively reduce the cost of producing vinyl pyrrolidone (NVP), more be conducive to suitability for industrialized production.
Description of drawings
Fig. 1 is the schema that the present invention produces the method for vinyl pyrrolidone (NVP).
Embodiment
For making purpose of the present invention, technical scheme and beneficial effect clearer, below embodiment of the present invention is described further in detail.
The invention provides the method for a kind of production vinyl pyrrolidone (NVP), its concrete grammar comprises the following steps:
A, prepare sylvite catalyzer a-pyrrolidone sylvite in reactor, and make the a-pyrrolidone excessive, put into the sylvite storage tank after a-pyrrolidone sylvite is fully dewatered;
B, add the diethylene glycol dimethyl ether of a-pyrrolidone sylvite weight 1 ± 0.05% in step a in the sylvite storage tank, and it is mixed;
C, be that the acetylene of 8:2 and the mixed gas of nitrogen pass into autoclave with volume ratio, sent into simultaneously the mixed solution of a-p sylvite, a-p and diethylene glycol dimethyl ether by volume pump, control temperature at 130 ℃～150 ℃, pressure-controlling is reacted 3h under 12 atmospheric pressure, unreacted a-p and NVP are told respectively in reacted mixed solution distillation, and the NVP that collection distills out rectifying again obtains target product vinyl pyrrolidone (NVP).
Embodiment 1:
A, 104ga-pyrrolidone and 2g potassium hydroxide are added in the sylvite reactor heat under decompression state, keep 110 ℃ of fully reactions, until distillate moisture stopped heating less than 0.05% time,
B, add the 1.06g diethylene glycol dimethyl ether in the sylvite storage tank, put into basin after mixing;
C, be that the acetylene of 8:2 and the mixed gas of nitrogen pass into autoclave with volume ratio, the mixed solution of a-p sylvite, a-p and the diethylene glycol dimethyl ether for preparing more than inciting somebody to action simultaneously pumps into high-pressure reactor and controls temperature at 130 ℃～150 ℃, pressure-controlling is reacted 3h under 12 atmospheric pressure, unreacted a-p and NVP are told respectively in reacted mixed solution distillation, and the NVP that collection distills out rectifying again obtains target product vinyl pyrrolidone (NVP).
Transformation efficiency is 89.6% after testing, and the yield of target product NVP is 99.8%.
Example two:
A, 260ga-pyrrolidone and 5g potassium hydroxide are added in the sylvite reactor heat under decompression state, keep 110 ℃ of fully reactions, until distillate moisture stopped heating less than 0.05% time;
B, add the 2.65g diethylene glycol dimethyl ether, put into basin after mixing;
C, volume ratio are that the acetylene of 8:2 and the mixed gas of nitrogen pass into autoclave, the mixed solution of a-p sylvite, a-p and the diethylene glycol dimethyl ether for preparing more than inciting somebody to action simultaneously pumps into high-pressure reactor and controls temperature at 130 ℃～150 ℃, pressure-controlling is reacted 3h under 12 atmospheric pressure, unreacted a-p and NVP are told respectively in reacted mixed solution distillation, and the NVP that collection distills out rectifying again obtains target product vinyl pyrrolidone (NVP).
Transformation efficiency is 88.9% after testing, and the yield of target product NVP is 98.6%.
Example three:
A, 1040ga-pyrrolidone and 20g potassium hydroxide are added in the sylvite reactor heat under decompression state, keep 110 ℃ of fully reactions, until distillate moisture stopped heating less than 0.05% time;
B, add the 10.6g diethylene glycol dimethyl ether, put into basin after mixing;
C, be that the acetylene of 8:2 and the mixed gas of nitrogen pass into autoclave with volume ratio, the mixed solution of a-p sylvite, a-p and the diethylene glycol dimethyl ether for preparing more than inciting somebody to action simultaneously pumps into high-pressure reactor and controls temperature at 130 ℃～150 ℃, pressure-controlling is reacted 3h under 12 atmospheric pressure, unreacted a-p and NVP are told respectively in reacted mixed solution distillation, and the NVP that collection distills out rectifying again obtains target product vinyl pyrrolidone (NVP).
Transformation efficiency is 88.7% after testing, and the yield of target product NVP is 98.8%.
Protection domain of the present invention is not limited to above-mentioned example, and every technology distortion of doing according to the technology of the present invention principle is within all falling into protection scope of the present invention.
Claims (1)
1. a method of producing vinyl pyrrolidone, is characterized in that, described production method comprises the following steps:
A, prepare sylvite catalyzer a-pyrrolidone sylvite in reactor, and make the a-pyrrolidone excessive, put into the sylvite storage tank after a-pyrrolidone sylvite is fully dewatered;
B, add the diethylene glycol dimethyl ether of a-pyrrolidone sylvite weight 1 ± 0.05% in step a in the sylvite storage tank, and it is mixed;
C, be that the acetylene of 8:2 and the mixed gas of nitrogen pass into autoclave with volume ratio, sent into simultaneously the mixed solution of a-p sylvite, a-p and diethylene glycol dimethyl ether by volume pump, control temperature at 130 ℃～150 ℃, pressure-controlling is reacted 3h under 12 atmospheric pressure, unreacted a-p and vinyl pyrrolidone are told respectively in reacted mixed solution distillation, and the vinyl pyrrolidone that collection distills out rectifying again obtains the target product vinyl pyrrolidone.
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| CN2013100479793A CN103102298A (en) | 2013-02-07 | 2013-02-07 | Method for producing n-vinyl pyrrolidone |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319391A (en) * | 2013-05-24 | 2013-09-25 | 中盐安徽红四方股份有限公司 | Novel process for synthesizing N-vinyl pyrrolidone (NVP) |
| CN105214570A (en) * | 2015-10-31 | 2016-01-06 | 张家口珂玛新材料科技有限公司 | A kind of vinyl pyrrolidone synthesis reactor |
| CN106166559A (en) * | 2016-06-13 | 2016-11-30 | 焦作中维特品药业有限公司 | During a kind of NVP produces, residual substances processes the method reclaimed |
| CN106432028A (en) * | 2016-08-26 | 2017-02-22 | 衢州建华东旭助剂有限公司 | Preparation method and application of 2-pyrrolidinone solution of alkali metal 2-pyrrolidinone salt |
| CN110903229A (en) * | 2019-12-19 | 2020-03-24 | 清华大学 | Synthesis method of N-vinyl pyrrolidone |
| CN112574088A (en) * | 2019-09-30 | 2021-03-30 | 中国石油化工股份有限公司 | Method for synthesizing N-vinyl pyrrolidone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2806848A (en) * | 1957-09-17 | Vinylation | ||
| US4410726A (en) * | 1981-06-12 | 1983-10-18 | Gaf Corporation | Vinylation reaction |
| US5665889A (en) * | 1996-01-22 | 1997-09-09 | Industrial Technology Research Institute | Method for the production of N-vinyl-2-pyrrolidone by vinylation |
-
2013
- 2013-02-07 CN CN2013100479793A patent/CN103102298A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2806848A (en) * | 1957-09-17 | Vinylation | ||
| US4410726A (en) * | 1981-06-12 | 1983-10-18 | Gaf Corporation | Vinylation reaction |
| US5665889A (en) * | 1996-01-22 | 1997-09-09 | Industrial Technology Research Institute | Method for the production of N-vinyl-2-pyrrolidone by vinylation |
Non-Patent Citations (1)
| Title |
|---|
| 秦振宝，等: "N-乙烯基吡咯烷酮的合成研究进展", 《合成技术及应用》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319391A (en) * | 2013-05-24 | 2013-09-25 | 中盐安徽红四方股份有限公司 | Novel process for synthesizing N-vinyl pyrrolidone (NVP) |
| CN105214570A (en) * | 2015-10-31 | 2016-01-06 | 张家口珂玛新材料科技有限公司 | A kind of vinyl pyrrolidone synthesis reactor |
| CN106166559A (en) * | 2016-06-13 | 2016-11-30 | 焦作中维特品药业有限公司 | During a kind of NVP produces, residual substances processes the method reclaimed |
| CN106166559B (en) * | 2016-06-13 | 2018-08-21 | 焦作中维特品药业有限公司 | The method of residual substances processing recycling in a kind of NVP production |
| CN106432028A (en) * | 2016-08-26 | 2017-02-22 | 衢州建华东旭助剂有限公司 | Preparation method and application of 2-pyrrolidinone solution of alkali metal 2-pyrrolidinone salt |
| CN106432028B (en) * | 2016-08-26 | 2019-10-25 | 衢州建华东旭助剂有限公司 | A kind of preparation method and its usage of the 2-Pyrrolidone solution of alkali metal 2-Pyrrolidone salt |
| CN112574088A (en) * | 2019-09-30 | 2021-03-30 | 中国石油化工股份有限公司 | Method for synthesizing N-vinyl pyrrolidone |
| CN112574088B (en) * | 2019-09-30 | 2022-11-04 | 中国石油化工股份有限公司 | Method for synthesizing N-vinyl pyrrolidone |
| CN110903229A (en) * | 2019-12-19 | 2020-03-24 | 清华大学 | Synthesis method of N-vinyl pyrrolidone |
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Application publication date: 20130515 |