CN101475525A - Preparation of piperidine nitroxyl radical anti-polymerization inhibitor - Google Patents
Preparation of piperidine nitroxyl radical anti-polymerization inhibitor Download PDFInfo
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- CN101475525A CN101475525A CNA2009100250947A CN200910025094A CN101475525A CN 101475525 A CN101475525 A CN 101475525A CN A2009100250947 A CNA2009100250947 A CN A2009100250947A CN 200910025094 A CN200910025094 A CN 200910025094A CN 101475525 A CN101475525 A CN 101475525A
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Abstract
The invention provides a method for preparing a piperidine nitrogen oxygen-derived free radical polymerization inhibitor, which has the advantages that: firstly, the reaction time is short, the reaction condition is mild, and the operation is simpler; secondly, a catalyst has cheaper price and low cost, is convenient to separate, and can be reused; thirdly, the yield is higher; and fourthly, water is taken as a solvent, and the method for direct drying by distillation cannot generate waste solution and wastewater, does not pollute the environment, and realizes zero release in industrial production in a real sense. Therefore, the method is a method for preparing piperidine nitrogen oxygen-derived free radicals, and provides convenience for industrial production.
Description
Technical field
The present invention relates to the preparation method of a kind of technology of preparing of anti-polymerization inhibitor, particularly a kind of piperidine nitroxyl radical anti-polymerization inhibitor.
Background technology
Piperidine nitroxide free-radical is a kind of organic chemical industry's product commonly used, both in organic polymer as photostabilizer, also can in organic synthesis, be used as oxygenant, in living things system research, also can be used as spin label.
The industrial process of the piperidine nitroxide free-radical of having reported at present mainly contains following several, is listed below:
Main employing sodium wolframate or phospho-wolframic acid are catalyzer in the traditional technology, and hydrogen peroxide is made solvent as oxygenant with methyl alcohol, water, methyl alcohol-acetonitrile, makes nitroxyl free radical through hydrogen peroxide oxidation.The shortcoming of this method is: the catalyzer price is more expensive, yield is low, long reaction time, localized heat release severity, generating by product easily makes quality product not reach requirement, big and the effective Separation and Recovery of catalyst levels simultaneously, can only adopt the crystalline method to obtain product, thereby produce a large amount of waste liquor contamination environment.(synthesis，1971，190：Z.Naturforsch，1976，31b，1376；Prakt.chem.，1985，327，1011)；
US5.218.116 adopts ZSM-5 to make catalyzer, though this catalyzer is a heterogeneous catalyst, catalyzer costs an arm and a leg, active decline soon, and low repetition, and can't regenerate, easily environment is polluted.
CN1235946A has introduced the method that a kind of spent ion exchange resin is made catalyzer, though this method has improved yield to a certain extent, but still can not reach the highest effect.Still there are a large amount of waste liquids to produce contaminate environment in the production process.And ion exchange resin cost height need constantly carry out activating and regenerating, and it is cumbersome to operate in industrial production.
It is the production method of catalyzer with the houghite that CN1683414A has introduced a kind of, though the catalyzer of this method can be recycled, can not cause environmental pollution, but have following shortcoming, and catalyst levels is big; Because there is the homogeneous phase ion in this catalyzer, not easily separated, so aftertreatment can only adopt the crystalline method, otherwise easily cause product residue on ignition disqualified upon inspection.Yield will reduce like this, and still can stay a large amount of waste liquor contamination environment.
In sum, the method for preparing piperidine nitroxide free-radical does not at present still reach best perfect condition, the needs that need a kind of new catalyzer of research and development and production method to satisfy industrial production and environmental protection.
Summary of the invention
At the problems referred to above, the preparation method of piperidine nitroxyl radical anti-polymerization inhibitor provided by the invention, select for use magnesium salts as this catalyst for reaction, thereby operate easier, reaction times short, yield is higher, the catalyzer cost is lower and production process realizes zero release, and environmentally safe.
The preparation method of piperidine nitroxyl radical anti-polymerization inhibitor provided by the invention, its reaction formula is expressed as follows:
Wherein X represents C=O, CH2 or CH2OH, this method also further may further comprise the steps: add solvent and piperidines in reactor, under 20 ℃-100 ℃, add catalyzer and oxygenant, described catalyzer is the magnesium salts precipitation, and described oxygenant is a hydrogen peroxide, stirring reaction 3-15 hours, wherein the mol ratio of hydrogen peroxide and piperidines is 1.5～4:1, and the quality of catalyzer is 0.01%～0.5% of a piperidines quality.
Preferably, above-mentioned solvent is one or more in water, ethanol, methyl alcohol and the acetonitrile, and above-mentioned magnesium salts is precipitated as magnesium oxide, sal epsom, magnesiumcarbonate or magnesium hydroxide.
Preferably, temperature of reaction is 60 ℃-90 ℃, and catalyzer is 0.01%～0.2% of a piperidines quality.
Preferably, also further comprise: reacted filtrate decompression is concentrated into does the back by the scraping machine scraping blade, gets finished product, and the water that condensation obtains in the concentration process can be used as solvent cycle and uses.
Compared with prior art, the present invention has following characteristics:
1, the precipitation of catalyzer magnesium ion, the solubleness in water is minimum, thereby is a kind of heterogeneous catalyst, is easy to separate, and can not bring influence to final product quality.Described magnesium salts is precipitated as magnesium oxide, magnesiumcarbonate, magnesium hydroxide or sal epsom;
2, the amount of catalyzer is 0.01%～0.5% of a raw material piperidines, and consumption is minimum;
3, catalyzer filters the back and directly reclaims use;
4, direct evaporate to dryness scraping blade behind the reacting liquid filtering gets finished product;
5, the water that condensation obtains in the concentration process is used for the solvent of next batch reaction.
The invention has the advantages that: 1, reaction times weak point, the reaction conditions gentleness is operated simpler; 2, the catalyzer price is more cheap, and cost is low, and convenient separation can be used repeatedly; 3, yield is higher; 4, solvent is a water, and directly the method for evaporate to dryness can not produce any waste liquid, waste water, and environmentally safe is realized the zero release of real meaning on the industrial production.Therefore, this method is a kind of production method of being convenient to the piperidine nitroxide free-radical of suitability for industrialized production more.
Embodiment
Embodiment 1:
The embodiment of the invention 1 may further comprise the steps:
1) in three mouthfuls of reaction flasks of 2L, adds 500g water and 500g (3.55mol) 2.2.6.6-tetramethyl piperidine, 50mg magnesium oxide, stir down at 75 ℃, utilizing dropping funnel to drip off 850g (7.5mol) concentration in one hour is 30% hydrogen peroxide, reacted four hours, vapor detection, the reaction solution transformation efficiency reaches more than 99.8%, stopped reaction;
2) suction filtration is isolated magnesium oxide, reclaims directly and utilizes;
3) after about 75 ℃ of filtrates were evaporated to and do, the scraping machine scraping blade obtained 552g orange finished product, and molar yield 99.87%, gas phase content 99.52%, fusing point 37.8～38.9, residue on ignition be less than 0.03%, transformation efficiency 100%.
Embodiment 2:
The embodiment of the invention 2 may further comprise the steps:
1) in three mouthfuls of reaction flasks of 2L, adds 500g water and 500g 2.2.6.6-tetramethyl piperidine, 50mg magnesium oxide, stir down at 20 ℃, utilizing dropping funnel to drip off 605g concentration in one hour is 30% hydrogen peroxide, reacted 3 hours, reaction solution content reaction solution transformation efficiency reaches more than 99.8% stopped reaction;
2) suction filtration is isolated magnesium oxide, reclaims directly and utilizes;
3) after about 20 ℃ of filtrates were evaporated to and do, the scraping machine scraping blade obtained 553g orange finished product, and molar yield 99.84%, gas phase content 99.5%, fusing point 37.4～38.8, residue on ignition be less than 0.03%, transformation efficiency 100%.
Embodiment 3:
The embodiment of the invention 3 may further comprise the steps:
1) in three mouthfuls of reaction flasks of 5L, adds 500g water and 500g 2.2.6.6-tetramethyl piperidine, 2.5g sal epsom, stir down at 100 ℃, utilizing dropping funnel to drip off 1610g concentration in one hour is 30% hydrogen peroxide, reacted 15 hours, reaction solution content reaction solution transformation efficiency reaches more than 99.8% stopped reaction;
2) suction filtration is isolated sal epsom, reclaims directly and utilizes;
3) after about 100 ℃ of filtrates were evaporated to and do, the scraping machine scraping blade obtained 554g orange finished product, and molar yield 99.89%, gas phase content 99.57%, fusing point 37.4～38.8, residue on ignition be less than 0.03%, transformation efficiency 100%.
Embodiment 4:
The embodiment of the invention 4 may further comprise the steps:
1) in three mouthfuls of reaction flasks of 5L, adds 500g water and 500g 2.2.6.6-tetramethyl piperidine, 1g magnesiumcarbonate, stir down at 60 ℃, utilizing dropping funnel to drip off 1000g concentration in one hour is 30% hydrogen peroxide, reacted 12 hours, reaction solution content reaction solution transformation efficiency reaches more than 99.8% stopped reaction;
2) suction filtration is isolated magnesiumcarbonate, reclaims directly and utilizes;
3) after about 60 ℃ of filtrates were evaporated to and do, the scraping machine scraping blade obtained 553g orange finished product, and molar yield 99.87%, gas phase content 99.56%, fusing point 37.4～38.8, residue on ignition be less than 0.03%, transformation efficiency 100%.
Embodiment 5:
The embodiment of the invention 5 may further comprise the steps:
1) in three mouthfuls of reaction flasks of 5L, adds 500g water and 500g 2.2.6.6-tetramethyl piperidine, the 1g magnesium hydroxide, stir down at 90 ℃, utilizing dropping funnel to drip off 1200g concentration in one hour is 30% hydrogen peroxide, reacted 11 hours, reaction solution content reaction solution transformation efficiency reaches more than 99.8% stopped reaction.
2) suction filtration is isolated magnesium hydroxide, reclaims directly and utilizes;
3) after about 90 ℃ of filtrates were evaporated to and do, the scraping machine scraping blade obtained 554g orange finished product, and molar yield 99.85%, gas phase content 99.54%, fusing point 37.4～38.8, residue on ignition be less than 0.03%, transformation efficiency 100%.
The preparation method's of the piperidine nitroxyl radical anti-polymerization inhibitor that the embodiment of the invention provides advantage is: 1, reaction times weak point, and the reaction conditions gentleness is operated simpler; 2, the catalyzer price is more cheap, and cost is low, and convenient separation can be used repeatedly; 3, yield is higher; 4, solvent is a water, and directly the method for evaporate to dryness can not produce any waste liquid, waste water, and environmentally safe is realized the zero release of real meaning on the industrial production.Therefore, this method is a kind of production method of being convenient to the piperidine nitroxide free-radical of suitability for industrialized production more.
Claims (4)
1, a kind of preparation method of piperidine nitroxyl radical anti-polymerization inhibitor, its reaction formula is expressed as follows:
Wherein X represents C=O, CH2 or CH2OH, it is characterized in that, further may further comprise the steps: in reactor, add solvent and piperidines, under 20 ℃-100 ℃, add catalyzer and oxygenant, described catalyzer is the magnesium salts precipitation, described oxygenant is a hydrogen peroxide, stirring reaction 3-15 hours, wherein the mol ratio of hydrogen peroxide and piperidines is 1.5～4:1, the quality of catalyzer is 0.01%～0.5% of a piperidines quality.
2, the preparation method of piperidine nitroxyl radical anti-polymerization inhibitor according to claim 1, it is characterized in that, above-mentioned solvent is one or more in water, ethanol, methyl alcohol and the acetonitrile, and above-mentioned magnesium salts is precipitated as magnesium oxide, sal epsom, magnesiumcarbonate or magnesium hydroxide.
3, the preparation method of piperidine nitroxyl radical anti-polymerization inhibitor according to claim 2 is characterized in that, temperature of reaction is 60 ℃-90 ℃, and catalyzer is 0.01%～0.2% of a piperidines quality.
4, the preparation method of piperidine nitroxyl radical anti-polymerization inhibitor according to claim 3, it is characterized in that, also further comprise: reacted filtrate decompression is concentrated into does the back by the scraping machine scraping blade, gets finished product, and the water that condensation obtains in the concentration process can be used as solvent cycle and uses.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030703A (en) * | 2010-11-12 | 2011-04-27 | 常熟市瑞凯添加剂科技有限公司 | Method for preparing piperidine nitroxide radical polymerization inhibitor |
| CN102049248A (en) * | 2010-11-23 | 2011-05-11 | 南京林业大学 | Catalyst for synthesizing piperidine nitroxide radical and preparation method thereof |
| CN102363609A (en) * | 2011-08-09 | 2012-02-29 | 袁佳豪 | Efficient stable polymerization inhibitor and preparation method thereof |
| CN102464609A (en) * | 2010-11-18 | 2012-05-23 | 南通市振兴精细化工有限公司 | Triacetonamine4-carbonyl-2,2,6,6-tetramethylpiperidine oxygen radical and preparation process thereof |
| CN108569996A (en) * | 2017-12-29 | 2018-09-25 | 江苏富比亚化学品有限公司 | A kind of synthetic method of high-efficiency polymerization inhibitor 701 |
| CN112707858A (en) * | 2020-12-28 | 2021-04-27 | 上海博栋化学科技有限公司 | Preparation method for synthesizing polymerization inhibitor 702 by using acetone and ammonia gas as raw materials through one-pot method |
| CN113403352A (en) * | 2021-06-03 | 2021-09-17 | 宿迁市振兴化工有限公司 | Preparation method of 2, 2, 6, 6-tetramethyl piperidine nitroxide free radical compound |
| CN113845470A (en) * | 2021-10-29 | 2021-12-28 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of polymerization inhibitor 701 |
-
2009
- 2009-02-18 CN CNA2009100250947A patent/CN101475525A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030703A (en) * | 2010-11-12 | 2011-04-27 | 常熟市瑞凯添加剂科技有限公司 | Method for preparing piperidine nitroxide radical polymerization inhibitor |
| CN102464609A (en) * | 2010-11-18 | 2012-05-23 | 南通市振兴精细化工有限公司 | Triacetonamine4-carbonyl-2,2,6,6-tetramethylpiperidine oxygen radical and preparation process thereof |
| CN102049248A (en) * | 2010-11-23 | 2011-05-11 | 南京林业大学 | Catalyst for synthesizing piperidine nitroxide radical and preparation method thereof |
| CN102049248B (en) * | 2010-11-23 | 2012-12-19 | 南京林业大学 | Catalyst for synthesizing piperidine nitroxide radical and preparation method thereof |
| CN102363609A (en) * | 2011-08-09 | 2012-02-29 | 袁佳豪 | Efficient stable polymerization inhibitor and preparation method thereof |
| CN108569996A (en) * | 2017-12-29 | 2018-09-25 | 江苏富比亚化学品有限公司 | A kind of synthetic method of high-efficiency polymerization inhibitor 701 |
| CN112707858A (en) * | 2020-12-28 | 2021-04-27 | 上海博栋化学科技有限公司 | Preparation method for synthesizing polymerization inhibitor 702 by using acetone and ammonia gas as raw materials through one-pot method |
| CN113403352A (en) * | 2021-06-03 | 2021-09-17 | 宿迁市振兴化工有限公司 | Preparation method of 2, 2, 6, 6-tetramethyl piperidine nitroxide free radical compound |
| CN113845470A (en) * | 2021-10-29 | 2021-12-28 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of polymerization inhibitor 701 |
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