CN1712432A - Method for eliminating residual monomer N-vinyl-pyrrolidone in polymer - Google Patents
Method for eliminating residual monomer N-vinyl-pyrrolidone in polymer Download PDFInfo
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- CN1712432A CN1712432A CN 200510036211 CN200510036211A CN1712432A CN 1712432 A CN1712432 A CN 1712432A CN 200510036211 CN200510036211 CN 200510036211 CN 200510036211 A CN200510036211 A CN 200510036211A CN 1712432 A CN1712432 A CN 1712432A
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- polymkeric substance
- residual monomer
- pvp
- vinyl pyrrolidone
- vinyl
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Abstract
Elimination of residual monomer N-vinyl ketopyrrolidine in polymer is carried out by synthesizing polymer product, preparing 1-80wt% solution or suspensoid from solution, extracting residual monomer N-vinyl ketopyrrolidine at 0-200 DEG C, radiating from supersonic wave, drying, and obtaining low-residual weight N-vinyl ketopyrrolidine polymer product. It achieves low cost, simple process and good effect.
Description
Technical field
The invention belongs to the polymer science field, relate to a kind of method of eliminating residual monomer N-vinyl pyrrolidone in the polymkeric substance specifically.
Background technology
The multipolymer of polyvidone (comprising PVP-K15, PVP-K30, PVP-K60 and PVP-K90) and N-vinyl pyrrolidone and vinyl acetate is to use medical auxiliary materials widely, polyvinylpolypyrrolidone or claim that crosslinked polyvinylpyrrolidone (PVPP) is respond well beer and beverage finings, tablet disintegrant.But, need reduce the content of residual monomer N-vinyl pyrrolidone (NVP) in the above-mentioned polymeric articles as much as possible because manufacturing raw material N-vinyl pyrrolidone (NVP) monomer of above-mentioned polymeric articles has toxicity.European patent EP 258854 adopts sorbent materials to eliminate N-vinyl pyrrolidone (NVP) in the polymkeric substance, but effect is difficult to reach the requirement of European Pharmacopoeia 2004 version (EP2004) to this series products of pharmaceutical grade.Chinese patent CN 1038036 adopts ultra-filtration techniques, but the highlyest NVP can only be reduced by 97%.Chinese patent CN 1147511 adopts the N-vinyl pyrrolidone (NVP) in the ion exchange method elimination polymkeric substance, the equipment more complicated, and throughput is lower.
Summary of the invention
The objective of the invention is to overcome prior art and eliminate the problem that the method for residual monomer N-vinyl pyrrolidone in the polymkeric substance exists, the method for residual monomer N-vinyl pyrrolidone in the elimination polymkeric substance a kind of simple to operate, respond well is provided.
To achieve these goals, the present invention adopts following technical scheme to be achieved:
Do not need extensive investment in order in industrial production, to make full use of existing installation, so in method of the present invention, at first utilize prior art to synthesize solid state of the present invention, the polymeric articles of solution state or gel state (comprises medical auxiliary materials polyvidone PVP-K15, PVP-K30, PVP-K60 and PVP-K90, polyvinylpolypyrrolidone or claim crosslinked polyvinylpyrrolidone PVPP, and the multipolymer of N-vinyl pyrrolidone and vinyl acetate), then with above-mentioned polymeric articles amine, monochloro methane, methylene dichloride, DMF, ethylene dichloride, trolamine, thanomin, diethanolamine, Virahol, propyl alcohol, isopropylcarbinol, chloroform, butanols, hexalin, tetracol phenixin, acetate, glycerine, ether, water, vinylformic acid, propylene glycol, methyl alcohol, ethanol, formic acid, ethylene glycol, propionic acid, methacrylic acid, polyoxyethylene glycol, the mixture of one or several in the acetone is formulated as solution or the suspension of 1～80 weight %, keeping temperature is extraction residual monomer N-vinyl pyrrolidone (NVP) wherein under 0～200 ℃ the situation, and uses the ultrasonic wave radiation simultaneously.In order to improve effect, can re-extract repeatedly.After the aforesaid operations step is finished, dry, low N-vinyl pyrrolidone (NVP) the based polyalcohol product of level of residual monomers be can obtain and (medical auxiliary materials polyvidone PVP-K15, PVP-K30, PVP-K60 and PVP-K90 comprised, polyvinylpolypyrrolidone or claim crosslinked polyvinylpyrrolidone PVPP, and the multipolymer of N-vinyl pyrrolidone and vinyl acetate).
Compared with prior art, the present invention has following beneficial effect: (1) equipment is simple, and throughput is big; (2) simple to operate, be convenient to reduce cost; (3) respond well, the content of residual monomer N-vinyl pyrrolidone (NVP) can be reduced to below the 1ppm.
Embodiment
Embodiment 1
With adopting prior art synthetic weight concentration is that the aqueous solution of 43% medical auxiliary materials polyvidone (PVP-K30) is poured in the reactor, keeping temperature is 100 ℃, with wavelength 60KHz, power is that the ultrasonic wave radiation of 100W is after 30 minutes, with this solution spray drying, obtain Powdered PVP-K30 product, the content of residual monomer N-vinyl pyrrolidone (NVP) is lower than 1ppm.
Embodiment 2
To adopt the Powdered PVP-K90 product of prior art synthetic to pour in the reactor, and add 32% ethanolic soln, and obtain mass concentration and be 5% solution, after stirring, keeping temperature is 42 ℃, is the ultrasonic wave radiation of 80W with wavelength 20KHz, power.After 130 minutes, with this solution spray drying, obtain Powdered PVP-K90 product, the content of residual monomer N-vinyl pyrrolidone (NVP) is lower than 1ppm.
Embodiment 3
Adopt prior art synthetic clarify beer agent polyvinylpolypyrrolidone (PVPP) to pour reactor into, add 1 part of vinylformic acid and 3 parts of mixtures that methacrylic acid is formed according to 1: 3 part by weight, after stirring, keeping temperature is 20 ℃, is the ultrasonic wave radiation of 100W with wavelength 60KHz, power.After 45 minutes, vacuum-drying is also pulverized, and obtains Powdered PVPP product, and the content of residual monomer N-vinyl pyrrolidone (NVP) is lower than 1ppm.
Embodiment 4
With the synthon molar ratio is that 1: 3 N-vinyl pyrrolidone and vinyl acetate copolymer poured in the reactor, add 2 part of 95% ethanol and 5 parts of mixtures that glycerine is formed by 3: 2 part by weight, after stirring, keeping temperature is 160 ℃, with wavelength 40KHz, power is the ultrasonic wave radiation 82 minutes of 100W, vacuum-drying is also pulverized, obtain pulverous N-vinyl pyrrolidone and vinyl acetate copolymer product, the content of residual monomer N-vinyl pyrrolidone (NVP) is lower than 1ppm.
Claims (4)
1. a method of eliminating residual monomer N-vinyl pyrrolidone in the polymkeric substance is characterized in that: after polymkeric substance is mixed with solution or suspension with solvent, 0～200 ℃ of extraction down, and use the ultrasonic wave radiation.
2. the method for claim 1 is characterized in that described polymkeric substance is the crosslinked polyvinylpyrrolidone PVPP of polyvidone PVP-K15, polyvidone PVP-K30, polyvidone PVP-K60, polyvidone PVP-K90, polyvinylpolypyrrolidone, title or the multipolymer of N-vinyl pyrrolidone and vinyl acetate.
3. method as claimed in claim 1 or 2 is characterized in that described solvent is one or several the mixture in amine, monochloro methane, methylene dichloride, DMF, ethylene dichloride, trolamine, thanomin, diethanolamine, Virahol, propyl alcohol, isopropylcarbinol, chloroform, butanols, hexalin, tetracol phenixin, acetate, glycerine, ether, water, vinylformic acid, propylene glycol, methyl alcohol, ethanol, formic acid, ethylene glycol, propionic acid, methacrylic acid, polyoxyethylene glycol, the acetone.
4. method as claimed in claim 3 is characterized in that described is 1～80 weight % with polymkeric substance with the concentration that solvent is mixed with solution or suspension.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100362111A CN100390224C (en) | 2005-08-02 | 2005-08-02 | Method for eliminating residual monomer N-vinyl-pyrrolidone in polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100362111A CN100390224C (en) | 2005-08-02 | 2005-08-02 | Method for eliminating residual monomer N-vinyl-pyrrolidone in polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1712432A true CN1712432A (en) | 2005-12-28 |
| CN100390224C CN100390224C (en) | 2008-05-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100362111A Expired - Fee Related CN100390224C (en) | 2005-08-02 | 2005-08-02 | Method for eliminating residual monomer N-vinyl-pyrrolidone in polymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898563A (en) * | 2012-10-24 | 2013-01-30 | 四川化工控股（集团）有限责任公司 | Catalyst for lowering N-vinyl-2-pyrrolidone in polyvinylpyrrolidone (PVP), and preparation method and application thereof |
| CN105294886A (en) * | 2015-11-29 | 2016-02-03 | 贵州省欣紫鸿药用辅料有限公司 | Removing method of N-vinyl pyrrolidone in povidone k30 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02298303A (en) * | 1989-05-11 | 1990-12-10 | Power Reactor & Nuclear Fuel Dev Corp | Process for extracting water-soluble substances in powder |
| DE4140086C2 (en) * | 1991-12-05 | 1994-08-25 | Basf Ag | Process for the preparation of highly pure N-vinylpyrrolidone polymers |
| JP2001354723A (en) * | 2000-06-15 | 2001-12-25 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for producing highly pure vinyl pyrrolidone polymer |
-
2005
- 2005-08-02 CN CNB2005100362111A patent/CN100390224C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898563A (en) * | 2012-10-24 | 2013-01-30 | 四川化工控股（集团）有限责任公司 | Catalyst for lowering N-vinyl-2-pyrrolidone in polyvinylpyrrolidone (PVP), and preparation method and application thereof |
| CN102898563B (en) * | 2012-10-24 | 2014-06-18 | 四川化工控股（集团）有限责任公司 | Catalyst for lowering N-vinyl-2-pyrrolidone in polyvinylpyrrolidone (PVP), and preparation method and application thereof |
| CN105294886A (en) * | 2015-11-29 | 2016-02-03 | 贵州省欣紫鸿药用辅料有限公司 | Removing method of N-vinyl pyrrolidone in povidone k30 |
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| Publication number | Publication date |
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| CN100390224C (en) | 2008-05-28 |
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Granted publication date: 20080528 Termination date: 20090802 |