EP0738289A1 - Process for making highly crosslinked polyvinylpyrrolidone - Google Patents
Process for making highly crosslinked polyvinylpyrrolidoneInfo
- Publication number
- EP0738289A1 EP0738289A1 EP94909726A EP94909726A EP0738289A1 EP 0738289 A1 EP0738289 A1 EP 0738289A1 EP 94909726 A EP94909726 A EP 94909726A EP 94909726 A EP94909726 A EP 94909726A EP 0738289 A1 EP0738289 A1 EP 0738289A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- temperature
- mixture
- monomer
- process according
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F26/10—N-Vinyl-pyrrolidone
Definitions
- an object of this invention is to provide a process for making highly crosslinked polyvinylpyrrolidone by popcorn polymerization of vinylpyrrolidone having a low swell volume, suitably less than 65 ml/10 g, preferably 40-65 ml/10 g, in the absence of added crosslinker.
- Another object herein is to provide popcorn polymerization process for making highly crosslinked PVP in which there is substantially no induction period.
- FIGURE 1 is a graphical representation of temperature vs. time profile for the 3-stage polymerization process according to U.S. Patents 3,277,066 and 3,306,886.
- FIGURE 2 is a similar graphical representation of temperature vs. time for the process steps of the present invention.
- FIGURE 3 is a contour plot of the operation parameters of base content vs. initial gas pressure in the process of the invention showing the effect of added pressure on the induction time of the process, and the swell volume of the crosslinked PVP product.
- FIGURE 1 there is shown a graphical representation of the temperature vs. time profile for the popcorn polymerization of VP of the prior art, e.g. as described in U.S. Patents 3,277,066 and 3,306,886.
- a reaction mixture of VP in an aqueous caustic solution is placed in a autoclave reactor, such as a Buchi reactor, under the following reaction conditions:
- reaction mixture initial pressure of reaction mixture - 0.14 bars
- the reaction mixture is kept under a minimum positive pressure of a nitrogen gas atmosphere in order to provide an inert gas atmosphere over the reactants.
- the mixture then is agitated at 814 rpm and heated to about 140°C. This period is referred to as (A) in Figure
- stage 1 of the process The heated mixture then is held at this temperature for a sufficient period of time to generate an active crosslinker in situ (stage 1 of the process) . This period requires about 4 hours in the process.
- the temperature of the reaction mixture containing the crosslinker then is reduced to about 100°C. (during B) and held at this lower temperature until onset of polymerization occurs (the induction period) . Typically, as shown, the induction period is about 1-1/2 hours (stage 2) .
- stage 3 The polymerization step itself (stage 3) then is spontaneous and follows immediately after the induction period.
- the mixture then is allowed to cool towards room temperature (C) .
- the pressure of the reactants developed in the autoclave rises and falls from an initial value of 0.14 bars to a maximum of about 4 bars at 140°C. to 0 bars after polymerization.
- the total time required for this process is about 7-1/4 hours.
- FIGURE 3 shows a contour plot of several parameters in the process illustrating the experimental conditions necessary to achieve the desired attributes of substantially no induction period during the process, i.e. less than 20 minutes, and a swell volume of crosslinked PVP product of less than 65 ml/10 g, preferably 40-65 ml/10 g.
- results are obtained at an initial external gas pressure of at least 2.0 bars, preferably 2.4-3.0 bars, at a caustic concentration of about 0.4-0.8%, for a VP monomer concentration of about 75-85%.
- the total time for the process shown is about 4-3/4 hours; subsequent examples were carried out with stage 1 (crosslinker generation) times of 2-1/2 hours providing even shorter process times.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US2664793A | 1993-03-05 | 1993-03-05 | |
US26647 | 1993-03-05 | ||
PCT/US1994/001827 WO1994020555A1 (en) | 1993-03-05 | 1994-02-25 | Process for making highly crosslinked polyvinylpyrrolidone |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0738289A4 EP0738289A4 (en) | 1996-07-01 |
EP0738289A1 true EP0738289A1 (en) | 1996-10-23 |
Family
ID=21833034
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94909726A Ceased EP0738289A1 (en) | 1993-03-05 | 1994-02-25 | Process for making highly crosslinked polyvinylpyrrolidone |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0738289A1 (en) |
CA (1) | CA2154767A1 (en) |
WO (1) | WO1994020555A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003529636A (en) * | 2000-03-10 | 2003-10-07 | ビーエーエスエフ アクチェンゲゼルシャフト | Use of crosslinked polyvinylpyrrolidone as a disintegrant in compact granular detergents and detergents |
US6512066B1 (en) * | 2002-02-14 | 2003-01-28 | Arco Chemical Technology, L.P. | Process for making crosslinked polyvinylpyrrolidone with low swell volume |
US6660800B1 (en) | 2002-10-17 | 2003-12-09 | Arco Chemical Technology, L.P. | Process for making crosslinked polyvinylpyrrolidone |
US7214753B2 (en) | 2004-03-24 | 2007-05-08 | Nippon Shokubai Co., Ltd. | N-vinyl amide polymer and production method thereof |
CN101935370A (en) * | 2010-08-06 | 2011-01-05 | 安徽山河药用辅料股份有限公司 | Method for preparing polyvinylpolypyrrolidone |
EP3523252A4 (en) | 2016-10-05 | 2020-07-01 | Boai NKY Medical Holdings Ltd. | Tablet compositions containing crosslinked polyvinylpyrrolidone and their use in beverage applications |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3306886A (en) * | 1963-10-23 | 1967-02-28 | Gen Aniline & Film Corp | Polymerization of n-vinyl lactams using plural stage heating in the presence of catalyst compositions of hydrides or borohydrides of alkali metals and water |
-
1994
- 1994-02-25 CA CA 2154767 patent/CA2154767A1/en not_active Abandoned
- 1994-02-25 WO PCT/US1994/001827 patent/WO1994020555A1/en not_active Application Discontinuation
- 1994-02-25 EP EP94909726A patent/EP0738289A1/en not_active Ceased
Non-Patent Citations (2)
Title |
---|
No further relevant documents disclosed * |
See also references of WO9420555A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2154767A1 (en) | 1994-09-15 |
WO1994020555A1 (en) | 1994-09-15 |
EP0738289A4 (en) | 1996-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8367784B2 (en) | Continuous dosing of extremely fast initiators during polymerization reactions | |
DE2965167D1 (en) | Process for producing an ethylene copolymer | |
EP0343986B1 (en) | Process for the suspension polymerization of 4-acetoxystyrene and hydrolysis to 4-hydroxystyrene polymers | |
US5286826A (en) | Process for making highly crosslinked polyvinylpyrrolidone having a low swell volume | |
US4058655A (en) | Manufacture of low molecular weight poly-N-vinylpyrrolidone-2 | |
EP0738289A1 (en) | Process for making highly crosslinked polyvinylpyrrolidone | |
KR100921640B1 (en) | A process for preparation of expandable styrene polymers, an aqueous suspension suitable therefor, expandable polystyrene produced thereby, and an article produced by shaping the polystyrene | |
US4554311A (en) | Method of preparing an aqueous solution comprising vinylpyrrolidone/vinyl acetate copolymers of various molecular weights using a single initiator system consisting essentially of t-Butylperoxypivalate | |
KR101144881B1 (en) | Increased polymerization reactor output by using a specific initiator system | |
JP2002526574A (en) | Continuous metering of very fast initiator during the polymerization reaction | |
US5338814A (en) | Process for making narrow molecular weight distribution polyvinylpyrrolidone K-90 polymers | |
US3624064A (en) | Polymerization of fluoroethylenes | |
US4962185A (en) | Process of rendering copolymer powders of maleic anhydride and an alkyl vinyl ether prepared in benzene solvent substantially benzene-free | |
KR100333407B1 (en) | Manufacturing method of macromonomer | |
US5342910A (en) | Process for preparing vinylidene chloride or vinyl chloride polymer by suspension polymerization | |
US5362815A (en) | Process for making polyvinylpyrrolidone polymer having predetermined characteristics | |
JPS5928211B2 (en) | Tetrafluoroethylene - Hexafluoropropylene | |
JP4571804B2 (en) | Adding organic initiator during pressure drop in vinyl chloride monomer polymerization reaction | |
US4205149A (en) | Method of removing vinyl chloride monomer from polyvinyl chloride resins | |
US5908905A (en) | Polymerization of vinyl chloride with t-butyl peroxyneoheptanoate and perester peroxide | |
US2377753A (en) | Process for producing ethylene polymers | |
US3740368A (en) | Polymerisation process | |
JPS6047037A (en) | Production of expandable styrene resin particle | |
CN115057955B (en) | Preparation method of polyvinylpyrrolidone homopolymer | |
US2901468A (en) | Process for manufacturing nitrogen-containing polymerizates insoluble in water |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A4 | Supplementary search report drawn up and despatched | ||
AK | Designated contracting states |
Kind code of ref document: A4 Designated state(s): AT BE CH DE DK ES FR GB IE IT LI NL PT SE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19950925 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB IE IT LI NL PT SE |
|
17Q | First examination report despatched |
Effective date: 19961223 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
18R | Application refused |
Effective date: 19980911 |