EP0523131A1 - Polyvinylpyrrolidones a forte masse molaire et procede de preparation - Google Patents

Polyvinylpyrrolidones a forte masse molaire et procede de preparation

Info

Publication number
EP0523131A1
EP0523131A1 EP91907294A EP91907294A EP0523131A1 EP 0523131 A1 EP0523131 A1 EP 0523131A1 EP 91907294 A EP91907294 A EP 91907294A EP 91907294 A EP91907294 A EP 91907294A EP 0523131 A1 EP0523131 A1 EP 0523131A1
Authority
EP
European Patent Office
Prior art keywords
water
reaction
polyvinylpyrrolidone
monomer
less
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.)
Withdrawn
Application number
EP91907294A
Other languages
German (de)
English (en)
Other versions
EP0523131A4 (en
Inventor
Mohammed Tazi
William L. Mandella
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ISP Investments LLC
Original Assignee
ISP Investments LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by ISP Investments LLC filed Critical ISP Investments LLC
Publication of EP0523131A1 publication Critical patent/EP0523131A1/fr
Publication of EP0523131A4 publication Critical patent/EP0523131A4/en
Withdrawn legal-status Critical Current

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

  • the invention relates to a novel high molecular weight water-soluble polyvinylpyrrolidone.
  • the invention relates to a novel method for the production of water-soluble polyvinylpyrrolidones having a K-value of from about 120 to 150.
  • Polyvinylpyrrolidone is a well-known polymer having numerous applications in the pharmaceutical, cosmetic, agricultural, food, and other industries.
  • N-vinyl-pyrrolidone are known. Normally, the polymerization is carried out either in aqueous solution or in suspension in an organic or non-solvent in the present of a free radical initiator.
  • K-value is the so-called Fikentscher K-value which is obtained by capillary vis ⁇ ometry utilizing the relative viscosity of a 0.1% w/v solution in water. (See, U.S. Patent 4,190,718, columns 5 and 6.)
  • This K-value is related to the molecular weight of the polymer in a well-known manner and is conventionally used to characterize the molecular weight of polyvinylpyrrolidone.
  • thickeners For various uses, such as, thickeners, cosmetic formulations, printing inks, and the like, higher viscosities are required.
  • other polymers such as, polyaerylie acids in 1 to 3% solutions, exhibit
  • a starting material of polyvinylpyrrolidone having a K-value of from 30 to 90 is treated by heating an aqueous solution of the polyvinylpyr rolidone in the presence of a water-insoluble organic peroxide and the absence of air.
  • these methods start from an already polymerized polyvinylpyrrolidone.
  • the polymerization consists of a sequence of four steps, namely, (1) initiation; (2) propagation; (3) transfer; and (4) termination. In general terms, these steps may be depicted as follows:
  • the increased viscosity has the effect of hampering the movement of the various moieties at their various states of polymerization in the mixture. This, in turn, decreases the possibility and the probability of the individual entities in the mixture from coming together to form additional polymer whether the entities are in the radical form or the polymer form.
  • the various entities in the reaction mixture increasingly lose their mobility due to the increased viscosity of the mixture.
  • the larger molecular weight moieties will always have less mobility in the mixture than the lower molecular weight moieties.
  • this lack of mobility is adverse to the propagation step but favors termination making it difficult to obtain a product having a molecular weight in excess of that represented by a K-value of about 90.
  • the high molecular weight polyvinylpyrrolidone of the invention may be prepared by subjecting a solution of N-vinylpyrrolidone monomer in water to polymerization conditions utilizing a free radical initiator and adding water and initiator to the reaction mixture incrementally in amounts and in time periods during the polymerization so that the propagation phase of the polymerization is maximized and the termination phase is minimized by the control of the process parameters.
  • a chelating agent added to the reaction mixture, we have found that it is possible to minimize the residual amount of vinylpyrrolidone monomer in the polymeric product.
  • high or excellent solubility means a solubility ratio of 5 as in accordance with the description in Preparative Methods of Polymer Chemistry; Sorenson and Campbell, Interscience, 1961;
  • control of water and initiator addition allow one to control the individual phases of the polymerization so as to allow increased mobility of the reacting moieties and thus allow the reaction to proceed to higher molecular weight final products than has heretofore been possible.
  • By controlling the addition of water and making the addition of initiator incremental and spacing it over the course of the reaction it is now possible to increase the propagation phase so as to reach higher molecular weights.
  • the amount should be accurately measured to be within the ranges specified here- in.
  • the temperature should be controlled within the specified range herein throughout the reaction. While the reaction is exothermic, it proceeds relatively slowly; thus moderate cooling is required during the reaction.
  • Atmospheric environment must be kept inert, i.e., with a nitrogen or inert gas purge.
  • the initial reagents need not be purified, although reactions have been carried out with N-vinylpyr- rolidone which has been treated with activated carbon.
  • reaction rate is somewhat faster than those with non-treated monomer, it is imperative that the monomer be filtered to remove all traces of carbon, which otherwise, can stop the reaction before high conversions are reached.
  • the initial concentration of monomer can have a significant effect on obtaining the inventive product.
  • the initial monomer concentration should be kept in the range from about 25 to 40% by weight based on the total weight of water and monomer. If the initial monomer concentration is below about 25% by weight, the inventive product is not obtained in any useful yield. When the initial monomer concentration is greater than about 40%, increased
  • agitation is required to achieve uniformity of the reaction mixture because of the relatively high viscosity.
  • the greater agitation results in increased shear which produces an undesirable shift in favor of the termination phase and adverse to the propagation phase.
  • a monomer concentration of 27 to 28% by weight is most desirable.
  • the present invention is utilizing an incremental addition of the initiator, i.e., adding the initiator to the reaction mixture more than one time. This has the effect of maintaining the reaction mixture viscosity uniform. It also increases the initiator efficiency resulting in an increase in the molecular weight of the vinyl product and a decrease in the amount of residual monomer. Specifically, we have found that the total amount of initiator added should be in at least two separate additions, the first, initially to begin the reaction, and the second at a later point in the reaction. It is also possible to add the initiator in three or four or more increments. We have found that two or three increments is preferred.
  • the total amount of initiator added generally is in the range from about 0.01 to 2.0% by weight based on the monomer and preferably, from about 0.1 to 0.2.
  • the amount added at each incremental addition would be an appropriate half, third, or the like of the total amount to be added.
  • the timing of the addition of the initiator may be varied over the course of the total time period of the reaction. Thus, if three additions are used (including the initial addition of initiator), the second and third additions could be spaced at one-third intervals over the entire course of the reaction. Similarly, the addition of initiator when only two additions are made could be at the half-time of the reaction. However, we have found in a preferred embodiment that when two additions of initiator are utilized (one in addition to the initial addition of initiator), the second is made at approximately the three- quarter point in the reaction.
  • a buffering and chelating agent is critical in obtaining a product with low residual monomer.
  • This agent performs a dual function in the reaction. Specifically, it complexes with traces of heavy metals introduced by the aqueous medium or by the reactor, which metals normally contaminate the product and poison the catalytic initiator.
  • the buffering agent also controls the pH at a critical level of not less than 5.5, preferably to a level on the basic side between about 6.1 and about 10. Below a pH of 5.5 the vinylpyrrolidone rate of polymerization is too slow to compete with the more active quaternized comonomer. thus, when the level approaches 5.5, additional quantities of buffer are added to increase basicity.
  • the amount of buffer employed represents between about 0.01 to 0.5 weight %, preferably between about 0.04 to 0.3 weight % of the vinylpyrrolidone monomer.
  • Suitable agents which combine buffering and chelating activity are those which have a pH greater than 5 and include ethylene diamine tetraacid disodium salt, tetrasodium pyrophosphate,
  • anhydrous dibasic sodium phosphate + monobasic potassium phosphate, borax, sodium carbonate + sodium bicarbonate, tribasic sodium phosphate and calcium hydroxide are employed as 0.005 molar to saturated aqueous solutions at 25°C. If the amount of buffer is too great, the ash content of the product may increase beyond product specification. For example, for pharmaceutical end uses, the ash should be less than about 0.1% by weight.
  • the viscosity of the reaction system increases.
  • the viscosity can be measured in a variety of manners, e.g., torque mea- surements and the like. Typical of such devices are the
  • reaction time corresponds to a reaction time of from about 210 to 240 minutes after the initiation of the reaction, when the reaction is carried out at approximately 57-58°C.
  • the time of addition of the water and the period of addition over which the water is added can be varied. What is important, however, is the discovery that by the addition of water in this manner as well as the variation of the other significant parameters as discussed hereinabove, the propagation phase of the reaction can be prolonged leading to higher molecular weight products.
  • the polymerization reaction is carried out under an inert atmosphere.
  • a nitrogen purge is most desirable, although other inert gases can be used.
  • the temperature at which the reaction is carried out does have an effect on the ultimate K-value of the polymer. Also, understandably, the temperature has an effect on the total time needed to carry out the reaction. Lower temperatures would require a more prolonged reaction time, whereas higher temperatures would lead to a shorter and perhaps uncontrollable polymerization as well as possible degradation of ingredients and/or product.
  • the preferred temperature range for the reaction is from about 55 to 65°C and most preferably, from about 57 to 60°C.
  • An important aspect of the invention is the conversion of the product into a dry powder.
  • the product must be redissolved in water and generally, dissolution rate decreases with decreasing particle size. Normally, this would be achieved by
  • the most desirable procedure is to utilize a drum dryer to produce the polymer in sheet form.
  • a belt dryer may be used.
  • the sheet is immediately passed through a pin shredder to break it into flakes and flakes are then ground to a desired powder size.
  • Particularly important in this procedure is that the product solution be dried as soon as possible after the reaction is complete to avoid any detrimental change in the product.
  • the drying temperature is generally in the range from about 250 to 260°C for belt drying and about 290 to 330°C for drum drying.
  • the dried product is then ground in a manner to minimize K-value degradation. While a variety of grinding devices may be used, we have found a Fitzmill to be particularly satisfactory. In particular, acceptable powder was produced using a Fitzmill with a 0.094 inch screen and rotor speed of 3600 rpm. the desirable product is in the form of a powder of which 80% is between 16 and 40 mesh and less than 10% passes a 40 mesh screen (U.S. Standard).
  • a 12 liter reactor equipped with a condenser, an anchor agitator with a speed/torque readout, a thermocouple, a nitrogen inlet, and a dropping funnel were utilized. All of the reagents were used without purification. Nitrogen was bubbled through the reaction mixture during the entire course of the reaction.
  • the addition of deionized water was begun at a feed rate of 10.4 grams per minute.
  • the total amount of water added in this manner was 2,187 grams so that the feed was completed after a reaction time of 420 minutes (a total feed time of 210 minutes).
  • the water was added continuously using a dropping funnel.
  • the addition rate of water was monitored by measuring the torque of the polymerization mixture.
  • the agitator was set at 110 rpm and the torque was maintained to at least the value observed at 210 minutes.
  • the reaction mixture had a Brookfield viscosity of 40,000 cps at 57°C, and the K-value of the polymer was 105 ⁇ 2.
  • the torque was 14.5 oz-inch.
  • the reaction was terminated by turning off the nitrogen purge and cooling the reactor.
  • the reactor was discharged at 55-60°C, the residual monomer of the polymer product in aqueous solution was less than 0.2% which is the limit of detection and the K-value of the polymer was 119-125.
  • W 1 sample and crucible before ashing
  • W 2 sample and crucible after ashing
  • a sample was weighed into a 250 ml Erlenmeyer flask, the sample was dissolved in 10 - 20 ml of distilled water or reagent grade alcohol as required. 10 ml of 5% sodium acetate is added. If the solution is cloudy, reagent alcohol is added until the solution clears. The contents are mixed well and then titrated with a 0.1 N iodine solution until a straw color appears. An additional 5 ml of the iodine solution is added. The total amount of iodine added is recorded.
  • the solution should be titrated without the starch because starch gives a poor endpoint. The titration is continued until a sharp colorless endpoint is obtained.

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)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne une polyvinylpyrrolidone non réticulée et soluble dans l'eau ayant une valeur K dépassant 120 et renfermant moins d'environ 0,1 % en poids de monomère résiduel. Un procédé permettant de préparer la polyvinylpyrrolidone à forte masse molaire est également présenté.
EP19910907294 1990-04-06 1991-03-28 High molecular weight polyvinylpyrrolidones and method for their preparation Withdrawn EP0523131A4 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US581382 1984-02-17
US50577390A 1990-04-06 1990-04-06
US58138290A 1990-09-12 1990-09-12
US505773 1995-07-21

Publications (2)

Publication Number Publication Date
EP0523131A1 true EP0523131A1 (fr) 1993-01-20
EP0523131A4 EP0523131A4 (en) 1993-04-21

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910907294 Withdrawn EP0523131A4 (en) 1990-04-06 1991-03-28 High molecular weight polyvinylpyrrolidones and method for their preparation

Country Status (5)

Country Link
EP (1) EP0523131A4 (fr)
JP (1) JPH05507097A (fr)
AU (1) AU649438B2 (fr)
CA (1) CA2079911A1 (fr)
WO (1) WO1991015522A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5928634A (en) * 1995-01-09 1999-07-27 S. C. Johnson & Son, Inc. Liquid insect bait

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004019179A1 (de) * 2004-04-16 2005-11-10 Basf Ag Verfahren zur Herstellung einer Wasser-in-Wasser-Dispersion von Polyvinyllactam mit einem K-Wert von > 120
JP4809194B2 (ja) * 2006-11-15 2011-11-09 株式会社日本触媒 ビニルピロリドン系重合体粉末の製造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB781783A (en) * 1954-12-23 1957-08-28 British Oxygen Co Ltd Improvements in or relating to the polymerisation of vinyl compounds

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2218935C3 (de) * 1972-04-19 1980-01-31 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von wäßrigen Lösungen von N-Vinylpyrrolidonpolymerisaten
DE2456807C3 (de) * 1974-11-30 1981-04-09 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Polymerisaten des Vinylpyrrolidons
DE2514127C3 (de) * 1975-03-29 1981-05-14 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Polymerisaten des N-vinylpyrrolidon-2
US4190718A (en) * 1975-05-27 1980-02-26 Gaf Corporation Process for increasing molecular weight of vinylpyrrolidone polymer
DE2942657A1 (de) * 1979-10-22 1981-04-30 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von polyvinylpyrrolidon, dessen waessrige loesung eine hohe viskositaet aufweist, durch waermebehandlung von waessrigen loesungen von ueblichem polyvinylpyrrolidon
US4554311A (en) * 1982-09-20 1985-11-19 Gaf Corporation 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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB781783A (en) * 1954-12-23 1957-08-28 British Oxygen Co Ltd Improvements in or relating to the polymerisation of vinyl compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9115522A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5928634A (en) * 1995-01-09 1999-07-27 S. C. Johnson & Son, Inc. Liquid insect bait

Also Published As

Publication number Publication date
WO1991015522A1 (fr) 1991-10-17
AU7553091A (en) 1991-10-30
CA2079911A1 (fr) 1991-10-07
EP0523131A4 (en) 1993-04-21
AU649438B2 (en) 1994-05-26
JPH05507097A (ja) 1993-10-14

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