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Patent US5779396 - Dispersing the polymer in a solution of cationic organic salts and ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsCompositions of precipitated anionic polymers containing mixtures of cationic organic salts and kosmotropic salts as well as processes for making and using the same to condition soil are disclosed....http://www.google.com/patents/US5779396?utm_source=gb-gplus-sharePatent US5779396 - Dispersing the polymer in a solution of cationic organic salts and kosmotropic saltAdvanced Patent SearchPublication numberUS5779396 APublication typeGrantApplication numberUS 08/726,158Publication dateJul 14, 1998Filing dateOct 3, 1996Priority dateOct 3, 1996Fee statusLapsedPublication number08726158, 726158, US 5779396 A, US 5779396A, US-A-5779396, US5779396 A, US5779396AInventorsJoseph J. Mallon, Raymond S. Farinato, Louis Rosati, John J. Freeman, Jr.Original AssigneeCytec Technology Corp.Export CitationBiBTeX, EndNote, RefManPatent Citations (46), Non-Patent Citations (6), Referenced by (8), Classifications (16), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetDispersing the polymer in a solution of cationic organic salts and kosmotropic saltUS 5779396 AAbstract Compositions of precipitated anionic polymers containing mixtures of cationic organic salts and kosmotropic salts as well as processes for making and using the same to condition soil are disclosed.
We claim: 1. A process of conditioning soil which comprises adding to the soil a soil-conditioning amount of an aqueous composition comprised of an effective amount of at least one cationic organic salt, an effective amount of at least one kosmotropic salt, and at least one precipitated anionic water-soluble polymer.
4. A process as claimed in claim 3, wherein said precipitated anionic water-soluble polymer further contains recurring (meth)acrylamide units.
6. A process as claimed in claim 1 wherein said aqueous composition is further comprised of a water-soluble polymer different from said precipitated anionic water-soluble polymer.
8. A process of conditioning soil which comprises adding to the soil an effective amount of a soil-conditioning solution made by diluting an aqueous composition comprised of precipitated anionic water-soluble polymer, from 0.02 to 12%, by weight based on total weight, of a tetraalkylammonium salt and from 0.1% to 30%, by weight based on total weight, of a sulfate salt, wherein said precipitated anionic water-soluble polymer is comprised of recurring units that contain carboxylic acid, carboxylic acid salt, sulfonic acid, or sulfonic acid salt groups.
FIELD OF THE INVENTION This invention relates generally to aqueous compositions of certain salts which contain precipitated anionic water-soluble polymers, methods for precipitating anionic water-soluble polymers in aqueous solutions containing certain salts, methods for polymerizing monomers in aqueous solutions containing certain salts to form precipitated anionic water-soluble polymers, optionally precipitated as polymer dispersions, and methods for using compositions of precipitated anionic water-soluble polymers in aqueous solutions of certain salts for various applications e.g. papermaking, mining, wastewater treatment, and soil conditioning.
BACKGROUND OF THE INVENTION High molecular weight water-soluble anionic polymers are useful in a number of applications e.g. the flocculation of suspended solids, recovery of minerals from mining operations, coal refuse dewatering, papermaking, paper sludge deinking, enhanced oil recovery, wastewater treatment, soil conditioning, etc. In many cases, the anionic polyelectrolytes are supplied to the user in the form of substantially dry polymer granules. The granules may be manufactured by the polymerization of water-soluble monomers in water to form a water-soluble polymer solution, followed by dehydration and grinding to form water-soluble polymer granules.
The effect of salts on the solubility of various substances in aqueous solution is well discussed in the scientific literature e.g., Kim D. Collins and Michael W. Washabaugh, Q. Rev. Biophys., Vol. 18(4) pp. 323-422 , 1985. "Kosmotropic" salts tend to reduce the solubility of substances in aqueous solution. There are numerous means known to those skilled in the art for determining whether a particular salt is kosmotropic. Representative salts which contain anions such as sulfate, fluoride, phosphate, acetate, citrate, tartrate and hydrogenphosphate are kosmotropic. Some salts are more kosmotropic than others, based on the well known "Hofmeister series" principles.
For instance, the effect of added sodium chloride is discussed on p. 313 of the review by E. D. Goddard, cited above, wherein the author states that "adding salt . . . substantially reduces the affinity of binding as seen by a steady increase in the concentration of surfactant! at which binding commences. . ." A similar view was advanced by Y. Li and P. Dubin, in "Structure and Flow in Surfactant Solutions, ACS Symposium Series 578, American Chemical Society, 1994, at p. 328 where the authors state: "In order to avoid precipitation in mixtures of strong polyelectrolytes with oppositely charged surfactant! micelles, the binding strength . . . must be reduced. Practically, several ways could be used to attenuate the strong electrostatic interaction between the polyelectrolyte and oppositely charged surfactant, such as . . . addition of salt."
SUMMARY OF THE INVENTION The present invention is directed to compositions of precipitated anionic polymers in solutions of cationic organic salts and kosmotropic salts, as well as processes for making and using the same. Compositions in which the polymer is dispersed in the form of small droplets are preferred, and methods of making these polymer dispersions which may include dispersants, are taught herein. A particularly preferred method is to form the dispersed polymer by polymerization of the monomers in solutions of the salts, optionally in the presence of one or more other water-soluble polymers which may act as dispersants. Since the polymer remains insoluble even at pH greater than 4, flowable polymer dispersions are obtained which may be readily used without pH adjustment. Methods of using the compositions of the instant invention for applications such as flocculation of suspended solids, solid-liquid separations, mining, papermaking, soil stabilization, etc. are also embodied herein.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS It has now been discovered, surprisingly, that the precipitation of anionic polymers by cationic organic salts is greatly enhanced by the addition of kosmotropic salts. For the purposes of this invention, a polymer is precipitated in a particular salt solution if the particular polymer does not dissolve to form a clear, homogeneous, solution when the particular polymer is stirred or agitated, for periods of up to about a week, in the salt solution at a particular temperature. A polymer is also considered to be precipitated when a solution of a polymer or polymers in the salt solution develops cloudiness or turbidity, when the temperature of the solution is changed. It is obvious from the foregoing that solubility of a polymer or polymers in a particular salt solution may be temperature dependent, so that a polymer may be precipitated in a particular salt solution at low temperatures, but dissolved at higher temperatures, or vice-versa. The polymer or polymers, salt or salts, and water may be mixed in any order, or the polymerization may be conducted in the presence of the salt or salts, or part of the salt or salts, in order to determine the solubility of the polymer in the salt solution. The polymer may be considered to be precipitated if all or only part, e.g. 10% or more, of the polymer is precipitated.
Cationic organic salts with the general structure Rn -M+ A31, where R comprises ester, alkyleneoxy, alkyl, or substituted alkyl with from about 1 to about 22 carbons, or aryl or substituted aryl with from about 6 to about 22 carbons, M is an cationic group such as ammonium, including monoalkyl, dialkyl, trialkyl and tetraalkyl ammonium, and A is an anion e.g chloride, bromide, iodide, methylsplfate, etc, are useful for the precipitation of anionic polymers, particularly in the presence of kosmotropic salts. The R group may be linear or branched, and may be substituted with more than one cationic M group. The cationic M group may be substituted with more than one R group; e.g. n may range from 1 to 4. Mixtures of cationic organic salts with each other are also useful, in admixture with kosmotropic salts. Tetraalkylammonium halides having from 4 to 22 carbon atoms, substituted tetraalkylammonium halides having from 4 to 22 carbon atoms, aryl trialkylammonium halides having from 9 to 22 carbon atoms, and substituted aryl trialkylammonium halides having from 9 to 22 carbon atoms are preferred. Cetylpyridinium chloride (CPC), cetylmethylammonium chloride (CMAC), and benzyltriethylammonium chloride (BTEAC) are most preferred.
Anionic copolymers may also be prepared by copolymerizing anionic monomers with other anionic comonomers, nonionic comonomers, and/or cationic comonomers. Anionic monomers may include acrylic acid, methacrylic acid, vinyl sulfate, 2-acrylamido-2methylpropane sulfonic acid, styrene sulfonic acid, their salts and the like. Polymers which become anionically charged after polymerization include polymers made by hydrolyzing cellulose, polymers made by hydrolyzing and/or hydroxamating polyacrylamide, and polymers made from maleic anhydride.
Polymerization of the monomers may be carried out in any manner known to those skilled in the art, including solution, bulk, precipitation, dispersion, suspension, emulsion, microemulsion, etc. Polymerization of the monomers may be carried out in the presence of part or all of the salt solution. Initiation may be effected with a variety of thermal and redox free radical initiators, including peroxides, e.g. t-butyl peroxide; azo compounds, e.g. azoisobisbutyronitrile; inorganic compounds, such as potassium persulfate and redox couples, such as ferrous ammonium sulfate/ammonium persulfate and sodium bromate/sulfur dioxide. Initiator addition may be effected any time prior to the actual initiation per se. Polymerization may also be effected by photochemical irradiation processes, such as by ultraviolet irradiation or by ionizing irradiation from a cobalt 60 source. The monomers may all be present when polymerization is initiated, or part of the monomers may be added at a later stage of the polymerization. Polymerization may be conducted in multiple stages. Additional materials such as pH adjusting agents, stabilizers chelating agents, sequestrants, etc. may also be added before, during or after polymerization.
Polymers useful as dispersants may include polyacrylamide and other nonionic polymers, e.g. poly(methacrylamide), poly(vinyl alcohol), poly(ethylene oxide), etc. and the like. Preferred dispersants are anionic polymers such as poly(acrylic acid), poly(AMMPS), copolymers of acrylic acid with acrylamide,. and copolymers of AMMPS with acrylamide. Preferably, dispersants are soluble or mostly soluble in the particular salt solution. It is generally preferable for the dispersant to have greater solubility in the particular salt solution than the precipitated polymer droplets which are being dispersed. Copolymers useful a dispersants may include copolymers of nonionic monomers e.g. acrylamide with up to about 20 mole %, preferably from about 5 to about 15 mole % of a cationic comonomer, e.g. quaternary salts of dialkylaminoalkyl(alk)acrylate, diallyidialkylammonium halide, etc., based on the total moles of recurring units in the polymer. Other copolymers useful as dispersants include copolymers of acrylamide with up to about 99 mole % of an anionic comonomer such as sodium 2-acrylamido-2-methylpropane sulfonic acid, preferably from about 5 to about 95 mole % comonomer, most preferably from about 25 to about 75 mole % comonomer, based on the total moles of recurring units in the polymer. Anionic monomers may include acrylic acid, styrene sulfonic acid, their salts and the like. Nonionic comonomers may include substantially water-soluble monomers such as methacrylamide, or monomers which are sparingly soluble in water such as t-butylacrylamide, diacetone acrylamide, ethyl acrylate, methyl methacrylate, methyl acrylate, styrene, butadiene, ethyl methacrylate, acrylonitrile, etc. and the like. Preferred nonionic monomers are acrylamide, t-butyl acrylamide, methacrylamide, methyl methacrylate, ethyl acrylate and styrene.
VISCOSITY MEASUREMENTS Standard viscosity (SV) is the viscosity of a 0.096% solution of water-soluble polymer in 1N sodium chloride at 25� C. The viscosity is measured by a Brookfield LVT viscometer with a UL adapter at 60 rpm. The polymer solution being measured is made by diluting a polymer dispersion or solution to a concentration of 0.2% by stirring with the appropriate amount of deionized water during about twelve hours, and then diluting with the appropriate amounts of deionized water and sodium chloride. The bulk viscosity (BV) of a polymer dispersion is the viscosity of the polymer dispersion as measured by a Brookfield LVT viscometer with spindle #4 at 30 rpm and 25� C.
pH Measurements The pH measurements were made with a conventional electronic pH meter, Jenco Electronics Microcomputer pH-Vision 6071 R equipped with a 3-in-1 electrode, Model 6000E. The pH meter was calibrated with commercial buffer solutions at pH 4.00 and pH 7.01.
EXAMPLE A A 50/50 mole percent poly(acrylamide/AMMPS) copolymer was prepared by adding 49.77 parts of 53.88% acrylamide solution, 78.97 parts of 99% 2-acrylamido-2-methyl-propanesulfonic acid, 3.02 parts 5% sodium ethylenediaminetetraacetate (EDTA) (chelating agent), 30.3 parts of 50% NaOH solution, and 563.79 parts deionized water to a suitable vessel equipped with mechanical stirring. The solution was stirred at 30� C., and 1.05 parts ammonium persulfate and 3.5 parts of 30% sodium meta-bisulfite solution were added. The solution was deoxygenated by sparging with nitrogen while raising the temperature to about 50� C. After 10 hours of stirring at 50� C., the viscous polymer solution was allowed to cool to give a 50/50 mole percent poly(acrylamide/AMMPS) solution with a polymer content of about 15% by weight. Part of the polymer solution was diluted in deionized water to give a 2% polymer solution for solubility determination.
Example B About 12 parts of deionized water was added to a suitable vessel, followed by about 1.5 parts of a 2% solution of BTEAC. About 1.5 parts of a 2% solution of a 50/50 mole percent poly(acrylamide/AMMPS) prepared as in Example A was added with stirring to give a clear solution. The pH was adjusted to about 4.6 by adding dilute hydrochloric acid. The solution remained clear, demonstrating that 0.2% 50/50 poly(acrylamide/AMMPS) was not precipitated in a 0.2% solution of BTEAC.
Example C About 9.26 parts of deionized water was added to a suitable vessel, followed by about 4.24 parts of 99.1% ammonium sulfate and about 1.5 parts of 2% BTEAC; the mixture was stirred to dissolve the salt. A clear solution with a pH of about 4.6 resulted, demonstrating that 0.2% BTEAC was not precipitated in a 28% ammonium sulfate solution.
Example D About 9.26 parts of deionized water was added to a suitable vessel, followed by about 4.24 parts of 99.1 % ammonium sulfate; the mixture was stirred to dissolve the salt. About 1.5 parts of a 2% solution of a 50/50 mole percent poly(acrylamide/AMMPS) prepared as in Example A was added with stirring to give a cloudy mixture with a pH of about 4.6. The mixture was heated with stirring until it became clear, then allowed to cool slowly. The solution became cloudy at 42� C., demonstrating that 0.2% 50/50 poly(acrylamide/AMMPS) had a cloud point of 42� C. in 28% ammonium sulfate solution.
Example 1 About 7.76 parts of deionized water was added to a suitable vessel, followed by about 4.24 parts of 99.1 % ammonium sulfate; the mixture was stirred to dissolve the salt. About 1.5 parts 2% BTEAC was added with stirring to give a clear solution. About 1.5 parts of a 2% solution of a 50/50 mole percent poly(acrylamide/AMMPS) prepared as in Example A was added with stirring to give a cloudy mixture with a pH of about 4.6. The mixture was heated with stirring up to a temperature of about 105� C. without dissolving the precipitated polymer. This result demonstrates that 0.2% 50/50 poly(acrylamide/AMMPS) had a cloud point greater than 105� C. in a solution of 28% ammonium sulfate and 0.2% BTEAC. The cloud point of the polymer was higher in a mixture of 28% ammonium sulfate and 0.2% BTEAC than in 28% ammonium sulfate alone (Example D) or 0.2% BTEAC alone (Example B).
Example E About 12 parts of deionized water was added to a suitable vessel, followed by about 1.5 parts of a 2% solution of BTEAC. About 1.5 parts of a 2% solution of a 50/50 mole percent poly(acrylamide/AMMPS) prepared as in Example A was added with stirring to give a clear solution. The pH was adjusted to about 8.5 by adding NaOH solution. The solution remained clear, demonstrating that 0.2% 50/50 poly(acrylamide/AMMPS) was not precipitated in a 0.2% solution of BTEAC at pH 8.5.
Example F About 9.26 parts of deionized water was added to a suitable vessel, followed by about 4.24 parts of 99.1% ammonium sulfate and about 1.5 parts of 2% BTEAC; the mixture was stirred to dissolve the salt. The resulting clear solution remained clear after adjusting the pH to about 8.5 by adding NaOH solution, demonstrating that 0.2% BTEAC was not precipitated in a 28% ammonium sulfate solution at pH 8.5.
Example G About 9.26 parts of deionized water was added to a suitable vessel, followed by about 4.24 parts of 99.1% ammonium sulfate; the mixture was stirred to dissolve the salt. About 1.5 parts of a 2% solution of a 50/50 mole percent poly(acrylamide/AMMPS) prepared as in Example A was added with stirring to give a cloudy mixture with a pH of about 4.6. The pH was adjusted to 8.5 by adding NaOH solution. The mixture was heated with stirring until it became clear, then allowed to cool slowly. The solution became cloudy at 33� C., demonstrating that 0.2% 50/50 poly(acrylamide/AMMPS) had a cloud point of 33 � C. in 28% ammonium sulfate solution at pH 8.5, versus 42� C. at pH 4.5 (Example D)
Example 2 About 7.76 parts of deionized water was added to a suitable vessel, followed by about 4.24 parts of 99.1% ammonium sulfate; the mixture was stirred to dissolve the salt. About 1.5 parts 2% BTEAC was added with stirring to give a clear solution. About 1.5 parts of a 2% solution of a 50/50 mole percent poly(acrylamide/AMMPS) prepared as in Example A was added with stirring to give a cloudy mixture with a pH of about 4.6. The pH was adjusted to 8.5 by adding NaOH solution. The mixture was heated with stirring up to a temperature of about 105� C. without dissolving the precipitated polymer. This result demonstrates that 0.2% 50/50 poly(acrylamide/AMMPS) had a cloud point greater than 105� C. in a solution of 28% ammonium sulfate and 0.2% BTEAC, even at a pH of about 8.5. The cloud point of the polymer was higher in a mixture of 28% ammonium sulfate and 0.2% BTEAC than in 28% ammonium sulfate alone (Example G) or 0.2% BTEAC alone (Example E).
Example H About 12 parts of deionized water was added to a suitable vessel, followed by about 1.5 parts of a 2% solution of BTEAC. About 1.5 parts of a 2% solution of a 50/50 mole percent poly(acrylamide/AMMPS) prepared as in Example A was added with stirring to give a clear solution. The pH was adjusted to about 6.4 by adding NaOH solution. The solution remained clear, demonstrating that 0.2% 50/50 poly(acrylamide/AMMPS) was not precipitated in a 0.2% solution of BTEAC at pH 6.4.
Example I About 9.26 parts of deionized water was added to a suitable vessel, followed by about 4.24 parts of 99.1% ammonium sulfate and about 1.5 parts of 2% BTEAC; the mixture was stirred to dissolve the salt. The resulting clear solution remained clear after adjusting the pH to about 6.4 by adding NaOH solution, demonstrating that 0.2% BTEAC was not precipitated in a 28% ammonium sulfate solution at pH 6.4.
Example J About 9.26 parts of deionized water was added to a suitable vessel, followed by about 4.24 parts of 99.1% ammonium sulfate; the mixture was stirred to dissolve the salt. About 1.5 parts of a 2% solution of a 50/50 mole percent poly(acrylamide/AMMPS) prepared as in Example A was added with stirring to give a cloudy mixture with a pH of about 4.6. The pH was adjusted to 6.4 by adding NaOH solution. The mixture was heated with stirring until it became clear, then allowed to cool slowly. The solution became cloudy at 39� C., demonstrating that 0.2% 50/50 poly(acrylamide/AMMPS) had a cloud point of 39� C. in 28% ammonium sulfate solution at pH 6.4, versus 42� C. at pH 4.5 (Example D) and 33� C. at pH 8.5 (Example G).
Example 3 About 7.76 parts of deionized water was added to a suitable vessel, followed by about 4.24 parts of 99.1% ammonium sulfate; the mixture was stirred to dissolve the salt. About 1.5 parts 2% BTEAC was added with stirring to give a clear solution. About 1.5 parts of a 2% solution of a 50/50 mole percent poly(acrylamide/AMMPS) prepared as in Example A was added with stirring to give a cloudy mixture with a pH of about 4.6. The pH was adjusted to 6.4 by adding NaOH solution. The mixture was heated with stirring up to a temperature of about 105� C. without dissolving the precipitated polymer. This result demonstrates that 0.2% 50/50 poly(acrylamide/AMMPS) had a cloud point greater than 105� C. in a solution of 28% ammonium sulfate and 0.2% BTEAC, even at a pH of about 6.4. The cloud point of the polymer was higher in a mixture of 28% ammonium sulfate and 0.2% BTEAC than in 28% ammonium sulfate alone (Example J) or 0.2% BTEAC alone (Example H).
Example 4 A copolymer of 22.5 mole% acrylic acid and 77.5% acrylamide was prepared in the form of a polymer dispersion at a pH of 4.3 as follows: About 1.97 parts of 98% CPC, 48.41 parts 53.88% acrylamide, 7.75 parts 99% acrylic acid, 60.38 parts 99% ammonium sulfate, 2.98 parts 5% sodium ethylenediaminetetraacetate (EDTA) (chelating agent), 4.01 parts of 28% NH4 OH solution, and 60.38 parts deionized water were added to a suitable vessel equipped with mechanical stirring. The mixture was stirred to form a clear solution. About 0.51 parts ammonium persulfate was added, followed by 73.6 parts of 15% poly(2-acrylamido-2-methyl-propanesulfonic acid) (a dispersant purchased commercially) to give a milky white mixture with a pH of 3.2. About 3.04 parts of 28% NH4 OH solution was added to raise the pH to 4.3. The mixture was deoxygenated by sparging with nitrogen for thirty minutes, while the temperature was raised to about 50�C. About 5 parts of 20% sodium metabisulfite solution was added over the course of 20 minutes. The reaction was stirred at 50� C. for about 5 hours, then allowed to cool. The resulting polymer dispersion had a bulk viscosity of about 5100 centipoise and a pH of about 4.2. The standard viscosity of the polymer was about 4.2 centipoise, indicating high molecular weight.
Example K A copolymer of 22.5 mole% acrylic acid and 77.5% acrylamide was prepared at a pH of 4.3 as in Example 4, except that 73.6 parts of deionized water were added to the mixture in place of the dispersant, 73.6 parts of 15% poly(2-acrylamido-2-methyl-propanesulfonic acid). Instead of forming a low viscosity dispersion, the polymer precipitated in the form of a gelatinous white mass that could not be stirred.
Example 5 A conditioning solution was prepared by diluting a dispersion prepared as in Example 4 with deionized water so that the concentration of the dissolved polymer in the resulting conditioning solution was 0.1%. About 3 parts of soil were added to a separate vessel containing 100 parts of deionized water, the mixture was stirred vigorously, and 1.0 parts of the conditioning solution were added. The resulting mixture was agitated for 15 minutes, then allowed to settle for 15 minutes. The turbidity of the supernatant was about 11 �5 ntu, as measured with a hand-held turbidity meter, indicating that this composition is likely to be useful for conditioning soil.
Example L Example 5 was repeated, except that deionized water was used in place of the conditioning solution. The turbidity of the supernatant was greater than 1000 ntu.
Example M Example 5 was repeated, except that the conditioning solution contained a commercially available copolymer of acrylamide and acrylic acid, known to be useful for conditioning soil, instead of a polymer prepared as in Example 4. The turbidity of the supernatant was 8.1�5 ntu.
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Washabaugh, The Hofmeister effect and the behaviour of water at interfaces, pp. 323-422.* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS5885032 *Dec 11, 1997Mar 23, 1999Cytec Technology Corp.Cationic water-soluble polymer precipitation in salt solutionsUS6040376 *Nov 5, 1998Mar 21, 2000Cytec Technology Corp.Kosmotropic salt and a cationic organic salt, wherein said salts are used in amounts effective to precipitate said at least one anionic water-soluble polymer.US6076997 *Oct 30, 1998Jun 20, 2000Mbt Holding AgDeep mix soil stabilization methodUS6488808 *Jan 19, 2001Dec 3, 2002Huntsman Petrochemical CorporationStyrene copolymers in de-inkingUS7708133 *Nov 7, 2003May 4, 2010Hewlett-Packard Development Company, L.P.Flexible member tensioningUS7922785 *Jun 22, 2005Apr 12, 2011Biocentral Laboratories LimitedBiodegradable polymeric concentrateUS8241388 *Oct 28, 2009Aug 14, 2012Ecoplus, Inc.Soil additiveUS20100043510 *Oct 28, 2009Feb 25, 2010Rogers Ralph WSoil additive* Cited by examinerClassifications U.S. Classification405/264, 405/263, 523/132, 71/903, 106/900International ClassificationC02F1/56, C09K17/48, C09K17/18Cooperative ClassificationC09K17/18, Y10S106/90, C09K17/48, C02F1/56, Y10S71/903European ClassificationC02F1/56, C09K17/48, C09K17/18Legal EventsDateCodeEventDescriptionSep 12, 2006FPExpired due to failure to pay maintenance feeEffective date: 20060714Jul 14, 2006LAPSLapse for failure to pay maintenance feesFeb 1, 2006REMIMaintenance fee reminder mailedDec 28, 2001FPAYFee paymentYear of fee payment: 4Oct 4, 1996ASAssignmentOwner name: CYTEC TECHNOLOGY CORP., DELAWAREFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MALLON, JOSEPH J.;FARINATO, RAYMOND S.;ROSATI, LOUIS;ANDOTHERS;REEL/FRAME:008278/0230Effective date: 19960930RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services