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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/44—Preparation of metal salts or ammonium salts
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
  • A61K6/35—Preparations for stabilising dentures in the mouth

Definitions

• TECHNICAL FIELD This invention relates to improvements in adhesives, in par ⁇ ticular improved denture adhesives.
• Dentures function as a substitute for missing teeth and serve as a replacement for all or a portion of the teeth ordinarily found in the oral cavity. Although dentures generally are skillfully prepared, often they do not fit perfectly. Moreover, no matter how satisfactory at first, after a period of time the fit of the denture becomes " loose and imperfect due to natural shrinkage and changes in the gums, mucous tissues, and the like. Loose and imperfectly fitted dentures usually are corrected and stabilized by the use of a denture stabilizer. Denture stabilizers are used to fill the interstices between the dentures and the gums or tissues.
• a denture stabilizer Prior to placement of the denture in the oral cavity, a denture stabilizer is applied to the denture-plate surface which, for a perfect fit, should uniformly contact the gums and mucous tissues.
• the denture stabilizer is formulated not only for its adherent proper- ties, but also to provide a cushion or gasket between the denture and the gums or tissues, thereby positioning the denture securely in the oral cavity.
• one daily application of such a composition should function as an effective means for insulating, cushioning, and securely posi ⁇ tioning the denture.
• the composition should retain its characteris ⁇ tics and properties in the typical powder and cream forms during storage under various climatic conditions such as high temperature and humidity; be readily and easily capable of application to the denture surface; not be irritating or uncomfortable to the user; be safe and nontoxic; have no disagreeable odor or color; have no unpalatable taste; optionally provide antiseptic and germicidal properties for preventing or inhibiting the growth of organisms ordinarily found in the mouth; and function as an agent for prevention of putrefaction or malodorous decomposition of foods or secretions lodging beneath or adjacent to the denture.
• the stabilizing material must be capable of 5 imbibing water and saliva and swelling, so as to fill the interstices between the denture and the gum or mucous tissues.
• the stabilizer should not attack or damage the denture, as by causing a crazing of the denture-plate material. Additionally, the stabilizer should be stable to bacteria, molds and enzyme systems found in the oral cavity, 10 and have a pH that is nonirritating to the oral mucosa, generally 5-8.5, preferably a pH around neutrality.
• the mechanical strength of the stabilizing mass be it gel or colloid, formed by imbibition of water should be great enough to securely maintain the position of the denture under normal use, and not so great as to make denture removal 15 difficult when desired, or as to damage or injure the gums, tissues or denture upon removal.
• European Patent 64,672 to Dhabhar and Schmidt, published November 17, 1982, relates to a hydrophilic denture adhesive containing an adhesive polymeric fraction comprising carboxymethylcellulose (CMC) and polyethylene oxide in a hydrophilic vehicle.
• CMC carboxymethylcellulose
• 25 European Patent Application 140,486 to A.J. Des aris, filed July 31, 1984 relates to denture adhesive compositions containing a hydro- phobically modified water-soluble polymer, alone or admixed with an alkali metal salt of CMC. Hydrophobically modified hydroxyalkyl celluloses and copolymers of ethylene oxide and long chain epoxy- 30 alkanes are preferred for use in the compositions.
• U.S. Patent 4,529,748 to H.G.P. Wienecke, issued July 16, 1985 relates to dental prosthesis adhesives formed from film-forming substances such as various cellulose derivatives, acrylate polymers, methacrylate polymers, and other film-providing substances.
• U.S. Patent 4,758,630 to Shah et al. issued July 19, 1988 relates to zinc and strontium partial salts of lower alkyl (C x to C 4 ) vinyl ether-maleic acid copolymers, wherein said zinc and strontium cations are "unmixed” with any other cations or ester functions in the copolymeric salt, the remaining initial carboxyl groups being unreact- ed.
• These lower alkyl vinyl ether-maleic acid copolymers are referred to hereinafter by the abbreviated term "AVE/MA copolymer” and the methyl vinyl ether-maleic acid copolymer as "MVE/MA copolymer”.
• the present invention encompasses adhesives and stabilizer compositions comprising: a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
• R represents a C x to C 4 alkyl radical
• n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25 ⁇ C and wherein said copolymer has a bulk density of from about 0.3 to about 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram.
• these copolymers are partial salts (mixed or unmixed, preferably mixed), said partial salts containing from about 10% to about 40% free acid, and as the cationic salt function, from about
• a cationic salt function selected from the group consisting of zinc cations, strontium cations, sodium cations, calcium cations, magnesium cations, potassium cations and ammonium cations and mixtures thereof and wherein said copolymer has a bulk density of from about 0.3 to about 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram.
• denture stabilizing compositions comprising a safe and adhesively effective amount of two or more denture adhesive components wherein one of said denture adhesive components is either the copolymer or the mixed partial salt(s) of " the present invention.
• these copolymers or mixed partial salts are used along with a water-sensitized polymeric material selected from the group consisting of natural gums, synthetic polymers, saccharide deriva ⁇ tives, cellulose derivatives, and mixtures thereof.
• the present invention encompasses stabilizer compositions com ⁇ prising: a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
• R represents a C x to C 4 alkyl radical
• n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25'C and wherein said copolymer has a bulk density of from about 0.3 to about 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram.
• these copolymers are partial salts, said partial salts containing from about 10% to about 40% free acid, and as the cationic salt function from about 0.1% to about 85% of the total initial carboxyl groups reacted with one or more of a cationic salt function selected from the group consisting of zinc cations, strontium cations, sodium cations, calcium cations, magnesium cations, potassium cations and ammonium cations and mixtures thereof and wherein said copolymer has a bulk density of from about 0.3 to about 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram.
• the partial salts comprise from about 0.1% to about 85% of one or more of the above mentioned cations in the following levels: from about 0.1% to about 65%, more pre ⁇ ferably from about 2% to about 45%, and most preferably from about 2.5% to about 30% zinc or strontium cations (preferably zinc), and from about 10% to about 75%, more preferably from about 20% to about 65%, and most preferably from about 40% to about 65% calcium cations, from about 0.1% to about 25%, and more preferably from about 0.1% to about 20% sodium cations and from about 10% to about 40%, most pre- ferably from about 20% to about 35% free acid.
• the subject polymeric salts are advantageously prepared by the interaction of the AVE/MA copolymer (I) with the optional cationic calcium, sodium, ammonium and either zinc or strontium compounds having a functional group typical of reactants of carboxylic acid, such as, for example, the hydroxide, acetate, carbonate, halide, lactate, etc. in an aqueous medium.
• carboxylic acid such as, for example, the hydroxide, acetate, carbonate, halide, lactate, etc.
• the oxide of zinc and the hydroxide of calcium and sodium are utilized. Since zinc hydroxide is not commercially available, its use as a reactant is readily and more economically accomplished by employing an aqueous slurry of particulate zinc oxide which, although practically insoluble in water, provides hydration to zinc hydroxide on the particulate surface.
• Calcium and sodium hydroxides as well as stron ⁇ tium hydroxide are available in either crystalline or powder form and are soluble in about 50 parts water.
• Strontium carbonate may also be used.
• Anions that form toxic, irritating or contaminating by-products should be avoided, or special precautions and treatment provided to assure the removal and absence of such by-products from the polymeric salt end-product.
• the particular compound used should be substantial ⁇ ly pure to assure obtaining a substantially pure, substantially off-white polymeric salt end-product.
• the lower alkyl vinyl ether aleic acid (AVE/MA) copolymers (I) are readily obtained by copoly erizing a lower alkyl vinyl ether monomer, such as methyl vinyl ether, ethyl vinyl ether, divinyl ether, propyl vinyl either and isobutyl vinyl ether, with maleic anhydride to yield the corresponding lower alkyl vinyl ether-maleic anhydride copolymer which is readily hydrolyzable to the acid copolymer (I). Both anhydride and acid forms are also available from commercial suppliers.
• a lower alkyl vinyl ether monomer such as methyl vinyl ether, ethyl vinyl ether, divinyl ether, propyl vinyl either and isobutyl vinyl ether
• the GAF Corporation Wayne, New Jersey, provides both the polymeric free acid form (I) and the corresponding anhydride form under its "GANTREZ” trademark as the "GANTREZ S Series" and "GANTREZ AN Series", respectively.
• Said acid and anhydride forms of AVE/MA copolymers having an average molecular weight of from about 50,000 to about 80,000 (as measured by membrane osmometry in 2-butanone 1-10 grams/1000 ml solution), are also characterized by having the previ ⁇ ously described specific viscosity parameter of more than 1.2.
• the anhydride copolymer dissolves in water, the anhydride linkage is cleaved so that the highly polar, polymeric free acid (I) is formed.
• the anhydride form which is relatively less expensive than the acid form, may be used as a convenient and cheaper precursor for the acid. Elevated temperatures may be advantageously employed to enhance the rate of anhydride-to-acid hydrolysis.
• the lower alkyl vinyl ether-maleic acid copolymer (I), or its corresponding anhydride is added to water preheated to about 70-80'C with vigorous stirring to form a homogeneous mixture. If the anhydride precursor is utilized, it is recommended that the aqueous mixture be further heated to about 90 * C with stirring to ensure complete hydrolysis of the anhydride to the acid form. Heating is then discontinued although mixing is continued until the batch turns clear with a simultaneous decrease in viscosity (about 65-75'C).
• an aqueous solution of the cationic zinc or strontium salt forming compound or, for example, an aqueous dispersion of particulate zinc oxide is combined with calcium hy ⁇ droxide in the form of a slurry, in an amount sufficient to provide the desired zinc and calcium cationic content desired in the end-product, is separately prepared at ambient temperature and slowly added to the hot polymeric acid solution with continuous vigorous mixing so as to prevent localized precipitation of the cationic polymeric salt. After the calcium and zinc have reacted, an aqueous solution of sodium hydroxide is added slowly, in the amount sufficient to provide the cation sodium content desired in the end-product. After addition is complete, mixing is continued to ensure that all the salt forming compounds are reacted with the copolymer.
• an aqueous solution containing the zinc and calcium source is preheated to 70-80'C with vigorous stirring to form a homogeneous slurry.
• the lower alkyl vinyl ether-maleic acid copolymer (I) or its corresponding anhydride is then added to the slurry while further heating to 90 * C and stirring to ensure complete hydrolysis.
• the AVE/MA copolymer, calcium, and strontium zinc oxide powders are slurried in water at 25 * and subsequently heated to 80'C - 90'C for reaction to occur. Upon completion of this reaction step an aqueous solution of sodium hy ⁇ droxide is slowly added.
• the zinc (or strontium), calcium, and sodium cations in the resultant mixed partial salt of AVE/MA copolymer should be sufficient to give a neutralization ranging from about 10% to about 75%, prefera ⁇ bly from about 20% to about 65%, and most preferably from about 40% to about 65% calcium, and from about 0.1% to about 65%, preferably from about 2% to about 45%, and most preferably from about 2.5% to about 30% zinc or strontium, and from about 0.1% to about 25%, preferably from 0.1% to about 20% sodium, resulting in a salt containing free acid in the range of from about 10% to about 40%, preferably from about 20% to about 35%.
• reaction batch is then dried using drum dryers maintained at 80-100 PSIG with hot steam to evaporate the water content and recover the polymeric salt with a high specific surface area, in the flake form.
• the resulting flakes are subjected to milling and screening to yield the desired physical properties to provide satisfactory denture stabilizing properties while maintaining the desired high specific surface areas.
• These surface areas can be obtained by any appropriate micronizing technique, preferably air jet milling or pin/disk or hammer milling as described in Remingtons Pharmaceutical Sciences (16th edition) pp. 1535-1539, incorporated by references herein.
• Said salts are friable so that appropriate particle size and bulk density can be obtained.
• drum dried particles should be milled to a preferred bulk density of about 0.3 to about 1.2 more preferably about 0.6 to about 1.2 and most preferably about 0.7 to about 1.2 grams per cubic centimeter while maintaining a specific surface area of about 0.5 to about 2.5, more preferably about 0.6 to about 2.5, and most preferably about 0.7 to about 2.0 square meters per gram.
• Ground particles should be capable of passage through a 140- to 200-mesh sieve (U.S.B.S. series) and preferably are less than 0.3 millimeters in their largest dimension.
• the subject acid copolymers and their respective salts have exceptional adhesive qualities when contacted with water or saliva such that they are extremely useful as denture adhesive materials in denture stabilizing compositions.
• the salt in particu- late form is preferably characterized by a particle size of at least minus 140-mesh U.S.B.S. sieve; a bulk density greater than 0.3 gram per cubic centimeter and preferably higher then 0.6 gram per cubic centimeter; and a pH between 3 and 8 and preferably between 5 and 7.5, the pH being determined on a one percent by weight dispersion in water.
• Each of the subject copolymer salts may be utilized in effective adhesive amounts, preferably at least 25 percent by weight, as the sole adhesive component or as a co-adhesive in joint usage with other active adhesive components in denture stabilizing compositions.
• said copolymer salt be used along with a co-adhesive in denture stabilizing compositions.
• the co-adhesive is a polymeric material selected from the group consisting of natural gums, synthetic polymers, saccharide derivatives, cellulose derivatives, and mixtures thereof. In general, from about 15 to about 70 percent, based on the total weight of the composition, of said mixed calcium/sodium/zinc or strontium salt is present.
• Preferred co-adhesives include a water-soluble hydrophilic colloid or polymer having the particular property of swelling upon exposure to moisture to form a mucilaginous mass.
• Such adhesive materials include both natural gums and synthetic polymeric gums and, among those commonly employed in denture stabilizing compositions and which are also suitable herein co-adhesive action with the subject mixe ⁇ AVE/MA copolymer salts, there may be mentioned, for example, karaya gum, gelatin, algin, sodium alginate, tragacanth, methylcellu ⁇ lose, acrylamide polymers, ethylene oxide polymers, polyvinylpyrroli- done, cationic polyarylamide polymers and, as the most preferred, sodium carboxymethylcellulose and mixed partial salts of poly(vinyl methylether-maleic acid) copolymer.
• a preferred aspect of the subject invention provides adhesives and denture stabilizing compositions having as a stabilizing component an effective adhesive amount of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
• R represents a C x to C 4 alkyl radical
• n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25"C and wherein said copolymer has a bulk density of from about 0.3 to about 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram.
• these copolymers are partial salts, said partial salts containing from about 10% to about 40% free acid, and as the cationic salt function from about 0.1% to about 85% of the total initial carboxyl groups reacted with one or more of a cationic salt function selected from the group consisting of zinc cations, strontium cations, sodium cations, calcium cations, magnesium cations, potassium cations and ammonium cations and mixtures thereof and wherein said copolymer has a bulk density of from about 0.3 to about 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram.
• Another preferred aspect of this invention provides a denture stabilizing composition
• a denture stabilizing composition comprising a safe and adhesively effective amount of at least two denture adhesive components, wherein one of said denture adhesive components is the acid or partial salt of a lower alkyl vinyl ether-maleic acid copolymer described above.
• one of said denture adhesive components is the acid or partial salt of a lower alkyl vinyl ether-maleic acid copolymer described above.
• the co-adhesive is as described above.
• compositions of the present invention can optionally include from about 0.01% to about 5% of one or more components which provide the user with sensory, including flavor, benefits.
• Suitable compo ⁇ nents include menthol, menthyl lactate, peppermint oil, spearmint oil, peppermint oil, leaf alcohol, as well as those paramenthane carboxy- amides flavoring agents available from Wilkinson-Sword (such as WS-3) which are described in U.S. Patent 4,136,163 to Watson et al., issued January 23, 1979 which is incorporated by reference herein.
• compositions of the present invention are manufactured in an art-recognized manner known to those skilled in the art, such as in a powder, cream, ointment, liquid, paste, water or film.
• the compo ⁇ sitions of the present invention are preferably manufactured with drum dried AVE/MA copolymers or their salts that are milled using appro ⁇ priate micronization techniques such as fluid energy or air jet or hammer milling of drum dried mixed partial salts of AVE/MA copolymer.
• Suitable examples of such formulations are disclosed in U.S. Patent 4,518,721, issued May 21, 1985 and U.S. Patent 4,514,528, issued April 30, 1985, both to Dhabhar et al . and both of which are hereby incor ⁇ porated by reference herein.
• compositions contain from about 10% to about
• this base is mineral oil or petrolatum, however polyethylene glycol, paraffin, glycerin and mixtures thereof are also useful. Most preferred is a mixture of mineral oil and petrolatum.
• the adhesive salts of the present invention can be used for a wide variety of general adhesive uses including, but not limited to, pharmaceutical uses (e.g., oral drug delivery and topical bandages); and aqueous adhesives (e.g., where adhesiveness in the presence of water is required).
• pharmaceutical uses e.g., oral drug delivery and topical bandages
• aqueous adhesives e.g., where adhesiveness in the presence of water is required.
• Example I Into a reaction vessel equipped with a high speed stirrer and containing 94 parts (4.7 kg) of purified water heated to 85'C, is slowly added 6 parts (300 grams) methyl vinyl ether-maleic anhydride copolymer to the reaction vessel over a 15 minute period. Temperature and mixing remain constant for 60 minutes after 15 minutes, the resulting adhesive polymeric dispersion is characterized by an in ⁇ crease in viscosity, and a decrease and stabilization of reaction pH which is a dispersion of said material in water, said material con ⁇ sisting of acid form of methyl vinyl ether-maleic acid copolymer.
• the resultant solution of the methyl vinyl ether-maleic acid (MVE/MA) copolymer is then dried using a drum dryer maintained at 80-100 PSIG with hot steam to evaporate the water content and recover the polymeric salt with a high specific surface area, in flake form.
• the thus obtained dried acid form of the MVE/MA copolymer is then ground using an air jet or hammer mill to a bulk density of about 0.7 to about 1.1 grams per cubic centimeter while maintaining a specific surface area ⁇ ⁇ f about 0.7 to about 1.5 square meters per gram.
• This copolymer is then screened through a 140-mesh sieve and then through a 200 mesh sieve (U.S.B.S. sieve series).
• the powder has a pH of about 2.5 for a one percent solution in water.
• This particular copolymer will be referred to hereinafter by the abbreviated term, "acid form of MVE/MA copolymer".
• Example II Into a reaction vessel equipped with a high speed stirrer and containing 92.1 parts (1.842 kg) of purified water heated to 85'C, is slowly added calcium hydroxide 1.9 parts (37.9 grams), and sodium hydroxide 0.3 parts (5.8 grams). After addition is complete, the temperature of the slurry is kept constant with high speed mixing. While keeping heat and mixing constant add 5.71 parts (114 grams) of methyl vinyl ether-maleic anhydride copolymer to the reaction vessel containing the alkali dispersion over a 15 minute period. Temperature and mixing remain constant for 60 minutes.
• the resulting adhesive polymeric dispersion is characterized by an in ⁇ crease in viscosity, and a decrease and stabilization of the reaction pH which is a dispersion of said material in water, said material consisting of mixed partial calcium sodium salt of methyl vinyl ether- maleic acid copolymer.
• the resultant solution of the calcium sodium salt of methyl vinyl ether-maleic acid (MVE/MA) copolymer is then dried using a drum dryer maintained at 80-100 PSIG with hot steam to evaporate the water content and recover the polymeric salt with a high specific surface area, in flake form.
• the thus obtained dried calcium sodium MVE/MA copolymer salt is then ground using an air jet or hammer mill to a bulk density of about 0.7 to about 1.1 grams per cubic centimeter while maintaining a specific surface area of about 0.7 to about 1.5 square meters per gram.
• This copolymer is then screened through a 140-mesh sieve and then through a 200 mesh sieve (U.S.B.S. sieve series).
• the powder has a pH of about 6.5 for a one percent solution in water. Analysis of the salt indicates about 70.0 percent neutrali ⁇ zation with calcium, 10.0 percent neutralized with sodium with 20% remaining carboxyl groups. This particular salt will be referred to hereinafter by the abbreviated term, "70% Ca/10% Na partial salt of MVE/MA copolymer".
• Example III Into a reaction vessel equipped with a high speed stirrer and containing 92.4 parts (4.6 kg) of purified water heated to 85'C, is slowly added 0.53 parts (26.3 grams) of zinc oxide and calcium hy- droxide 1.30 parts (64.6 grams). After addition is complete, the temperature of the slurry is kept constant with high speed mixing. While keeping heat and mixing constant add 5.76 parts (288 grams) of methyl vinyl ether-maleic anhydride copolymer to the reaction vessel containing the alkali dispersion over a 15 minute period. Temperature and mixing remain constant for 60 minutes.
• the resulting adhesive polymeric dispersion is characterized by an in ⁇ crease in viscosity, and a decrease and stabilization of the reaction pH which is a dispersion of said material in water, said material consisting of mixed partial calcium zinc salt of methyl vinyl ether- maleic acid copolymer.
• the resultant solution of the calcium zinc salt of methyl vinyl ether-maleic acid (MVE/MA) copolymer is then dried using a drum dryer maintained at 80-100 PSIG with hot steam to evaporate the water content and recover the polymeric salt with a high specific surface area, in flake form.
• the thus obtained dried calcium zinc MVE/MA copolymer salt is then ground using an air jet or hammer mill to a bulk density of about 0.7 to about 1.1 grams per cubic centimeter while maintaining a specific surface area of about 0.7 to about 1.5 square meters per gram.
• This copolymer is then screened through a 140-mesh sieve and then through a 200 mesh sieve (U.S.B.S. sieve series).
• the powder has a pH of about 5.4 for a one percent solution in water. Analysis of the salt indicates about 47.5 percent neutrali ⁇ zation with calcium, 17.5 percent neutralized with zinc with 35% remaining carboxyl groups. This particular salt will be referred to hereinafter by the abbreviated term, "47.5% Ca/17.5% Zn partial salt of MVE/MA copolymer".
• Example IV Into a reaction vessel equipped with a high speed stirrer and containing 84.7 parts (7.6 kg) of purified water heated to 85 ⁇ C, is slowly added. 0.2 parts (18 grams) of zinc oxide and calcium hy- droxide 0.92 parts (82.7 grams). After addition is complete, the temperature of the slurry is kept constant with high speed mixing. While keeping heat and mixing constant add 3.9 parts (348 grams) of methyl vinyl ether-maleic anhydride copolymer to the reaction vessel containing the alkali dispersion over a 15 minute period.
• the resulting adhesive polymeric dispersion is characterized by an increase in viscosity, and a decrease and stabilization of the reaction pH which is a dispersion of said material in water, said material consisting of mixed partial calcium zinc salt of methyl vinyl ether-maleic acid copolymer. Temperature and mixing remain constant for 60 minutes. Next, 890 grams of a 1% solution of sodium hydroxide is slowly added over a 30 minute period and the reaction is allowed to go to completion as indicated by the stabilization of the reaction pH.
• the resultant solution of the calcium zinc salt of methyl vinyl ether-maleic acid (MVE/MA) copolymer is then dried using a drum dryer maintained at 80-100 PSIG with hot steam to evaporate the water content and recover the polymeric salt with a high specific surface area, in flake form.
• the thus obtained dried calcium zinc MVE/MA copolymer salt is then ground using an air jet or hammer mill to a bulk density of about 0.7 to about 1.1 grams per cubic centimeter while maintaining a specific surface area of about 0.7 to about 1.5 square meters per gram.
• This copolymer is then screened through a 140-mesh sieve and then through a 200 mesh sieve (U.S.B.S. sieve series).
• the powder has a pH of about 5.7 for a one percent solution in water. Analysis of the salt would indicate about 50 percent of the carboxyl groups neutralized with calcium, 9.9 percent neutralized with zinc and 5% neutralized with sodium with 35% carboxyl groups remaining unreacted. This particular salt will be referred to here ⁇ inafter by the abbreviated term, "50% Ca/9.9% Zn/ 5% Na partial salt of MVE/MA copolymer".
• the product when used in conjunction with conventional denture adhesives and applied to wet dentures with normal usage, provides denture stabilizing characteristics superior to those obtained by the particular conventional denture adhesive itself.
• Example V Into a reaction vessel equipped with a high speed stirrer and containing 85.1 parts (7.7 kg) of purified water heated to 85 * C, is slowly added 0.1 parts (9 grams) of zinc oxide and calcium hydroxide 1.1 parts (98.9 grams). After addition is complete, the temperature of the slurry is kept constant with high speed mixing. While keeping heat and mixing constant add 3.9 parts (347.2 grams) of methyl vinyl ether-maleic anhydride copolymer to the reaction vessel containing the alkali dispersion over a 15 minute period.
• the resulting adhesive polymeric dispersion is characterized by an in ⁇ crease in viscosity, and a decrease and stabilization of the reaction pH of the dispersion of said material in water, said material con ⁇ sisting of mixed partial calcium zinc salt of methyl vinyl ether- maleic acid copolymer. Temperature and mixing remain constant for 60 minutes. Next, 890 grams of a 1% solution of sodium hydroxide is slowly added over a 30 minute period and the reaction is allowed to go to completion as indicated by stabilization of the reaction pH.
• the resultant solution of the calcium zinc salt of methyl vinyl ether-maleic acid (MVE/MA) copolymer is then dried using a drum dryer maintained at 80-100 PSIG with hot steam to evaporate the water content and recover the polymeric salt with a high specific surface area, in flake form.
• the thus obtained dried calcium zinc MVE/MA copolymer salt is then ground using an air jet or hammer mill to a bulk density of about 0.7 to about 1.1 grams per cubic centimeter while maintaining a specific surface area of about 0.7 to about 1.5 square meters per gram.
• This copolymer is then screened through a 140-mesh sieve and then through a 200 mesh sieve (U.S.B.S. sieve series).
• the powder has a pH of about 6.0 for a one percent solution in water. Analysis of the salt would indicate about 60% of the carboxyl groups neutralized with calcium, 5% neutralized with zinc, and 5% neutralized with sodium with 30% of the carboxyl groups re ⁇ maining unreacted.
• This particular salt will be referred to here ⁇ inafter by the abbreviated term, "60% Ca/5% Zn/5% Na partial salt of MVE/MA copolymer".
• the product when used in conjunction with conventional denture adhesives and applied to wet dentures with normal usage, provides denture stabilizing characteristics superior to those obtained by the particular conventional denture adhesive itself. Examol e VI
• Example I The procedure of Example I is repeated except that the following amounts of reactants are employed: 3.9 parts (77.3 grams) of the anhydride copolymer, 94.9 parts (1.9 kg) purified water; and 0.2 parts (3.99 grams) of zinc oxide; 0.2 parts (3.99 grams) of sodium hydroxide and 0.83 parts (16.5 grams) calcium hydroxide.
• the resultant powder would have a bulk density of about 0.7 to about 1.1 grams per cubic centimeter and a specific surface area of about 0.7 to about 1.5 square meters per gram.
• Analysis of the salt indicates about 45 percent calcium neutralization of the total initial carboxyl groups in the copolymer salt molecule; 9.9 percent neutrali ⁇ zation with zinc and 10% neutralization with sodium will be referred to hereinafter by the abbreviated term "45% calcium/9.9% zinc/10% sodium partial salt of MVE/MA copolymer".
• Each of the indicated MVE/MA copolymer salts which would have, for the minus 140-mesh U.S.B.S. sieve powder, a bulk density greater than 0.5 grams per cubic centimeter, while maintaining a specific surface area greater than 0.6 square meters per gram and provides markedly beneficial denture stabilizing characteristics.
• Each of the indicated salts may be abbreviated by the percent of calcium/percent of zinc/percent sodium neutralization as done in Examples I through V.
• Example V The MVE/MA copolymeric anhydride-to-acid hydrolysis procedure outlined in Example V is repeated. To a vessel containing 8.5 kg of purified water heated to 85°C is added 16.5 grams of strontium hy- droxide octahydrate. With vigorous mixing, 99.4 grams of calcium hydroxide is slowly added. After addition is complete, the tempera ⁇ ture of the slurry is kept constant with high speed mixing. While maintaining the heat and constant mixing, 34.9 grams of methyl vinyl ether-maleic anhydride copolymer are added to the reaction vessel containing the alkali dispersion over a 20 minute period. This produces a mixed partial calcium strontium salt of methyl vinyl ether-maleic acid copolymer.
• Example IX Denture stabilizing powder compositions are prepared by blending together the following:
• Example X In use, the above powders (typically 0.1-1 g) are placed on a premoistened denture, allowed to hydrate briefly, and the denture is inserted in the mouth and pressed into place, all in the manner of denture adhesives well-known in the art.
• Example X In use, the above powders (typically 0.1-1 g) are placed on a premoistened denture, allowed to hydrate briefly, and the denture is inserted in the mouth and pressed into place, all in the manner of denture adhesives well-known in the art.
• Example X In use, the above powders (typically 0.1-1 g) are placed on a premoistened denture, allowed to hydrate briefly, and the denture is inserted in the mouth and pressed into place, all in the manner of denture adhesives well-known in the art.
• Example X In use, the above powders (typically 0.1-1 g) are placed on a premoistened denture, allowed to hydrate briefly,
• Liquid-type denture stabilizing compositions are prepared by mixing together the following:
• Example XI Cream-type denture stabilizing compositions are prepared by mixing together the following:

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• 1991
  • 1991-12-16 WO PCT/US1991/009467 patent/WO1992010988A1/en not_active Application Discontinuation
  • 1991-12-16 AU AU91700/91A patent/AU9170091A/en not_active Abandoned
  • 1991-12-16 HU HU9301817A patent/HUT65213A/hu unknown
  • 1991-12-16 CA CA002098488A patent/CA2098488A1/en not_active Abandoned
  • 1991-12-16 JP JP4503360A patent/JPH06503350A/ja active Pending
  • 1991-12-16 SK SK633-93A patent/SK63393A3/sk unknown
  • 1991-12-16 BR BR919107181A patent/BR9107181A/pt not_active Application Discontinuation
  • 1991-12-16 EP EP19920903466 patent/EP0563285A1/de not_active Withdrawn
  • 1991-12-16 CZ CS931221A patent/CZ122193A3/cs unknown
  • 1991-12-20 IE IE451291A patent/IE914512A1/en not_active Application Discontinuation
  • 1991-12-20 PT PT99915A patent/PT99915A/pt not_active Application Discontinuation
• 1993
  • 1993-06-16 NO NO93932215A patent/NO932215L/no unknown
  • 1993-06-18 FI FI932841A patent/FI932841A/fi not_active Application Discontinuation

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