AU8408691A - Terpolymers of maleic anhydride, c1-c5 alkyl vinyl ether and isobutylene or a c12-c14 alpha-olefin, and crosslinked products thereof - Google Patents

Terpolymers of maleic anhydride, c1-c5 alkyl vinyl ether and isobutylene or a c12-c14 alpha-olefin, and crosslinked products thereof

Info

Publication number
AU8408691A
AU8408691A AU84086/91A AU8408691A AU8408691A AU 8408691 A AU8408691 A AU 8408691A AU 84086/91 A AU84086/91 A AU 84086/91A AU 8408691 A AU8408691 A AU 8408691A AU 8408691 A AU8408691 A AU 8408691A
Authority
AU
Australia
Prior art keywords
vinyl ether
maleic anhydride
terpolymer
alkyl vinyl
isobutylene
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.)
Granted
Application number
AU84086/91A
Other versions
AU646291B2 (en
Inventor
Balgopal Gangadharan
Rama K Haldar
Yoon T Kwak
Robert B. Login
Krystyna Plochocka
Thomas Rizzo
Mohammed Tazi
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
Priority claimed from US07/557,354 external-priority patent/US5082913A/en
Priority claimed from US07/557,356 external-priority patent/US5037924A/en
Priority claimed from US07/564,920 external-priority patent/US5034486A/en
Application filed by ISP Investments LLC filed Critical ISP Investments LLC
Publication of AU8408691A publication Critical patent/AU8408691A/en
Application granted granted Critical
Publication of AU646291B2 publication Critical patent/AU646291B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8164Compositions of homopolymers or 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 carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/30Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
    • A61K6/35Preparations for stabilising dentures in the mouth
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers 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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04Anhydrides, e.g. cyclic anhydrides
    • C08F222/06Maleic anhydride

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Epidemiology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Birds (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Dental Preparations (AREA)

Description

This invention relates to terpolymers of maleic anhydride, a C-^-Cg alkyl vinyl ether and isobutylene or a ~i2~-l4 alpha~°lef -n ι and to crosslinked products thereof, which are provided within predetermined compositional ranges for application in denture adhesive, sunscreen, hair spray and waterproofing compositions, and for effective compatibility with organic solvents.
Copolymers of maleic anhydride and alkyl vinyl ethers are well known in the art and are conventionally prepared by free radical precipitation polymerization of the monomer mixture in an aromatic hydrocarbon solvent such as benzene in the presence of a protective colloid. Another method involves copolymerization of maleic anhydride, an alkyl vinyl ether and/or a C3-C10 alkene in contact with a powder bed. In the latter method, disclosed in U.S. Patent 4,370,454, a large excess of the alkyl vinyl ether and/or alkene, e.g. 3 to 25, preferably 5 to 15, moles thereof, per mole of maleic anhydride monomer, is present during the polymerization, instead of the usual 1:1 mole ratio required of the copolymer. In the powder bed method, the heat generated during polymerization is removed by evaporating the excess alkyl vinyl ether and/or alkene which boils at a lower temperature than maleic anhydride. The examples in this patent were directed to copolymers of maleic anhydride and alkyl vinyl ethers, or copolymers of maleic anhydride and alkene. What is provided herein are terpolymers of maleic anhydride (MA) , a C-^-C- alkyl vinyl ether (AVE) and isobutylene (IB) or a C12-C14 alpha-olefin (AO) , and crosslinked products thereof, for use in thickener, denture adhesive, sunscreen, hair spray and waterproofing compositions.
Suitably, the molar ratio of MA:AVE:AO in the terpolymer is about 1:0.90-0.99:0.01-0.10, preferably about 1:0.94-0.96:0.04-0.06, respectively. Representative c l~c5 alky! vinyl ethers include methyl vinyl ether, propyl vinyl ether and butyl vinyl ether. Suitable 12~ 14 alpha'Olefi113 are straight chain unsaturated hydrocarbons such as dodecene and tetradecene. Crosslinked products of such terpolymers with such crosslinking agents as 1,7-octadiene and 1,9-decadiene also are provided herein.
Suitably the molar ratio of MA:AVE:IB is about 1:0.4-0.9:0.1-0.6, preferably about 1:0.5-0.8:0.2-0.5. As denture adhesives, the terpolymer provided has a weight average molecular weight of about 30,000 to 40,000, preferably about 50,000 to 350,000, and in the form of a mixed, partial salt such as the calcium/sodium salts wherein the equivalent ratio of calcium to sodium cations may range from 2:1 to 10:1, preferably between 3:1 to 7:1, and the degree of neutralization of initial carboxyl groups is from 0.5 to 0.95, preferably from 0.7 to 0.9.
The terpolymers products of the invention are particularly characterized by a predetermined ratio between the hydrophobic, straight chain unsaturated C12-C14 hydrocarbon component and the hydrophilic, maleic anhydride component, which ratio affords a suitable hydrophilic-lipophilic balance (HLB) for the terpolymer and its crosslinked derivative. A preferred process for making the terpolymers of the invention also is characterized in that the monomers are polymerized in a mixed solvent comprising a cycloaliphatic hydrocarbon such as cyclohexane and an aliphatic carboxylic ester such as ethyl acetate.
In this process, a suitable reactor is provided with appropriate inlet tubes, agitation means, and heater and temperature control means. The reactor is first purged with nitrogen to remove air from the system. Generally three separate purges are employed, at about 3 bars pressure and about 40°C. The reactor is precharged with maleic anhydride and the crosslinking agent in a suitable solvent which may be an aromatic hydrocarbon such as benzene or toluene but is preferably a mixed solvent of a cycloaliphatic hydrocarbon such as cyclohexane and an ester of an aliphatic carboxylic acid such as ethyl acetate. A solvent system which is a 50:50 mixture of cyclohexane and ethyl acetate is preferred.
The precharged reactor is purged with nitrogen at about 58°C. and a free-radical polymerization initiator is introduced in three stages during the polymerization, generally at the beginning, after about 1-1/2 hours and finally after about 3 hours, for a polymerization period of about 3 hours. Alternately, the initiator can be introduced in a continuous manner, e.g. as a solution in the reaction solvent. Any suitable initiator known in the art may be used including but not limited to peroxides. Tertiary butyl or tertiary amylperoxy pivalate are preferred. The concentration of initiator may vary widely, although suitably the initiator comprises about 0.05 to 2% by weight of the maleic anhydride reactant. Then, simultaneously with feeding of initiator, the alkyl vinyl ether and isobutylene or alpha-olefin monomers are introduced separately or together into the precharged reactor, and at a controlled rate, during the course of the polymerization.
Overall, the molar ratio of maleic anhydride to the combined alkyl vinyl ether and isobutylene or alpha-olefin monomers in the process is set at about less than 1:1. In practice about a 10% excess of the alkyl vinyl ether over the 1:1 ratio is used to ensure complete conversion of the maleic anhydride to the terpolymer. The molar amounts of alkyl vinyl ether present in the terpolymer is about 0.4-0.9, preferably 0.6-0.8, and the molar amounts of isobutylene present in the terpolymer is about 0.1-0.6, preferably about 0.2-0.5.
The molar amount of C12-C14 alpha-olefin present in the resultant terpolymer is about 0.01-0.10, preferably 0.04-0.06. The crosslinker, when present, corresponds to about 5 wt. % of total monomers in the terpolymer. The predetermined amount of hydrophobic c12~c14 alpha-olefin in the terpolymer will provide terpolymers with a suitable HLB for various commercial applications.
Of course, during the polymerization, the reaction mixture is agitated effectively, and, at the conclusion of the polymerization, the reaction product is held at the polymerization temperature for about 1-1/2 hours. Then excess alkyl vinyl ether is vented and the product is discharged, filtered and the fine powders of the terpolymer is dried.
For use as a denture adhesive, the terpolymer is converted to its mixed, partial salt, which preferably is employed as a dry powder having a particle size of less than 250 μ, and, more desirably, a particle size of from about 5 to about 200 u. Denture adhesive compositions are provided herein by incorporating dry powders of the above adhesive copoly er as mixed salts into a liquid base carrier by mixing until a homogeneous cream paste suspension or collodial dispersion is obtained, usually within a period of from about 20 minutes to about 5 hours. The resulting composition contains an effective adhesive amount of the adhesive copolymer mixed salt, generally between about 5 and about 50 wt. %, and preferably between about 10 and about 35 wt. %, of the final composition.
Suitable mixed partial salts herein include the calcium/sodium mixed partial salts which are prepared by reacting the copolymer with suitable bases. Preferably the equivalent ratio of calcium cations to sodium cations in the mixed partial salts may range from 2:1 to 10:1 and most preferably is between 3:1 and 7:1 (on a mole ratio basis, the range of calcium to sodium cations is from 1:1 to 5:1, most preferably from 1.5:1 to 3.5:1). The sum total of cations in the mixed partial salt should be sufficient to give a degree of neutralization of from 0.5 to 0.95 and preferably 0.7 to 0.9 of the total initial carboxyl groups in the copolymer. In the determination of the total initial carboxyl groups in the copolymer, the anhydride radical is considered as containing 2 initial carboxyl groups.
The base carrier portion of the composition generally includes a water soluble or partially water soluble hydrophilic carrier which is capable of swelling upon exposure to moisture to form a mucilaginous mass. Such carrier materials include natural and synthetic gums, viscous liquids, gels and powders. Among those suitably employed as base carriers in the composition are karaya gum, gelatine, gum tragacanth, gum acacia, gum shiraz, algin, sodium alginate, tragacanth, methyl cellulose, a mixture of petrolatum and mineral oil, glycerine, polyvinylpyrrolidone, K-30 and K-90, carboxymethyl cellulose, ethylene oxide polymers, of which the preferred is a mixture of petrolatum and mineral oil in a ratio of 40:60-60:40.
The adhesive terpolymer of the invention can be employed as the sole adhesive component in the denture adhesive composition or it can be used as a coadhesive with another adhesive material. Such adhesive additive, if present, will generally comprise about 5-20% by weight of the composition. Suitable adhesive additives include natural or synthetic polymers such as cellulose, karaya gum, gum tragacanth, gum acacia, carboxymethyl cellulose or salt thereof, polymethacrylate, polyvinylpyrrolidone, polyvinyl acetate, or any mixture of the above.
The compositions of the invention are particularly useful for affixing dentures and can also be used in surgical procedures which require temporary displacement of tissue. As a denture adhesive, the thermal stability of the present composition, over a temperature range which is at least sufficient to embrace all conditions encountered by living tissue, e.g. 5°-50°C. , is particularly desirable. Because of their increased adhesive strength and thermal stability, the composition retains its adhesive properties over a long period of time, i.e. up to 24 hours.
The following illustrates a few representative formulations into which the adhesive terpolymer can be added in effective amounts up to about 50%. Cream Denture Adhesive Composition Wt. %
Mineral Oil 30
Petrolatum 25
Sodium carboxymethyl cellulose 20
(adhesive additive)
Colorant l
Flavoring Agent 0.5
Material of Invention 23.5
Paste Ostomy Adhesive Composition Wt. %
Mineral oil (heavy) 35
Glycerine 5
Polyvinylpyrrolidone 20
Carboxymethyl cellulose 5
Tosylate of quat. amino-N-propylpyrrolidone 0.5
Matrial of Invention 34.5
Denture Adhesive Powder Composition Wt. %
Gum tragacanth 40
Gum acacia 20
Spearmint oil 0.05
Material of Invention 39.05 - 8 -
EXAMPLE 1
98 g. (1.00 mole) of maleic anhydride (MA) and 21.04 g. (0.125 mole) of dodecene (DD) in 534 g. of toluene was precharged in a reactor equipped with suitable inlet tubes, agitation means, and heater and temperature control means, and the reactor was purged three times with nitrogen at 50 psi nitrogen pressure at 58°C. Then 3.92 g. (4 wt. % on MA) of Lupersol 11 in 15 g. of toluene was added at a rate of 9.9 ml/min. Simutaneously, 55.12 g. (72.13 ml) (0.95 mole) of methyl vinyl ether (MVE) was fed into the reactor over a period of 4 hours while agitating the reaction mixture at about 280 rpm. The reactant monomers corresponds to 23% solids in this solvent system. The reactor was held at 58°C. for 1 hour, cooled, excess methyl vinyl ether was vented, the product was discharged from the reactor, filtered, washed, and dried.
A solid product was obtained which had a molar ratio of maleic anhydride to methyl vinyl ether to dodecene (MA:MVE:DD) of about 1.0:0.95:0.05. The yield was 147.3 g. (91.2%). The specific viscosity was 0.15 as measured in 1% methyl ethyl ketone, viscometer I 616, size 100.
EXAMPLE 2
60.0 g. (0.612 mole) of maleic anhydride was precharged into a reactor with 4.78 g. (0.343 mole) of tetradecene, 4.78 g. (0.0434 mole) of 1,7-octadiene and 420 g. of a 50:50 mixture of cyclohexane and ethyl acetate. The reactor was purged with nitrogen and heated to 58°C. Then a mixture of 39.09 g. (50.88 ml., 0.365 mole) of methyl vinyl ether was admitted into the reactor slowly over a period of 3 hours. Simultaneously, three portions of 0.1 g. each (0.5% based on MA) of Lupersol 11 were admitted during the polymerization. After 3 hours, the reaction product was held at 58°C. for 1-1/2 hours, cooled to room temperature, excess methyl vinyl ether vented and the product was discharged, filtered and dried to provide a fine, dry crosslinked terpolymer product.
The crosslinked terpolymer comprised a molar ratio of maleic anhydride to methyl vinyl ether to tetradecene (MA:MVE:TD) of about 1.0:0.96:0.04 and was crosslinked with 5.0% by weight of 1,7-octadiene based on the total weight of the terpolymer.
EXAMPLE 3
The terpolymer was crosslinked with other crosslinking agents selected from dienes, divinyl ethers and allyl carbohydrates with similar results.
EXAMPLE 4
The 1,7-octadiene crosslinker was introduced with the externally fed monomers. The reaction product slurry was thick but filterable, and it was dried at 65°C. in vacuum oven.
The crosslinked terpolymers prepared above found particular application in thickener, adhesive, sunscreen, hair spray and waterproofing compositions.
EXAMPLE 1A
65 g. (0.67 mole) of maleic anhydride in 194 g. of a 50:50 mixture of cyclohexane and ethyl acetate was precharged in a reactor equipped with suitable inlet tubes, agitation means, and heater and temperature control means, and the reactor was purged three times with nitrogen at 3 bars pressure and at 58°C. Then 0.217 g. of Lupersol 11 in 2 g. of a 50:50 mixture of cyclohexane and ethyl acetate was added. Simutaneously, a mixture of 28.9 g. (37.6 ml., 0.5 mole) of methyl vinyl ether and 9.3 g. (15.8 ml., 0.17 mole) of isobutylene was fed into the reactor over a period of 3 hours while agitating the reaction mixture at about 180 rpm. Two additional portions of initiator of 0.217 g. each were introduced after 1-1/2 and 3 hours. The reactant monomers constitute a 20% solids mixture in this solvent system. The reactor then was held at 58°C. for 1-1/2 hours, cooled, excess methyl vinyl ether was vented and the product was discharged from the reactor. The desired powder terpolymer was obtained by filtration; it had a molar ratio of maleic anhydride to methyl vinyl ether to isobutylene of 1:0.75:0.25, which was substantially the same ratio as the reactants used in the process.
EXAMPLES 2A - 12A
The process of Example 1A was followed to provide the terpolymers of desired compositions using monomers of different feeding composition and in various solvent systems.
TABLE 1
Molar Composition of Reactant Monomers in Examples 2A - 12A
Maleic
The molar composition of the terpolymer obtained was substantially the same as that of charged reactant monomers in the process. EXAMPLE 13 A
65.0 g. (0.663 mole) of maleic anhydride was precharged into a reactor with 5.33 g. (0.048 mole) of 1,7-octadiene and 535 g. of toluene. The reactor was purged with nitrogen and heated to 58°C. Then a mixture of 21.17 g. (27.67 ml., 0.365 mole) of methyl vinyl ether and 20.46 g. (34.81 ml., 0.365 mole) of isobutylene was admitted into the reactor slowly over a period of 4 hours. Simultaneously, three portions of 0.65 g. each of Lupersol 11 was admitted during the polymerization of 4 hours. Then the reaction product was held at 58°C. for l hour, cooled to room temperature, excess methyl vinyl ether was vented and the product was filtered. 100.5 g. of dry terpolymer powder was collected.
The crosslinked terpolymer obtained in this manner had a molar ratio of maleic anhydride to methyl vinyl ether to isobutylene of 1:0.50:0.50 and was crosslinked with 5.0% by weight of 1,7-octadiene based on the total weight of the terpolymer.
EXAMPLE 14A
The terpolymer was crosslinked with other crosslinking agents selected from dienes, divinyl ethers and allyl carbohydrates with similar results.
EXAMPLE 15A
The 1,7-octadiene crosslinker was introduced with the externally fed monomers. The reaction product slurry was thick but filterable, and it was dried at 65°C. in vacuum oven. 98.9 g. of a dry product comprising the crosslinked terpolymer was obtained. EXAMPLE IB
A l-liter resin kettle was equipped with a stirrer, reflux condenser, a N2 inlet tube and an inlet closed with a rubber septum for introduction of a polymerization initiator. The kettle was charged with 60.0 g. (0.61 mole) of maleic anhydride (MA), 97.9 g. (50 wt. %) of ethyl acetate (EA) and 97.9 g. (50 wt. %) of cyclohexane (CH) . Agitation of the mixture at 180 rp was begun, and the system was purged by bubbling in N2 for 30 minutes, during which time the maleic anhydride dissolved completely. The reaction mixture was then warmed to 58°C. and 0.2 g. of Lupersol 11 (Pennwalt) was injected through the septum to initiate polymerization. Simultaneously, dropwise addition of 19.6 g. (0.33 mole) of methyl vinyl ether (MVE) and 18.88 g. (0.33 mole) of isobutylene (IB) was begun and continued over a period of 3 hours. Lupersol 11 was added in an amount of 0.4 g. after 1-1/2 hours. After completion of all additions, which required 58°C, the resulting mixture was maintained at 58°C. for . 1-1/2 hours. Thereafter, the reaction mixture was cooled to room temperature, excess MVE vented and the slurry was pumped out of the kettle into a filtration unit. There the slurry was filtered and the polymer product was dried for about 12 hours at 65°C. in a forced air oven. The polymer product was a uniform, fine white powder, having a molar ratio of MA:MVE:IB of 1:0.55:0.55.
EXAMPLE 2B
The procedure of Example IB was followed to provide copolymers of varying compositions within the molar range of 1:0.4-0.9:0.1-0.6, including one at 1.0:0.75:0.25. EXAMPLE 3B
PREPARATION OF DENTURE ADHESIVE COMPOSITIONS OF INVENTION
The terpolymers of Examples IB - 2B were converted to their mixed, partial salts illustrated as follows: 58.6 g. of the terpolymer was charged into a 250 ml round bottom, 3-necked flask together with 260 g. of isopropyl alcohol. The contents were agitated to make a slurry and 18.1 g. of calcium hydroxide was added slowly with agitation during 15 minutes. Then 2.85 g. of sodium hydroxide dissolved in 112.5 g. of water was added with agitation. The mixture was heated at 45°C. with agitation for 4-1/2 hours. The pH of the liquid phase was 6.1. The mixture was filtered and the precipitate was dried in a vacuum oven overnight at 65°C. to provide 93.4 g. of a dried product. Similar copolymer conversions to the mixed partial salts were effected for the terpolymers of Example 2B.
EXAMPLE 4B
PREPARATION OF ADHESIVE COMPOSITIONS FOR INSTRON TESTING
The dry, mixed salt of the MA/MVE/IB terpolymer of Example IB was milled to pass through a number 60 mesh sieve (250 u) and the resulting powder was then dispersed at a temperature of 55-65°C. , followed by cooling to 20-25°C, into a petrolatum base using mechanical stirring. The ratio of copolymer to base by weight was 1:2. The resulting cream dispersion was collected as the desired adhesive composition. EXAMPLE 5B
Adhesive compositions of GANTREZ MS-955, which is a commercial mixed salt copolymer of maleic anhydride and methyl vinyl ether, also were prepared for testing in the same manner as described above for Examples IB - 2B.
EXAMPLE 6B
EVALUATION OF DENTURE ADHESIVE COMPOSITIONS
2 g. samples of each of the above prepared compositions were evaluated for adhesion characteristics by Instron testing according to the following procedure:
In the first step, the upper and lower plates of the Instron apparatus were brought together to obtain a zero position. The upper plate was then raised 0.06 inch and the upper cycle limit on the Instron indicator is set at this point. The upper plate was then lowered and the lower cycle limit was set. In its lowest position, the upper plate was distanced 0.03 inch above the lower plate.
With these Instron settings determined, the upper plate was then raised and 2 g. of the test sample was uniformly spread over the surface of the lower plate in a 1/16 to 1/8 inch thickness; thereafter simulated salivary fluid was applied over the sample so that it was barely covered.
The Instron crosshead was cycled between the previously set limits at a crosshead speed of 0.2 in./min. The Instron chart was set in the continuous mode at a speed of 2 in./min. to record the compression and adhesion force for each cycle, 5 to 100 cycles. At the end of 100 cycles, the motion of the upper plate was halted and raised high enough to clean the surface before the next adhesive test.
Each recording was analyzed and the adhesional forces (lbs.) for the 1st, 5th, 10th, 20th, 40th 100th cycles were recorded and then plotted graphically.
The results of this study are shown in the FIGURE which data show that significantly better initial stick strength and long term adhesion is obtained for adhesive formulations containing the terpolymer compositions of the invention as compared to a related copolymer composition (MS-955) , which is considered useful as a denture adhesive.

Claims (6)

WHAT IS CLAIMED IS:
1. A terpolymer characterized by comprising maleic anhydride, a C-^-C- alkyl vinyl ether and isobutylene or a C12-C14 alpha-olefin, optionally crosslinked with a crosslinking agent.
2. A terpolymer according to claim 1 which is further characterized by comprising maleic anhydride, a C-^-Cg alkyl vinyl ether and a C12-C14 alpha olefin in the molar ratio of about 1.0:0.90-0.99:0.01-0.10.
3. A terpolymer according to claim 1 which is further characterized by comprising maleic anhydride, a c l~c5 alkyl vinyl ether and isobutylene in the molar ratio of 1:0.4-0.9:0.1-0.6.
4. A terpolymer according to claim 3 still further characterized in having a weight average molecular weight of about 30,000 to 400,000.
5. A terpolymer according to claim 4 further characterized by being in the form of a mixed, partial salt which is particularly useful as a denture adhesive composition when mixed with a base carrier.
6. A terpolymer according to claim 5 still further characterized in being in the form of a mixed, partial calcium/sodium salt wherein the calcium to sodium cation equivalent ratio is 2:1 to 10:1 and has a degree of neutralization of from 0.5 to 0.95 of the total initial carboxyl groups.
AU84086/91A 1990-07-25 1991-06-07 Terpolymers of maleic anhydride, C1-C5 alkyl vinyl ether and isobutylene or a C12-C14 alpha-olefin, and crosslinked products thereof Expired - Fee Related AU646291B2 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US07/557,354 US5082913A (en) 1990-07-25 1990-07-25 Terpolymers of maleic anhydride, alkyl vinyl ethers and isobutylene and crosslinked products thereof
US07/557,356 US5037924A (en) 1990-07-25 1990-07-25 Denture adhesive
US557356 1990-07-25
US557354 1990-07-25
US07/564,920 US5034486A (en) 1990-08-09 1990-08-09 Terpolymers of maleic anhydride, C1 -C5 alkyl vinyl ether and a C12 -C14 alpha-olefin, and crosslinked products thereof
US564920 1990-08-09

Publications (2)

Publication Number Publication Date
AU8408691A true AU8408691A (en) 1992-02-18
AU646291B2 AU646291B2 (en) 1994-02-17

Family

ID=27415747

Family Applications (1)

Application Number Title Priority Date Filing Date
AU84086/91A Expired - Fee Related AU646291B2 (en) 1990-07-25 1991-06-07 Terpolymers of maleic anhydride, C1-C5 alkyl vinyl ether and isobutylene or a C12-C14 alpha-olefin, and crosslinked products thereof

Country Status (4)

Country Link
EP (1) EP0517863A4 (en)
AU (1) AU646291B2 (en)
CA (1) CA2079799A1 (en)
WO (1) WO1992001724A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0510944B1 (en) * 1991-04-22 1998-04-15 Colgate-Palmolive Company Linear viscoelastic automatic dishwasher compositions
US5362789A (en) * 1993-12-21 1994-11-08 Isp Investments Inc. Crosslinked terpolymers of high salt tolerance
DE19600324A1 (en) 1996-01-08 1997-07-10 Basf Ag Granules for cosmetic and pharmaceutical preparations
GB2551510B (en) * 2016-06-20 2019-04-03 Reckitt Benckiser Brands Ltd Denture adhesive composition
EP3914627A4 (en) * 2019-01-25 2022-09-28 Boai NKY Medical Holdings Ltd. Ultra-pure methyl vinyl ether-co-maleic anhydride copolymers and methods for preparing same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL291450A (en) * 1962-04-13
DE3108100A1 (en) * 1981-03-04 1982-09-16 Basf Ag, 6700 Ludwigshafen METHOD FOR THE PRODUCTION OF COPOLYMERISATEN OF MALEINSAEUREANHYDRID
JPS5968392A (en) * 1982-10-09 1984-04-18 Nippon Oil & Fats Co Ltd Additive for coal/water slurry
US4910247A (en) * 1989-03-27 1990-03-20 Gaf Chemicals Corporation Adhesive composition
US5034488A (en) * 1990-01-11 1991-07-23 Gaf Chemicals Corporation Slurry polymerization of crosslinked maleic anhydride-alkyl vinyl ether copolymers in a solvent system comprising a carboxylic acid ester and a saturated hydrocarbon

Also Published As

Publication number Publication date
EP0517863A4 (en) 1993-01-27
WO1992001724A1 (en) 1992-02-06
CA2079799A1 (en) 1992-01-26
EP0517863A1 (en) 1992-12-16
AU646291B2 (en) 1994-02-17

Similar Documents

Publication Publication Date Title
US5037924A (en) Denture adhesive
US5034486A (en) Terpolymers of maleic anhydride, C1 -C5 alkyl vinyl ether and a C12 -C14 alpha-olefin, and crosslinked products thereof
US5082913A (en) Terpolymers of maleic anhydride, alkyl vinyl ethers and isobutylene and crosslinked products thereof
DE60124896T2 (en) POLYMER DISTRIBUTION AND INHIBITION SYSTEMS FOR ORAL CARE SUBSTANCES
KR940010338B1 (en) Polycarboxylic acids with small amount of residual monomer
JPH05504984A (en) Crosslinked or non-crosslinked maleic anhydride-alkyl vinyl ether polymer slurry
US5635169A (en) Soluble copolymers for hair cosmetics
WO2002042342A2 (en) Highly functional polymer latex
WO2002079270A2 (en) Highly functional polymer latex
JPH05239122A (en) Absorbent polymer, its preparation and its use for sanitary article
US5763554A (en) Denture adhesive
JPWO2019044680A1 (en) Carboxylic group-containing polymer composition and method for producing the same
AU646291B2 (en) Terpolymers of maleic anhydride, C1-C5 alkyl vinyl ether and isobutylene or a C12-C14 alpha-olefin, and crosslinked products thereof
JPS62252408A (en) Production of water absorbable and swellable polysaccharidesgraft polymer
KR100298515B1 (en) Manufacturing method of crosslinked polymer containing carboxyl group
US5147941A (en) Denture adhesive
US3956244A (en) Crosslinked vinyl acetate-maleic anhydride heteropolymers and derivatives prepared from them
AU640474B2 (en) Copolymers of maleic anhydride and acrylic acid useful in denture adhesives
WO1993002117A1 (en) Sunscreen composition
Denchev et al. Thermal behaviour and adhesive properties of some cyanoacrylate adhesives with increased heat resistance
US6794467B2 (en) Process for the preparation of polymeric absorbents
CA1271888A (en) Method of preparing pulverulent olefin-maleic anhydride copolymers
JPH09511012A (en) Terpene copolymer
US5045614A (en) Process for polymerizing vinyl monomers using amine containing compounds which simultaneously act as initiators and crosslinking agents as part of a redox initiator system
AU7875191A (en) Precipitation polymerization of copolymers of a vinyl lactam and a polymerizable carboxylic acid using sub-surface feeding