CA2426128A1 - Rheology modifying copolymer composition - Google Patents
Rheology modifying copolymer composition Download PDFInfo
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- CA2426128A1 CA2426128A1 CA002426128A CA2426128A CA2426128A1 CA 2426128 A1 CA2426128 A1 CA 2426128A1 CA 002426128 A CA002426128 A CA 002426128A CA 2426128 A CA2426128 A CA 2426128A CA 2426128 A1 CA2426128 A1 CA 2426128A1
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A rheology modifying copolymer composition containing a cross-linked copolymer of unsaturated carboxylic acid, a hydrophobic monomer, a hydrophobic chain transfer agent, a cross linking agent, and, optionally, a steric stabilizer, provides increased viscosity in aqueous electrolyte-containing environments.
Description
RHEOLOGY MODIFYING COPOLYMER COMPOSITION
BACKGROUND OF THE INVENTION
1. Field of the Invention The invention is directed to a theology-modifying copolymer composition utilizing a hydrophobic chain transfer agent which .provides increased viscosity in electrolyte-containing environments.
BACKGROUND OF THE INVENTION
1. Field of the Invention The invention is directed to a theology-modifying copolymer composition utilizing a hydrophobic chain transfer agent which .provides increased viscosity in electrolyte-containing environments.
2. Description of the Prior Art Polymeric theology modifiers provide various theological properties to aqueous systems, including thickening and viscosity. For example, various such aqueous compositions may provide improved stability, pigment suspension and application properties. Various theological modified compositions for cosmetics and personal care items provide smoothness and silkiness, while in pharmaceutical applications, the compositions can provide suspension of insoluble materials or controlled release of pharmaceutical actives, or bioadhesive properties.
Carboxyl-containing polymers of vinyl or vinylidene monomers .containing at least one terminal CH2 = C< for use as theology modifiers are well-known.
Such polymers can be homopolymers of unsaturated polymerizable carboxylic acids, such as acrylic acid, methacrylic acid, malefic acid, malefic anhydride, itaconic acid, and the like. The polymers may also be copolymers of the aforesaid acids or anhydride monomers with (meth)acrylate esters, (meth)acrylamides, olefins, malefic anhydrides, vinyl esters, vinyl ethers, and styrenics, or copolymers with other vinyl or vinylidene monomers. Copolymers of these acids are often crosslinked with small amounts of crosslinking agents.
Carboxyl-containing polymers of vinyl or vinylidene monomers .containing at least one terminal CH2 = C< for use as theology modifiers are well-known.
Such polymers can be homopolymers of unsaturated polymerizable carboxylic acids, such as acrylic acid, methacrylic acid, malefic acid, malefic anhydride, itaconic acid, and the like. The polymers may also be copolymers of the aforesaid acids or anhydride monomers with (meth)acrylate esters, (meth)acrylamides, olefins, malefic anhydrides, vinyl esters, vinyl ethers, and styrenics, or copolymers with other vinyl or vinylidene monomers. Copolymers of these acids are often crosslinked with small amounts of crosslinking agents.
Such polymers have been disclosed in U.S. Patent Nos. 2,798,053, 3,915,921, 3,940,351, 4,062,817, 4,066,583, 4,267,103, 5,349,030, and 5,373,044.
These theology-modifying polymers, however, are frequently pH
dependent, are hydrolytically unstable, require their use in large amounts to effectively increase viscosity, or are sensitive to ionic components of the formulation. Additionally, these polymers are efficient only in aqueous systems having no electrolyte, such as sodium chloride.
Naturally occurring substances are also known for use as theology modifiers in aqueous systems. Natural theology modifiers include casein, alginates, gum tragacanth, and modified cellulose, including methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and carbomethoxy cellulose.
These products, however, vary in their thickening efficiency, generally provide poor flow and leveling properties, and are subject to microbial attack, thereby requiring the presence of antimicrobial agents.
The use of "associative" thickeners as theology modifiers in aqueous systems is also known in the art. An associative thickener refers to a water-soluble or water-swellable polymer having chemically attached groups capable of hydrophobic associations similar to those of conventional surfactants. These hydrophobic associations promote water insolubility and include such chemical groups as alkyl and aralkyl groups containing from about 4 to about 30 carbon atoms, or complex hydrophobic comonomers. Such associative thickeners have been disclosed in U.S. Patent 4,384,096 which describes associative polymers made via emulsion polymerization known as Hydrophobically-Modified Alkali-Soluble Emulsion Polymers CHASE). These polymers include both complex hydrophobes and conventional hydrophobes. However, while small amounts (0.01 to 5% by weight of monomer) of mercaptan-containing chain transfer agents have been disclosed for use in the polymerization of the HASE polymers, their use is not recommended as the mercaptan-containing chain transfer agent reduces the molecular weight of the polymer and, therefore, the polymer's thickening efficiency. , SUMMARY OF THE INVENTION
There has now been found a rheology-modifying copolymer composition desirably formed by dispersion or precipitation polymerization which, when introduced into an aqueous electrolyte-containing environment, will increase the viscosity of the solution. The polymeric rheology modifier is generally derived from one or more carboxylic acid monomers and hydrophobic monomers, with the incorporation of a hydrophobic mercaptan, a thioester or amino acid containing chain transfer agent into the copolymer composition, and a crosslinking agent. Optionally, a steric stabilizer can be included in the copolymer composition of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A monomeric component of the present invention utilized to form the polymeric rheology modifier is one or more monounsaturated carboxylic acid monomers having a total of from about 3 to about 12 carbon atoms. The monomer can be monocarboxylic or polycarboxylic. More specifically, the carboxylic monomers are the olefinically-unsaturated carboxylic acids containing at least one activated carbon-to-carbon olefinic double bond, and at least one carboxyl group;
that is, an acid or function readily converted to an acid containing an olefinic double bond either in the alpha-beta position with respect to a carboxyl group, C=C-COOH; or as part of a terminal methylene grouping, CH2=C<. Olefinically-unsaturated acids of this class include acrylic acids typified by acrylic acid itself, methacrylic acid, ethacrylic acid, alpha- cyano acrylic acid, beta methylacrylic acid (crotonic acid), alpha-phenyl acrylic acid, beta-acryloxy propionic acid, cinnamic acid, p-chloro cinnamic acid, 1-carboxy-4-phenyl butadiene-1,3, 3-acrylamido-3-methylbutanoic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, malefic acid, fumaric acid, and tricarboxy ethylene. As used herein, the term "carboxylic acid" includes the polycarboxylic acids and those acid anhydrides, such as malefic anhydride, wherein the anhydride group is formed by the elimination of one molecule of water from two carboxyl groups located on the same carboxylic acid molecule. Malefic anhydride and other acid anhydrides useful herein have the general structure R ~O
~ G- C~
to ~~ o R~ C- C
wherein R and R', independently, is hydrogen, halogen, or cyanogens, (C=N) or a hydrocarbon having a total of from 1 to 18 carbon atoms, such as alkyl, aryl, alkaryl, aralkyl, and cycloalkyl groups such as methyl, ethyl, propyl, octyl, decyl, phenyl, tol"yl, xylyl, benzyl, cyclohexyl, and the like.
The preferred carboxylic monomers are the monoolefinic acrylic acids having the general structure C H~ ~ - COOH
wherein RZ is a substituent such as hydrogen, halogen, and the cyanogens (C=N) groups, monovalent alkyl radicals, monovalent aryl radicals, monovalent aralkyl radicals, monovalent alkaryl radicals and the monovalent cycloaliphatic radicals having a total of from 1 to 4 carbon atoms. Of this class, acrylic and methacrylic acid are most preferred.
The amounts of such carboxylic acid monomers is generally from about 60% to 98% by weight, and preferably from about 80% to about 95% by weight based upon the total weight of the unsaturated acid monomers and the hydrophobic monomers.
These theology-modifying polymers, however, are frequently pH
dependent, are hydrolytically unstable, require their use in large amounts to effectively increase viscosity, or are sensitive to ionic components of the formulation. Additionally, these polymers are efficient only in aqueous systems having no electrolyte, such as sodium chloride.
Naturally occurring substances are also known for use as theology modifiers in aqueous systems. Natural theology modifiers include casein, alginates, gum tragacanth, and modified cellulose, including methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and carbomethoxy cellulose.
These products, however, vary in their thickening efficiency, generally provide poor flow and leveling properties, and are subject to microbial attack, thereby requiring the presence of antimicrobial agents.
The use of "associative" thickeners as theology modifiers in aqueous systems is also known in the art. An associative thickener refers to a water-soluble or water-swellable polymer having chemically attached groups capable of hydrophobic associations similar to those of conventional surfactants. These hydrophobic associations promote water insolubility and include such chemical groups as alkyl and aralkyl groups containing from about 4 to about 30 carbon atoms, or complex hydrophobic comonomers. Such associative thickeners have been disclosed in U.S. Patent 4,384,096 which describes associative polymers made via emulsion polymerization known as Hydrophobically-Modified Alkali-Soluble Emulsion Polymers CHASE). These polymers include both complex hydrophobes and conventional hydrophobes. However, while small amounts (0.01 to 5% by weight of monomer) of mercaptan-containing chain transfer agents have been disclosed for use in the polymerization of the HASE polymers, their use is not recommended as the mercaptan-containing chain transfer agent reduces the molecular weight of the polymer and, therefore, the polymer's thickening efficiency. , SUMMARY OF THE INVENTION
There has now been found a rheology-modifying copolymer composition desirably formed by dispersion or precipitation polymerization which, when introduced into an aqueous electrolyte-containing environment, will increase the viscosity of the solution. The polymeric rheology modifier is generally derived from one or more carboxylic acid monomers and hydrophobic monomers, with the incorporation of a hydrophobic mercaptan, a thioester or amino acid containing chain transfer agent into the copolymer composition, and a crosslinking agent. Optionally, a steric stabilizer can be included in the copolymer composition of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A monomeric component of the present invention utilized to form the polymeric rheology modifier is one or more monounsaturated carboxylic acid monomers having a total of from about 3 to about 12 carbon atoms. The monomer can be monocarboxylic or polycarboxylic. More specifically, the carboxylic monomers are the olefinically-unsaturated carboxylic acids containing at least one activated carbon-to-carbon olefinic double bond, and at least one carboxyl group;
that is, an acid or function readily converted to an acid containing an olefinic double bond either in the alpha-beta position with respect to a carboxyl group, C=C-COOH; or as part of a terminal methylene grouping, CH2=C<. Olefinically-unsaturated acids of this class include acrylic acids typified by acrylic acid itself, methacrylic acid, ethacrylic acid, alpha- cyano acrylic acid, beta methylacrylic acid (crotonic acid), alpha-phenyl acrylic acid, beta-acryloxy propionic acid, cinnamic acid, p-chloro cinnamic acid, 1-carboxy-4-phenyl butadiene-1,3, 3-acrylamido-3-methylbutanoic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, malefic acid, fumaric acid, and tricarboxy ethylene. As used herein, the term "carboxylic acid" includes the polycarboxylic acids and those acid anhydrides, such as malefic anhydride, wherein the anhydride group is formed by the elimination of one molecule of water from two carboxyl groups located on the same carboxylic acid molecule. Malefic anhydride and other acid anhydrides useful herein have the general structure R ~O
~ G- C~
to ~~ o R~ C- C
wherein R and R', independently, is hydrogen, halogen, or cyanogens, (C=N) or a hydrocarbon having a total of from 1 to 18 carbon atoms, such as alkyl, aryl, alkaryl, aralkyl, and cycloalkyl groups such as methyl, ethyl, propyl, octyl, decyl, phenyl, tol"yl, xylyl, benzyl, cyclohexyl, and the like.
The preferred carboxylic monomers are the monoolefinic acrylic acids having the general structure C H~ ~ - COOH
wherein RZ is a substituent such as hydrogen, halogen, and the cyanogens (C=N) groups, monovalent alkyl radicals, monovalent aryl radicals, monovalent aralkyl radicals, monovalent alkaryl radicals and the monovalent cycloaliphatic radicals having a total of from 1 to 4 carbon atoms. Of this class, acrylic and methacrylic acid are most preferred.
The amounts of such carboxylic acid monomers is generally from about 60% to 98% by weight, and preferably from about 80% to about 95% by weight based upon the total weight of the unsaturated acid monomers and the hydrophobic monomers.
Another monomeric component is a hydrophobic comonomer, these generally being esters of acids, and include the various (meth)acrylates or (meth)acrylamides of the formula:
CH2 = CH - C-X - R4 with R3 = H or methyl; X = O or NH; and Rø containing an alkyl, an amide such as an acrylamide and the like, or an alkoxy derivative or an cyano derivative thereof, having from about 2 to about 30 carbon atoms with 6 to about 30 carbon atoms being desirable and 12 to about 30 carbon atoms being preferred. The alkyl structure can contain primary, secondary, or tertiary carbon configurations.
Examples of such acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, n-pentyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-methyl-pentyl acrylate, n-octyl acrylate, 2-ethylhexyi acrylate, n-decyl acrylate, n-dodecyl acrylate, n-hexadecyl acrylate, n-octadecyl acrylate, behenyl acrylate, and the like; and also alkoxy derivatives thereof, such as methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate, and the like; and cyano derivatives thereof, such as a,f3-cyanoethyl acrylate, a, ~3 and b-cyanopropyl acrylate, cyanobutyf acrylate, cyanohexyl acrylate, cyanooctyl acrylte, and the like; methacrylates such as steryl methacrylate, methyl methacrylate, ethyl methacryiate, octyl methacrylate, isopropyl methacrylate, 2-ethylhexyl methacrylate, n-hexyl methacrylate, octadecyl methacrylate, behenyl methacrylate, dodecyl methacrylate, hexadecylmethacrylate, and the like. Mixtures of two or three or more long chain acrylic esters may be successfully polymerized with one of the carboxylic monomers. The (meth)acrylic amides include (meth)acrylamide, N-t-butyl (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, octadecyl (meth)acrylamide, behenyl (meth)acrylamide, dodecyl (meth)acrylamide, hexadecyl (meth)acrylamide, and the like, where "meth" is understood to mean . Additionally, the hydrophobic monomer can be a branched hydrophobe where R4 is (CH2)~C(CH3)3 and n= 1 to 3.
The preferred hydrophobic monomers are the linear, long chain hydrophobic monomers where R4 is an alkyl amide, or alkyl having at least12 carbon atoms, such as stearyl methacrylate, hexadecyl methacrylate, and behenyl methacrylate.
Optionally, or in lieu of the hydrophobic monomers described above, a complex hydrophobe can be utilized containing polyalkyleneoxide branches capped with hydrophobic alkyl or alkylaryl groups and having the formula (CH2 CH20)" R6 where R5 is H or methyl, R6 is C8-~x4 alkyl, alkaryl or the residue of a polycyciic hydrocarbyl, X is O or NH and n=1 to about 750.
For a (meth)acrylic acid ester of an alkoxylated alcohol R6 may typically be C$-C24 alkyl; alkylaryl, including alkylphenyl groups such as octylphenyl and nonylphenyl; or the residue of a polycyclic hydrocarbyl compound such as lanolin or cholesterol. Alkyl groups include, for example, octyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, palmityl, stearyl, eicosyl, and behenyl or docosyl.
Mixtures may also be used, such as alkyl groups resulting from the alkoxylation of a mixture of lauryl, stearyl, cetyl, and palmityi alcohols. Preferably, the esters are ethoxylated derivatives. Additionally, the complex hydrophobic monomers can include ethoxylated (4) nonyl phenol (meth)acrylate, ethoxylated (23) fauryl _7_ alcohol (methacrylate), ethoxylated (40) steryl alcohol (meth)acrylate, ethoxylated (23) behenyl alcohol (meth)acrylate, behenylethoxy (25) methacrylate, ethoxylated (25) tristyrlphenol (meth)acrylate, 3-phenoxy-2-hydroxypropyl methacrylate ,and methacrylated polystyrene.
The hydrophobic comonomer andlor the complex hydrophobic comonomer can be present in an amount from about 2 to about 40% by weight, and preferably from 5 to about 20% by weight based upon the total weight of the hydrophobic monomers and the unsaturated acid monomers.
Optionally, the polymer can contain nonionic, cationic, anionic and amphoteric or zwitterionic monomers. Examples of nonionic monomers include various hydroxy(meth)alkylacrylates where the alkyl portion has 1 to 10 carbon atoms such as hydroxyethyl(meth)acrylate; acrylamide; vinyl alcohol; vinyl esters such as vinyl acetate; n-vinylpyrrolidone, 1-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate; and the like including mixtures thereof.
Illustrative cationic monomers can include ammonium, sulfonium and phosphonium salts, quarternary ammonium salts such as diallyldimethylammonium chloride, diallyldiethylammonium chloride, diethylaminoethyl methacrylate, dimethyiaminoethyl methacrylate, methacryloyloxyethyltrimethy(ammonium sulfate, methacryloyloxyethyltrimethylammonium chloride, 3-(methacrylamido)propyltrimethylammonium chloride, and the like including mixtures thereof. Illustrative anionic monomers include p-styrene sulfonic acids, vinyl sulfonic acid, 2-acryiamido-2-methylpropane sulfonic acid, and the like including mixtures thereof. Illustrative amphoteric or zwitterionic monomers include 3-(2-acrylamido-2-methylpropyldimethylammonio)-1-propanesulfonate, co-N,N-dimethyl-N-methacroylamidoproplyammoniopropanesulfonate, N-vinylpyrrolidone-co-2-vinylpyridiniopropanesulfonate, and the like including mixtures thereof. These one or more monomers can be present in an amount from about 0.1 to about 15 parts by weight per' 100 parts by weight of the unsaturated acid monomers and the hydrophobic monomers.
_g_ An important component of the composition of the invention is the use of a hydrophobic chain transfer agent, which serves to attach hydrophobic groups on the ends of the crosslinked copolymer and act as pseudo non-polar crosslinks.
Typical of such hydrophobic chain transfer agents are, for example, long chain alkyl mercaptans and thioesters having from about 4 to about 30 carbon atoms, and preferably from about 8 carbon atoms to about 30 carbon atoms. Typical monomers useful as chain transfer agents include, for example, long chain alkyl mercaptans and thioesters such ~as n-dodecyl mercaptan, t-dodecyl mercaptan, octyl decyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, butyl thioglycolate, isoctyl thioglycolate and dodecyl thioglycolate; and thiols such as butane thiol, decanethiol, dodecanethiol, 1-hexadecane thiol, nonanethiol, octadecanethiol, tetradecanethiol, tridecane thiol,undecane thiol, 2,4-dimethylbenzene thiol, 2,5-dimethylbenzene thiol, perfluorodecanethiol, 1-napthalenethiol, 2,4-di-t-butyl thiophenol. Additionally, amino-carboxylic acid-mercaptan containing compounds, generally referred to as amino acids, or peptide fragments containing from 2 to 15 amino acids where at least one amino acid is cysteine or homocysteine, such as HS-glutathione. The preferred chain transfer agents for use in the invention are octadecyl mercaptan or dodecyl mercaptan.
The hydrophobic chain transfer agent can be present in an amount from about 0.05 to about 5, desirably from about 0.1 to about 3, and preferably from about 0.2 to about 1.5 parts by weight based upon 100 total parts by weight of the unsaturated acid and hydrophobic comonomers.
The copolymer of the present invention desirably is crosslinked by a crosslinking monomer. Various polyunsaturated monomers are utilized to generate either a partially or substantially-crosslinked three-dimensional network.
Crosslinking monomers include, for example, allyl ethers of sucrose or of pentaerythritol, or similar compounds, diallyl esters, dimethallyl ethers, allyl or methallyl acrylates and acrylamides, tetraallyl tin, tetravinyl silane, polyalkenyl _g_ urethanes, diacrylates and dimethacrylates, divinyl compounds such as divinyl benzene, divinyl glycol, polyallyl phosphate, diallyloxy compounds, phosphate esters, and the like. Typical of such polyunsaturated monomers are di, tri, or tetra, penta, or hexa-allyl sucrose; di, tri, or tetra-allyl pentaerythritol;
diallylphthalate, diallyl itaconate, diallyl fumarate, diallylmaleate, divinylbenzene, allylmethacrylate, allyl citrate, ethylene glycol di(meth)acrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, tetramethylene diethacrylate, tetramethylene dicarylate, ethylene diacrylate, ethylene dimethacrylate, triethylene glycol methacrylate, methylene bisacrylamide, and the like. Castor oils or polyols, esterfied with ethylenically unsaturated carboxylic acid and the like can also be used. Preferred crosslinking agents include allyl pentaerythritoi, allyl sucrose, trimethylolpropane allyl ether, and divinyl glycol.
The cross-linking monomer can be used in an amount from about 0.005 to about 10 parts by weight, desirably from about 0.01 to about 5.0 parts by weight, and preferably from about 0.05 to about 2.5 parts by weight based upon 100 parts by weight of all of the unsaturated acid and the hydrophobic monomers forming the copolymer.
A steric stabilizer may optionally be included in the copolymer composition in order to increase the solids content of the polymer slurry. Various steric stabilizers can be utilized, including triblock copolymers of stearyl esters.
The steric stabilizers have a hydrophilic group and a hydrophobic group and are generally block copolymers comprising a soluble block and an anchor block having a molecular weight (i.e.; chain length) usually well above 1000, but a hydrophobe length of more than 50 Angstroms. When the steric stabilizer is a linear block copolymer, it is defined by the formula ABA where A is a hydrophilic moiety having a molecular weight of from about 300 to about 60,000 and a solubility of less than 1 % in water at 25°C. Where the steric stabilizer is a random copolymeric comb steric stabilizer, it is defined by the formula R~Z",QnR2 where R and R are terminating groups an may be the same or different and will be different from Z and Q, Z is a hydrophobic moiety having a solubility of less than 1 % in water at 25°C, Q is a hydrophilic moiety having a solubility of more than 1 % in water at 25°C, and m and n are integers of 1 or more, and are selected such that the molecular weight of the polymer is from about 100 to about 250,000. Such steric stabilizers are described in U.S. Patent Nos.
5,373,044 and 5,349,030, and are hereby incorporated by reference.
Preferred steric stabilizers of the present invention include dimethicone copolyols, dimethicone copolyol esters, and dimethicone copolyol phthalate, al!
distributed by B. F. Goodrich. Examples of commercial compounds include Hypermer B-246 manufactured by ICI Surfactants and Pecosil~ distributed by Phoenix Chemical.
When the optional steric stabilizer is present, the polymeric mixture will usually contain from about 0.1 to about 10 parts by weight per 100 parts by weight of the unsaturated acid and the hydrophobic monomers forming the copolymer.
The polymers of the present invention are preferably made by dispersion or precipitation polymerization. Such polymerization processes are well-known in the art and have been previously described as in U.S. Patents 2,798,053; 3, 915,921; 3,940,351; 4,062,817; 4,066,583; 4,267,103; 5,349,030; and 5,373,044;
which are fully incorporated herein by reference.
Polymerization of the monomers is usually carried out in the presence of a free radical catalyst in a closed vessel in an inert atmosphere such as nitrogen, carbon dioxide, or argon under autogenous or artificially-induced pressure or optionally under reflux at atmospheric pressure. The temperature of the polymerization can vary from about 20°C to about 135°C, desirably from about 25°C to about 120°C and preferably from about 25°C to 100°C.
The polymerizations may be either batch, semi-batch or continuous. The agitation may be any agitation sufficient to maintain the slurry and obtain effective heat transfer including, for example, helical agitation, pitched turbines, and the like. Normal polymerization time is from about 1 to about 16 hours.
Typical free-radical forming catalysts include persulfates such as sodium, potassium or ammonium persulfates, peroxygen compounds such as caprylyl peroxide, benzoyl peroxide, hydrogen peroxide, pelargonyl peroxide, cumene hydroperoxides, diisopropyl peroxydicarbonate, tertiary butyl diperphthalate,tertiary butyl perbenzoate, sodium peracetate, di-(2-ethylhexyl) peroxy dicarbonate, and the like, as well as azo catalysts such as azobis(isobutyronitrile). Other catalysts utilizable are the so-called "redox"
type of catalyst, the heavy metal activated catalyst systems, and living free radical polymerization catalysts, including the s,s'-bis-(a, a' - disubstituted-a" -acetic acid) - trithiocarbonate and generally described by the formula:
R' S R' HOOC- ~- S- C-S- C-COOH
' wherein R' and R2, independently, can be the same or different, and can be linear or branched alkyls having from 1 to about 6 carbon atoms, or a C~ to about C6 alkyl having one or more substituents, or one or more aryls or a substituted aryl group having 1 to 6 substituents on the aryl ring, where the one or more substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms;
or an aryl; or a halogen such as fluorine or chlorine; or a cyano group; or an ether having a total of from 2 to about 20 carbon atoms such as methoxy, or hexanoxy; or a vitro; or combinations thereof. Examples of such compounds include s,s'-bis-2-methyl-2-propanoic acid-trithiocarbonate and s,s'-bis-(2-phenyl-2-propanoic acid)-trithiocarbonate. R' and R2 can also form or be a part of a cyclic ring having from 5 to about 12 total carbon atoms. R~ and R2 are preferably, independently, methyl or phenyl groups. Some systems polymerize solely by heat, but catalysts generally provide better control. The monomers may be batch charged or continuously added during the course of polymerization or by any other manner of polymerization techniques conventionally used.
The polymerization reactions described herein are normally conducted in inert diluents such as organic fluids or mixtures of organic fluids, in which the monomers are preferably soluble but in which the polymer is substantially insoluble, so that the polymer product is preferably obtained as a fine friable or fluffy precipitate. Suitable solvents include liquid hydrocarbons such as hexane and heptane; cycloalkanes such as cyclohexane; aromatics such as benzene and alkyl-subsituted benzenes such as toluene and xylene; alkyl carboxylates such as ethyl acetate, isopropyl acetate, propyl acetate, methyl acetate or butyl acetate; haloalkanes and chlorofluoroalkanes such as methylene chloride, ethylene dichloride and 1,1,1-trichloroethane, and mixtures thereof; ketones;
and mineral spirits with a flash point greater than abut 130°C, or mineral oil; and liquid or supercritical carbon dioxide and the like.
The amount by weight of polymerized solid product based upon the total weight of the solution will generally be from about 1 to about 50% and desirably from about 5 to about 50% and preferably from about 8 to about 40%.
Subsequent to the formation of the polymer composition, solvent is removed, as by filtration and/or evaporation, and the like.
The polymeric compositions described herein are most useful in an electrolyte-containing environment, including salt solutions and buffering systems. Various electrolytes can include sodium chloride, lithium chloride, potassium chloride, salts of magnesium, calcium, zinc, phosphorus, ammonium, sulfate, phosphate and carbonate. Such electrolyte solutions can be simple, or mixtures of dissolved ionic material may be present. Additionally, compounds with multiple charges and mixtures of charges may be used to make up the electrolyte solutions. Complex ions such as charged organic compounds (organic cations, organic anions), transition metal complexes such as metal oxides and charged organometallic compounds which dissolve to give ionic compounds, can be used to make up electrolyte solutions.
Where the electrolyte solution will be used under physiological conditions, ionic buffers and salt-containing solutions are generally useful. The pH and ionic make-up of such solutions are dependent upon the physiological location and condition under treatment.
A preferred electrolyte solution for the present invention can be a solution containing charged compounds, cations and anions, in a concentration generally from about 0.001 to about 5 weight %, and preferably from about 0.2 to about 3 weight %.
When the polymeric rheology modifier of the present invention is placed in an electrolytic solution, an unexpected increase in the viscosity of the solution is experienced. Such increase is generally from about 10, 25 or 50% up to about 400, 500 or 600%, or even 1000%. An increase in viscosity from about 100, 150 or 200% up to about 300 or 350% is preferred.
The polymeric compositions described herein are useful in a variety of systems, applications, with various compounds, and the like.
For example, the polymeric rheology modifier can be used in aqueous systems, including aqueous organic alcohols and emulsions, such as textile coatings (woven and non-woven), latex paint formulations, cosmetic formulations, pigment dispersions and slurries, dentrifices, hand lotions, liquid detergents, quenchants, agricultural chemicals, concrete additives, transmission fluids, waste water treatment, turbulent drag reduction, aircraft anti-icing, automative coatings, architectural coatings, industrial coatings, and the like.
The polymeric compositions of the present invention may have application in personal care applications, home care applications, and pharmaceutical applications.
Examples of various personal care applications include products such as the following: shampoos, for example 2-in-1 shampoos; baby shampoos;
conditioning shampoos; bodifying shampoos; temporary hair color shampoos; 3-in-1 shampoos; anti-dandruff shampoos; hair color maintenance shampoos; acid (neutralizing) shampoos; salicylic acid shampoos;
Skin and body cleansers, for example moisturizing washes; antibacterial body washes; bath gels; shower gels; hand soaps; bar soaps; body scrubs;
bubble baths; facial scrubs; foot scrubs;
Creams and lotions, for example alpha-hydroxy acid lotions and creams;
beta-hydroxy acid creams and lotions; sin whiteners; self tanning lotions;
sunscreen lotions; barrier lotions; moisturizers; hair styling creams; Vitamin C
creams; liquid talc products and ~ antibacterial lotions; and other moisturizing lotions and creams; and lotion treatments in non-woven substrates.
Skin and hair gels, for example facial masks, body masks, hydroalcoholic gels; hair gels; body gels; sunscreen gels; and the like, as well as other personal care applications such as permanent hair color, and the like.
Examples of home care applications include products such as: home care and industrial and institutional products, such as laundry detergents;
dishwashing detergents (automatic and manual); hard surface cleaners; disinfecting treatments on non-woven substrates; hand soaps, cleaners and sanitizers;
polishes (shoe, furniture, metal, etc.); automotive waxes, polishes, protectants, and cleaners, and the like.
Examples of pharmaceutical applications include topical formulations in the form of creams, lotions, ointments, or gels, where the polymeric theology modifier may be used as a wetting aid for the pharmaceutically active material, or as a skin penetration enhancer, or as an emulsifier for a solvent phase having an aesthetic effect, or present to enhance the solubility or bioavailability of the pharmaceutically active material, or as a bioadhesive agent for mucus membranes including ophthalmic, nasal, buccal, vaginal, gastrointestinal, urologic, esophageal, gastric, intestinal, and rectal. Similar formulations for internal application within the living body, or oral administration, or administration by mechanical means, can be utilized.
These formulations could be administered or applied to either human or veterinary conditions for the full breadth of indications treatable by pharmaceutical means, such as fever, irritation, dermatitis, rash; viral, fungal, or bacterial infection; organic disease; etc.
The pharmaceutical applications could have any appropriate function for treatment of the condition, and can.be a mixture of one or more pharmaceutically active materials, such as emetics, antiemetics, febrifuge, fungicide, biocide, bactericide, antibiotic, antipyretic, NSAID, emollient, analgesics, antineoplastics, cardiovascular agents, CNS stimulants, CNS depressants, enzymes, proteins, hormones, steroids, antipruritics, antirheumatic agents, biologicals, cough and cold treatments, dandruff products, gastrointestinal treatment agents, muscle relaxants, psychotherapeutic agents, skin and mucous membrane agents, skin care products, vaginal preparations, wound care agents, and other appropriate classes of pharmaceutically active agents capable of appropriate administration via dosage form.
Additionally, the polymeric compositions may be utilized in conjunction with various compounds such as a biological ingredient, e.g., active, such as pharmaceutical, medicinal, nutritional, and the like.
Examples of biological ingredients include Tretinoin; Progesterone; Methyl Salicylate, Capsaicin; Lidocaine; Prilocaine; Methyl Nicotinate; Crotamiton;
Avobenzone; Oxybenzone; Kaolin; Pectin, Sulfamethoxazole; Fentoin;
Albendazole, Pilocarpine HCI; Phenylpropanolamine HCI; Fluocinonide;
Formulated Actives in the 1998 Physicians Desk Reference~ and the like.
Various classes of medicinals which can be utilized include the following androgenotherapy; anesthetic; anorectic; anti-allergy; anti-asthmatic;
antibacterial; antibacterial keratolytic; antibiotics; anti-depressants;
antidermatosis; anti-diarrhea; anti-emetics; antifungal; anti-inflammatory;
anti-inflammatory, analgesic; anti-inflammatory, anti-pruritics; anti-inflammatory, vasoconstrictive; anti-malaria; anti-parasitic; anti-protozoal; antiseptic;
antiviral;
anti-vomiting; babies gum treatment; bronchitis; burns; conjunctiva, contraceptive agent; cornea therapy; cough; estrogen; eye moisturizer; gastro-intestinal treatment; glaucoma; hemorrhoids treatment; hair loss; heart disease; heart rhythm disorder; hormones; impotency; laxative; progestogen; revulsive; skin moisturizer; slimming; spasmophilia; spermacide; tooth health; urology;
vaccine adjuvant; vaginal moisturizer; vasodilative; vein therapy; viracide; wound treatment; and the like, and mixtures thereof.
Various other active medicinal ingredients which can be utilized include acetazolamide; aescin; aesculi hippocastan; allantoine; amfepramone;
aminopropylon; amorolfine; androstanolone; arnica; bamethan sulfate;
~5 benproperinembonate; benzalkonium chloride; benzocaine; benzoyl peroxide;
benzyl nicotinate; betamethasone; betaxolol chlohydrate; buphenine hydrochloride; caffeine; calendula; campher; cetylpyridinium chloride;
chloroquin phosphate; clarithromycin; clemastinhydrogene fumarate; clindamycin-2-dihydrogene phosphate; clobetasol-propionate; clotrimazole; codeine phosphate;
croconazole; crotamiton; dexamethasone acetate; dexpanthenol; diclofenac;
diethylamine salicylate; diflucortolone; diflucortolone valerate;
diflucortone, chlorquinaldol; difluoroprednate; dimethyl sulfoxide; dimeticone 350-silicium dioxide; dimetinden; dimetindenmaleat; disopyramide; domperidone; ergotoxine;
estradiol; estriol; etofenamate; felbinac; flubendazole; flufenamic acid;
fluocinolone; fluocinolone acetonide; fluocortolone; fusidic acid;
gelacturoglycani;
heparine; hydrocortisone; hydroxyehtyl salicylate; ibuprofen; idoxuridine;
imidazole salicylate;indomethacin; isoprenaline sulfate; ketoprofen;
levomenthol;
lidocaine hydrochloride; lindane; menthol; mepyramine; mesalazine; methyl nicotinate; methyl salicylate; metronidazole; miconazole; minoxidil; naftifin;
nalixidic acid; naproxen; niflumic acid; nifuratel; nifuratel nystatine;
nifuroxazide;
nitroglycerin; nonivamid; nystatinnifuratel; omoconazole nitrate; o-rutoside;
oxatomide; oxerutin; oxyphenbutazone; pancreatine; pentosane polysulfate;
phenolphthalein; phenylbutazone-piperazine; phenylephrine; pilocarpine;
piroxicam; plant extracts; polidoncanol; polycarbophil; polysaccharide;
potassium phosphate; prednisolone; prilocaine; primycin sulphafie lidocaine;
progesterone;
proteins; racem campher; verapamil; viloxazine; vintamin B6; xylitol;
xylometazolie; zincum hyaluronicum.
Other active medicinal compounds include rectacnyl tritinoin; retinal palmitate; salicylamide; salicylic' acid; sobrerol; sodium alginate; sodium bicarbonate; sodium fluoride; sodium pentosan polysulfate; sodium phosphate;
terpine; theophylline; thromboplastin; thymol; tocopherol acetate; tolmetin;
tretinoin; troxerutine.
Various pharmaceutical agents which can be utilized include Ascorbic Acid; Guaifenesin; Quinidine Gluconate; Aspirin; Isosorbide Dinitrate;
Quinidine Sulfate; Atenolol; Isoniazid; Sodium Valproate; Caramiphen HCI; Lithium Carbonate; Sulfamethizole; Chlorpheniramine Maleate; Mepyramine Maleate;
Theophylline; Dexchlorpheniramine; Methadone HCI; Thiamine; Diethyl Propion HCI; Metoclopramide; Tridecamine; Diphenhydramine; Nitrofurantoin; erapamil HCI; Ephedrine HCI; Phenylpropanolamine HCI; Viloxazine; Furosemide;
Pseudoephedrine; 2-Ethylnexyl Salicylate; Clocortolone pivalate; Kaolin;
Permethrin; Adapalene; Crotamiton; Lidocaine; Phenylbenzimidazole Sulfonic Acid; Albendazole; Desoximetasone; Menthol; Phenyl propanolamine;
Avobenzone; Dimethicone; Mesalamine; Pifocarpine HCI; Benzafkonium Chloride; Methyl Nicotinate; Piperonyl Butoxide; Benzocaine; Erythromycin;
Methyl Salicylate; Prilocaine; Benzoyl Peroxide; Ehtylhexyl p-Methoxycinnamate;
Metronidazole; Progesterone; Betamethasone dipropionate; Fenytoin; Naftifine HCI; Pyrethrum Extract; Betaxolol HCI; Fluocinonide; Nalicixic acid;
Rimexolone;
Camphor; Guaifenesin; Nitrofurantoin monohydrate; Simethicone; Capsaicins;
Homosalate; Octyl Methoxycinnamate; Sulfamethoxazole; Carithromycin;
Hydrocortisone; Oxybenzone Tretinoin; Clindamycin phosphate; Hydrocortisone valeratei; Padimate; Zinc Chloride; Clobetasol propionate; Hydroquinone;
Pectin;
2-Ethylhexyl Salicylate; Clocortolone pivalate; Kaolin; Permethrin; Adapalene;
Crotamiton; Lidocaine; Phenylbenzimidazole Sulfonic Acid; Albendazole;
Desoximetasone; Menthol; Phenylpropanolamine; Avobenzone; Dimethicone;
and Mesalamine.
The following examples show ways in which the invention can be practiced, as well as showing comparative examples. However, the examples should not be construed as limiting the invention.
20a EXAMPLE OF PREPARATION OF THE COPOLYMER
In order to illustrate the present invention, a polymerization reaction was conducted in a water jacketed two liter Pyrex resin kettle equipped with mechanical stirrer, a thermometer and reflux condenser topped with a nitrogen inlet connected to a bubbler to provide a slightly positive pressure of nitrogen throughout the polymerization. The water jacket was connected to a constant temperature circulator. In producing a copolymer, the resin kettle was charged with solvent, polymerizable monomers, crosslinker and chain transfer agent. A
steric stabilizing surface active agent may also be added. In accordance with the present invention, a varied amount of these monomers were added based upon the weight of the acrylic acid and co-acrylate ester monomers (i.e., phm or parts per hundred monomer). In all cases, the mixture was sparged with nitrogen for 30 minutes while the reactor was heated to the reaction temperature. Upon reaching the reaction temperature, the sparging tube was removed while a nitrogen purge was maintained, stirring was begun, and the recipe amount of di-(2-ethylhexyl)-peroxydicarbonate ( in an amount of 0.275g to 0.98g) was added.
Polymerization was evident in a matter of minutes as the solution became hazy with precipitated polymer. If polymerization did not start within 15 minutes, the mixture was resparged. After several hours the mixture became a thick slurry, and the polymerization continued for a total of 8 hours. The polymer slurry was then transferred to a single neck flask and the solvent was removed by a rotary evaporator at 95°C to 105°C at 27 inches vacuum. The resulting dry polymer product was a fine white powder. When dispersed in water, the polymer hydrates.
Thickening Viscosity A 1 % stock dispersion of the dry powder (8g/792g water) was prepared in demineralized water using a Li~htnin'mixer at 1,000 with a 3-blade marine impeller. The resin was introduced through a 20 mesh screen with stirring and the dispersion was mixed for a total of one hour.
The viscosity of the dispersion was then measured using a Brookfield RVT-DV Viscometer at 20 rpm. The viscosity of the dispersion is referred to as the Dispersion Viscosity or Un-neutralized Viscosity.
The dispersion was then neutralized to pH 7.3-7.8 with 18% NaOH using an S-paddle at 300 rpm for 3-5 minutes, after which the mucilages were allowed to stand at room temperature for at least 30 minutes.
The sample was then measured for Brookfiefd viscosity using a Brookfield RVT-DV Viscometer at 20 rpm. The viscosity of the neutralized dispersion is referred to as the Neutralized Viscosity.
Salt Sensitivity Sodium chloride was then added to the sample in solid form with stirring using an S-paddle at 300 rpm for 3-5 minutes. Salt additions of 2.0 g were made with the Brookfield viscosities being read between additions.
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CH2 = CH - C-X - R4 with R3 = H or methyl; X = O or NH; and Rø containing an alkyl, an amide such as an acrylamide and the like, or an alkoxy derivative or an cyano derivative thereof, having from about 2 to about 30 carbon atoms with 6 to about 30 carbon atoms being desirable and 12 to about 30 carbon atoms being preferred. The alkyl structure can contain primary, secondary, or tertiary carbon configurations.
Examples of such acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, n-pentyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-methyl-pentyl acrylate, n-octyl acrylate, 2-ethylhexyi acrylate, n-decyl acrylate, n-dodecyl acrylate, n-hexadecyl acrylate, n-octadecyl acrylate, behenyl acrylate, and the like; and also alkoxy derivatives thereof, such as methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate, and the like; and cyano derivatives thereof, such as a,f3-cyanoethyl acrylate, a, ~3 and b-cyanopropyl acrylate, cyanobutyf acrylate, cyanohexyl acrylate, cyanooctyl acrylte, and the like; methacrylates such as steryl methacrylate, methyl methacrylate, ethyl methacryiate, octyl methacrylate, isopropyl methacrylate, 2-ethylhexyl methacrylate, n-hexyl methacrylate, octadecyl methacrylate, behenyl methacrylate, dodecyl methacrylate, hexadecylmethacrylate, and the like. Mixtures of two or three or more long chain acrylic esters may be successfully polymerized with one of the carboxylic monomers. The (meth)acrylic amides include (meth)acrylamide, N-t-butyl (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, octadecyl (meth)acrylamide, behenyl (meth)acrylamide, dodecyl (meth)acrylamide, hexadecyl (meth)acrylamide, and the like, where "meth" is understood to mean . Additionally, the hydrophobic monomer can be a branched hydrophobe where R4 is (CH2)~C(CH3)3 and n= 1 to 3.
The preferred hydrophobic monomers are the linear, long chain hydrophobic monomers where R4 is an alkyl amide, or alkyl having at least12 carbon atoms, such as stearyl methacrylate, hexadecyl methacrylate, and behenyl methacrylate.
Optionally, or in lieu of the hydrophobic monomers described above, a complex hydrophobe can be utilized containing polyalkyleneoxide branches capped with hydrophobic alkyl or alkylaryl groups and having the formula (CH2 CH20)" R6 where R5 is H or methyl, R6 is C8-~x4 alkyl, alkaryl or the residue of a polycyciic hydrocarbyl, X is O or NH and n=1 to about 750.
For a (meth)acrylic acid ester of an alkoxylated alcohol R6 may typically be C$-C24 alkyl; alkylaryl, including alkylphenyl groups such as octylphenyl and nonylphenyl; or the residue of a polycyclic hydrocarbyl compound such as lanolin or cholesterol. Alkyl groups include, for example, octyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, palmityl, stearyl, eicosyl, and behenyl or docosyl.
Mixtures may also be used, such as alkyl groups resulting from the alkoxylation of a mixture of lauryl, stearyl, cetyl, and palmityi alcohols. Preferably, the esters are ethoxylated derivatives. Additionally, the complex hydrophobic monomers can include ethoxylated (4) nonyl phenol (meth)acrylate, ethoxylated (23) fauryl _7_ alcohol (methacrylate), ethoxylated (40) steryl alcohol (meth)acrylate, ethoxylated (23) behenyl alcohol (meth)acrylate, behenylethoxy (25) methacrylate, ethoxylated (25) tristyrlphenol (meth)acrylate, 3-phenoxy-2-hydroxypropyl methacrylate ,and methacrylated polystyrene.
The hydrophobic comonomer andlor the complex hydrophobic comonomer can be present in an amount from about 2 to about 40% by weight, and preferably from 5 to about 20% by weight based upon the total weight of the hydrophobic monomers and the unsaturated acid monomers.
Optionally, the polymer can contain nonionic, cationic, anionic and amphoteric or zwitterionic monomers. Examples of nonionic monomers include various hydroxy(meth)alkylacrylates where the alkyl portion has 1 to 10 carbon atoms such as hydroxyethyl(meth)acrylate; acrylamide; vinyl alcohol; vinyl esters such as vinyl acetate; n-vinylpyrrolidone, 1-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate; and the like including mixtures thereof.
Illustrative cationic monomers can include ammonium, sulfonium and phosphonium salts, quarternary ammonium salts such as diallyldimethylammonium chloride, diallyldiethylammonium chloride, diethylaminoethyl methacrylate, dimethyiaminoethyl methacrylate, methacryloyloxyethyltrimethy(ammonium sulfate, methacryloyloxyethyltrimethylammonium chloride, 3-(methacrylamido)propyltrimethylammonium chloride, and the like including mixtures thereof. Illustrative anionic monomers include p-styrene sulfonic acids, vinyl sulfonic acid, 2-acryiamido-2-methylpropane sulfonic acid, and the like including mixtures thereof. Illustrative amphoteric or zwitterionic monomers include 3-(2-acrylamido-2-methylpropyldimethylammonio)-1-propanesulfonate, co-N,N-dimethyl-N-methacroylamidoproplyammoniopropanesulfonate, N-vinylpyrrolidone-co-2-vinylpyridiniopropanesulfonate, and the like including mixtures thereof. These one or more monomers can be present in an amount from about 0.1 to about 15 parts by weight per' 100 parts by weight of the unsaturated acid monomers and the hydrophobic monomers.
_g_ An important component of the composition of the invention is the use of a hydrophobic chain transfer agent, which serves to attach hydrophobic groups on the ends of the crosslinked copolymer and act as pseudo non-polar crosslinks.
Typical of such hydrophobic chain transfer agents are, for example, long chain alkyl mercaptans and thioesters having from about 4 to about 30 carbon atoms, and preferably from about 8 carbon atoms to about 30 carbon atoms. Typical monomers useful as chain transfer agents include, for example, long chain alkyl mercaptans and thioesters such ~as n-dodecyl mercaptan, t-dodecyl mercaptan, octyl decyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, butyl thioglycolate, isoctyl thioglycolate and dodecyl thioglycolate; and thiols such as butane thiol, decanethiol, dodecanethiol, 1-hexadecane thiol, nonanethiol, octadecanethiol, tetradecanethiol, tridecane thiol,undecane thiol, 2,4-dimethylbenzene thiol, 2,5-dimethylbenzene thiol, perfluorodecanethiol, 1-napthalenethiol, 2,4-di-t-butyl thiophenol. Additionally, amino-carboxylic acid-mercaptan containing compounds, generally referred to as amino acids, or peptide fragments containing from 2 to 15 amino acids where at least one amino acid is cysteine or homocysteine, such as HS-glutathione. The preferred chain transfer agents for use in the invention are octadecyl mercaptan or dodecyl mercaptan.
The hydrophobic chain transfer agent can be present in an amount from about 0.05 to about 5, desirably from about 0.1 to about 3, and preferably from about 0.2 to about 1.5 parts by weight based upon 100 total parts by weight of the unsaturated acid and hydrophobic comonomers.
The copolymer of the present invention desirably is crosslinked by a crosslinking monomer. Various polyunsaturated monomers are utilized to generate either a partially or substantially-crosslinked three-dimensional network.
Crosslinking monomers include, for example, allyl ethers of sucrose or of pentaerythritol, or similar compounds, diallyl esters, dimethallyl ethers, allyl or methallyl acrylates and acrylamides, tetraallyl tin, tetravinyl silane, polyalkenyl _g_ urethanes, diacrylates and dimethacrylates, divinyl compounds such as divinyl benzene, divinyl glycol, polyallyl phosphate, diallyloxy compounds, phosphate esters, and the like. Typical of such polyunsaturated monomers are di, tri, or tetra, penta, or hexa-allyl sucrose; di, tri, or tetra-allyl pentaerythritol;
diallylphthalate, diallyl itaconate, diallyl fumarate, diallylmaleate, divinylbenzene, allylmethacrylate, allyl citrate, ethylene glycol di(meth)acrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, tetramethylene diethacrylate, tetramethylene dicarylate, ethylene diacrylate, ethylene dimethacrylate, triethylene glycol methacrylate, methylene bisacrylamide, and the like. Castor oils or polyols, esterfied with ethylenically unsaturated carboxylic acid and the like can also be used. Preferred crosslinking agents include allyl pentaerythritoi, allyl sucrose, trimethylolpropane allyl ether, and divinyl glycol.
The cross-linking monomer can be used in an amount from about 0.005 to about 10 parts by weight, desirably from about 0.01 to about 5.0 parts by weight, and preferably from about 0.05 to about 2.5 parts by weight based upon 100 parts by weight of all of the unsaturated acid and the hydrophobic monomers forming the copolymer.
A steric stabilizer may optionally be included in the copolymer composition in order to increase the solids content of the polymer slurry. Various steric stabilizers can be utilized, including triblock copolymers of stearyl esters.
The steric stabilizers have a hydrophilic group and a hydrophobic group and are generally block copolymers comprising a soluble block and an anchor block having a molecular weight (i.e.; chain length) usually well above 1000, but a hydrophobe length of more than 50 Angstroms. When the steric stabilizer is a linear block copolymer, it is defined by the formula ABA where A is a hydrophilic moiety having a molecular weight of from about 300 to about 60,000 and a solubility of less than 1 % in water at 25°C. Where the steric stabilizer is a random copolymeric comb steric stabilizer, it is defined by the formula R~Z",QnR2 where R and R are terminating groups an may be the same or different and will be different from Z and Q, Z is a hydrophobic moiety having a solubility of less than 1 % in water at 25°C, Q is a hydrophilic moiety having a solubility of more than 1 % in water at 25°C, and m and n are integers of 1 or more, and are selected such that the molecular weight of the polymer is from about 100 to about 250,000. Such steric stabilizers are described in U.S. Patent Nos.
5,373,044 and 5,349,030, and are hereby incorporated by reference.
Preferred steric stabilizers of the present invention include dimethicone copolyols, dimethicone copolyol esters, and dimethicone copolyol phthalate, al!
distributed by B. F. Goodrich. Examples of commercial compounds include Hypermer B-246 manufactured by ICI Surfactants and Pecosil~ distributed by Phoenix Chemical.
When the optional steric stabilizer is present, the polymeric mixture will usually contain from about 0.1 to about 10 parts by weight per 100 parts by weight of the unsaturated acid and the hydrophobic monomers forming the copolymer.
The polymers of the present invention are preferably made by dispersion or precipitation polymerization. Such polymerization processes are well-known in the art and have been previously described as in U.S. Patents 2,798,053; 3, 915,921; 3,940,351; 4,062,817; 4,066,583; 4,267,103; 5,349,030; and 5,373,044;
which are fully incorporated herein by reference.
Polymerization of the monomers is usually carried out in the presence of a free radical catalyst in a closed vessel in an inert atmosphere such as nitrogen, carbon dioxide, or argon under autogenous or artificially-induced pressure or optionally under reflux at atmospheric pressure. The temperature of the polymerization can vary from about 20°C to about 135°C, desirably from about 25°C to about 120°C and preferably from about 25°C to 100°C.
The polymerizations may be either batch, semi-batch or continuous. The agitation may be any agitation sufficient to maintain the slurry and obtain effective heat transfer including, for example, helical agitation, pitched turbines, and the like. Normal polymerization time is from about 1 to about 16 hours.
Typical free-radical forming catalysts include persulfates such as sodium, potassium or ammonium persulfates, peroxygen compounds such as caprylyl peroxide, benzoyl peroxide, hydrogen peroxide, pelargonyl peroxide, cumene hydroperoxides, diisopropyl peroxydicarbonate, tertiary butyl diperphthalate,tertiary butyl perbenzoate, sodium peracetate, di-(2-ethylhexyl) peroxy dicarbonate, and the like, as well as azo catalysts such as azobis(isobutyronitrile). Other catalysts utilizable are the so-called "redox"
type of catalyst, the heavy metal activated catalyst systems, and living free radical polymerization catalysts, including the s,s'-bis-(a, a' - disubstituted-a" -acetic acid) - trithiocarbonate and generally described by the formula:
R' S R' HOOC- ~- S- C-S- C-COOH
' wherein R' and R2, independently, can be the same or different, and can be linear or branched alkyls having from 1 to about 6 carbon atoms, or a C~ to about C6 alkyl having one or more substituents, or one or more aryls or a substituted aryl group having 1 to 6 substituents on the aryl ring, where the one or more substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms;
or an aryl; or a halogen such as fluorine or chlorine; or a cyano group; or an ether having a total of from 2 to about 20 carbon atoms such as methoxy, or hexanoxy; or a vitro; or combinations thereof. Examples of such compounds include s,s'-bis-2-methyl-2-propanoic acid-trithiocarbonate and s,s'-bis-(2-phenyl-2-propanoic acid)-trithiocarbonate. R' and R2 can also form or be a part of a cyclic ring having from 5 to about 12 total carbon atoms. R~ and R2 are preferably, independently, methyl or phenyl groups. Some systems polymerize solely by heat, but catalysts generally provide better control. The monomers may be batch charged or continuously added during the course of polymerization or by any other manner of polymerization techniques conventionally used.
The polymerization reactions described herein are normally conducted in inert diluents such as organic fluids or mixtures of organic fluids, in which the monomers are preferably soluble but in which the polymer is substantially insoluble, so that the polymer product is preferably obtained as a fine friable or fluffy precipitate. Suitable solvents include liquid hydrocarbons such as hexane and heptane; cycloalkanes such as cyclohexane; aromatics such as benzene and alkyl-subsituted benzenes such as toluene and xylene; alkyl carboxylates such as ethyl acetate, isopropyl acetate, propyl acetate, methyl acetate or butyl acetate; haloalkanes and chlorofluoroalkanes such as methylene chloride, ethylene dichloride and 1,1,1-trichloroethane, and mixtures thereof; ketones;
and mineral spirits with a flash point greater than abut 130°C, or mineral oil; and liquid or supercritical carbon dioxide and the like.
The amount by weight of polymerized solid product based upon the total weight of the solution will generally be from about 1 to about 50% and desirably from about 5 to about 50% and preferably from about 8 to about 40%.
Subsequent to the formation of the polymer composition, solvent is removed, as by filtration and/or evaporation, and the like.
The polymeric compositions described herein are most useful in an electrolyte-containing environment, including salt solutions and buffering systems. Various electrolytes can include sodium chloride, lithium chloride, potassium chloride, salts of magnesium, calcium, zinc, phosphorus, ammonium, sulfate, phosphate and carbonate. Such electrolyte solutions can be simple, or mixtures of dissolved ionic material may be present. Additionally, compounds with multiple charges and mixtures of charges may be used to make up the electrolyte solutions. Complex ions such as charged organic compounds (organic cations, organic anions), transition metal complexes such as metal oxides and charged organometallic compounds which dissolve to give ionic compounds, can be used to make up electrolyte solutions.
Where the electrolyte solution will be used under physiological conditions, ionic buffers and salt-containing solutions are generally useful. The pH and ionic make-up of such solutions are dependent upon the physiological location and condition under treatment.
A preferred electrolyte solution for the present invention can be a solution containing charged compounds, cations and anions, in a concentration generally from about 0.001 to about 5 weight %, and preferably from about 0.2 to about 3 weight %.
When the polymeric rheology modifier of the present invention is placed in an electrolytic solution, an unexpected increase in the viscosity of the solution is experienced. Such increase is generally from about 10, 25 or 50% up to about 400, 500 or 600%, or even 1000%. An increase in viscosity from about 100, 150 or 200% up to about 300 or 350% is preferred.
The polymeric compositions described herein are useful in a variety of systems, applications, with various compounds, and the like.
For example, the polymeric rheology modifier can be used in aqueous systems, including aqueous organic alcohols and emulsions, such as textile coatings (woven and non-woven), latex paint formulations, cosmetic formulations, pigment dispersions and slurries, dentrifices, hand lotions, liquid detergents, quenchants, agricultural chemicals, concrete additives, transmission fluids, waste water treatment, turbulent drag reduction, aircraft anti-icing, automative coatings, architectural coatings, industrial coatings, and the like.
The polymeric compositions of the present invention may have application in personal care applications, home care applications, and pharmaceutical applications.
Examples of various personal care applications include products such as the following: shampoos, for example 2-in-1 shampoos; baby shampoos;
conditioning shampoos; bodifying shampoos; temporary hair color shampoos; 3-in-1 shampoos; anti-dandruff shampoos; hair color maintenance shampoos; acid (neutralizing) shampoos; salicylic acid shampoos;
Skin and body cleansers, for example moisturizing washes; antibacterial body washes; bath gels; shower gels; hand soaps; bar soaps; body scrubs;
bubble baths; facial scrubs; foot scrubs;
Creams and lotions, for example alpha-hydroxy acid lotions and creams;
beta-hydroxy acid creams and lotions; sin whiteners; self tanning lotions;
sunscreen lotions; barrier lotions; moisturizers; hair styling creams; Vitamin C
creams; liquid talc products and ~ antibacterial lotions; and other moisturizing lotions and creams; and lotion treatments in non-woven substrates.
Skin and hair gels, for example facial masks, body masks, hydroalcoholic gels; hair gels; body gels; sunscreen gels; and the like, as well as other personal care applications such as permanent hair color, and the like.
Examples of home care applications include products such as: home care and industrial and institutional products, such as laundry detergents;
dishwashing detergents (automatic and manual); hard surface cleaners; disinfecting treatments on non-woven substrates; hand soaps, cleaners and sanitizers;
polishes (shoe, furniture, metal, etc.); automotive waxes, polishes, protectants, and cleaners, and the like.
Examples of pharmaceutical applications include topical formulations in the form of creams, lotions, ointments, or gels, where the polymeric theology modifier may be used as a wetting aid for the pharmaceutically active material, or as a skin penetration enhancer, or as an emulsifier for a solvent phase having an aesthetic effect, or present to enhance the solubility or bioavailability of the pharmaceutically active material, or as a bioadhesive agent for mucus membranes including ophthalmic, nasal, buccal, vaginal, gastrointestinal, urologic, esophageal, gastric, intestinal, and rectal. Similar formulations for internal application within the living body, or oral administration, or administration by mechanical means, can be utilized.
These formulations could be administered or applied to either human or veterinary conditions for the full breadth of indications treatable by pharmaceutical means, such as fever, irritation, dermatitis, rash; viral, fungal, or bacterial infection; organic disease; etc.
The pharmaceutical applications could have any appropriate function for treatment of the condition, and can.be a mixture of one or more pharmaceutically active materials, such as emetics, antiemetics, febrifuge, fungicide, biocide, bactericide, antibiotic, antipyretic, NSAID, emollient, analgesics, antineoplastics, cardiovascular agents, CNS stimulants, CNS depressants, enzymes, proteins, hormones, steroids, antipruritics, antirheumatic agents, biologicals, cough and cold treatments, dandruff products, gastrointestinal treatment agents, muscle relaxants, psychotherapeutic agents, skin and mucous membrane agents, skin care products, vaginal preparations, wound care agents, and other appropriate classes of pharmaceutically active agents capable of appropriate administration via dosage form.
Additionally, the polymeric compositions may be utilized in conjunction with various compounds such as a biological ingredient, e.g., active, such as pharmaceutical, medicinal, nutritional, and the like.
Examples of biological ingredients include Tretinoin; Progesterone; Methyl Salicylate, Capsaicin; Lidocaine; Prilocaine; Methyl Nicotinate; Crotamiton;
Avobenzone; Oxybenzone; Kaolin; Pectin, Sulfamethoxazole; Fentoin;
Albendazole, Pilocarpine HCI; Phenylpropanolamine HCI; Fluocinonide;
Formulated Actives in the 1998 Physicians Desk Reference~ and the like.
Various classes of medicinals which can be utilized include the following androgenotherapy; anesthetic; anorectic; anti-allergy; anti-asthmatic;
antibacterial; antibacterial keratolytic; antibiotics; anti-depressants;
antidermatosis; anti-diarrhea; anti-emetics; antifungal; anti-inflammatory;
anti-inflammatory, analgesic; anti-inflammatory, anti-pruritics; anti-inflammatory, vasoconstrictive; anti-malaria; anti-parasitic; anti-protozoal; antiseptic;
antiviral;
anti-vomiting; babies gum treatment; bronchitis; burns; conjunctiva, contraceptive agent; cornea therapy; cough; estrogen; eye moisturizer; gastro-intestinal treatment; glaucoma; hemorrhoids treatment; hair loss; heart disease; heart rhythm disorder; hormones; impotency; laxative; progestogen; revulsive; skin moisturizer; slimming; spasmophilia; spermacide; tooth health; urology;
vaccine adjuvant; vaginal moisturizer; vasodilative; vein therapy; viracide; wound treatment; and the like, and mixtures thereof.
Various other active medicinal ingredients which can be utilized include acetazolamide; aescin; aesculi hippocastan; allantoine; amfepramone;
aminopropylon; amorolfine; androstanolone; arnica; bamethan sulfate;
~5 benproperinembonate; benzalkonium chloride; benzocaine; benzoyl peroxide;
benzyl nicotinate; betamethasone; betaxolol chlohydrate; buphenine hydrochloride; caffeine; calendula; campher; cetylpyridinium chloride;
chloroquin phosphate; clarithromycin; clemastinhydrogene fumarate; clindamycin-2-dihydrogene phosphate; clobetasol-propionate; clotrimazole; codeine phosphate;
croconazole; crotamiton; dexamethasone acetate; dexpanthenol; diclofenac;
diethylamine salicylate; diflucortolone; diflucortolone valerate;
diflucortone, chlorquinaldol; difluoroprednate; dimethyl sulfoxide; dimeticone 350-silicium dioxide; dimetinden; dimetindenmaleat; disopyramide; domperidone; ergotoxine;
estradiol; estriol; etofenamate; felbinac; flubendazole; flufenamic acid;
fluocinolone; fluocinolone acetonide; fluocortolone; fusidic acid;
gelacturoglycani;
heparine; hydrocortisone; hydroxyehtyl salicylate; ibuprofen; idoxuridine;
imidazole salicylate;indomethacin; isoprenaline sulfate; ketoprofen;
levomenthol;
lidocaine hydrochloride; lindane; menthol; mepyramine; mesalazine; methyl nicotinate; methyl salicylate; metronidazole; miconazole; minoxidil; naftifin;
nalixidic acid; naproxen; niflumic acid; nifuratel; nifuratel nystatine;
nifuroxazide;
nitroglycerin; nonivamid; nystatinnifuratel; omoconazole nitrate; o-rutoside;
oxatomide; oxerutin; oxyphenbutazone; pancreatine; pentosane polysulfate;
phenolphthalein; phenylbutazone-piperazine; phenylephrine; pilocarpine;
piroxicam; plant extracts; polidoncanol; polycarbophil; polysaccharide;
potassium phosphate; prednisolone; prilocaine; primycin sulphafie lidocaine;
progesterone;
proteins; racem campher; verapamil; viloxazine; vintamin B6; xylitol;
xylometazolie; zincum hyaluronicum.
Other active medicinal compounds include rectacnyl tritinoin; retinal palmitate; salicylamide; salicylic' acid; sobrerol; sodium alginate; sodium bicarbonate; sodium fluoride; sodium pentosan polysulfate; sodium phosphate;
terpine; theophylline; thromboplastin; thymol; tocopherol acetate; tolmetin;
tretinoin; troxerutine.
Various pharmaceutical agents which can be utilized include Ascorbic Acid; Guaifenesin; Quinidine Gluconate; Aspirin; Isosorbide Dinitrate;
Quinidine Sulfate; Atenolol; Isoniazid; Sodium Valproate; Caramiphen HCI; Lithium Carbonate; Sulfamethizole; Chlorpheniramine Maleate; Mepyramine Maleate;
Theophylline; Dexchlorpheniramine; Methadone HCI; Thiamine; Diethyl Propion HCI; Metoclopramide; Tridecamine; Diphenhydramine; Nitrofurantoin; erapamil HCI; Ephedrine HCI; Phenylpropanolamine HCI; Viloxazine; Furosemide;
Pseudoephedrine; 2-Ethylnexyl Salicylate; Clocortolone pivalate; Kaolin;
Permethrin; Adapalene; Crotamiton; Lidocaine; Phenylbenzimidazole Sulfonic Acid; Albendazole; Desoximetasone; Menthol; Phenyl propanolamine;
Avobenzone; Dimethicone; Mesalamine; Pifocarpine HCI; Benzafkonium Chloride; Methyl Nicotinate; Piperonyl Butoxide; Benzocaine; Erythromycin;
Methyl Salicylate; Prilocaine; Benzoyl Peroxide; Ehtylhexyl p-Methoxycinnamate;
Metronidazole; Progesterone; Betamethasone dipropionate; Fenytoin; Naftifine HCI; Pyrethrum Extract; Betaxolol HCI; Fluocinonide; Nalicixic acid;
Rimexolone;
Camphor; Guaifenesin; Nitrofurantoin monohydrate; Simethicone; Capsaicins;
Homosalate; Octyl Methoxycinnamate; Sulfamethoxazole; Carithromycin;
Hydrocortisone; Oxybenzone Tretinoin; Clindamycin phosphate; Hydrocortisone valeratei; Padimate; Zinc Chloride; Clobetasol propionate; Hydroquinone;
Pectin;
2-Ethylhexyl Salicylate; Clocortolone pivalate; Kaolin; Permethrin; Adapalene;
Crotamiton; Lidocaine; Phenylbenzimidazole Sulfonic Acid; Albendazole;
Desoximetasone; Menthol; Phenylpropanolamine; Avobenzone; Dimethicone;
and Mesalamine.
The following examples show ways in which the invention can be practiced, as well as showing comparative examples. However, the examples should not be construed as limiting the invention.
20a EXAMPLE OF PREPARATION OF THE COPOLYMER
In order to illustrate the present invention, a polymerization reaction was conducted in a water jacketed two liter Pyrex resin kettle equipped with mechanical stirrer, a thermometer and reflux condenser topped with a nitrogen inlet connected to a bubbler to provide a slightly positive pressure of nitrogen throughout the polymerization. The water jacket was connected to a constant temperature circulator. In producing a copolymer, the resin kettle was charged with solvent, polymerizable monomers, crosslinker and chain transfer agent. A
steric stabilizing surface active agent may also be added. In accordance with the present invention, a varied amount of these monomers were added based upon the weight of the acrylic acid and co-acrylate ester monomers (i.e., phm or parts per hundred monomer). In all cases, the mixture was sparged with nitrogen for 30 minutes while the reactor was heated to the reaction temperature. Upon reaching the reaction temperature, the sparging tube was removed while a nitrogen purge was maintained, stirring was begun, and the recipe amount of di-(2-ethylhexyl)-peroxydicarbonate ( in an amount of 0.275g to 0.98g) was added.
Polymerization was evident in a matter of minutes as the solution became hazy with precipitated polymer. If polymerization did not start within 15 minutes, the mixture was resparged. After several hours the mixture became a thick slurry, and the polymerization continued for a total of 8 hours. The polymer slurry was then transferred to a single neck flask and the solvent was removed by a rotary evaporator at 95°C to 105°C at 27 inches vacuum. The resulting dry polymer product was a fine white powder. When dispersed in water, the polymer hydrates.
Thickening Viscosity A 1 % stock dispersion of the dry powder (8g/792g water) was prepared in demineralized water using a Li~htnin'mixer at 1,000 with a 3-blade marine impeller. The resin was introduced through a 20 mesh screen with stirring and the dispersion was mixed for a total of one hour.
The viscosity of the dispersion was then measured using a Brookfield RVT-DV Viscometer at 20 rpm. The viscosity of the dispersion is referred to as the Dispersion Viscosity or Un-neutralized Viscosity.
The dispersion was then neutralized to pH 7.3-7.8 with 18% NaOH using an S-paddle at 300 rpm for 3-5 minutes, after which the mucilages were allowed to stand at room temperature for at least 30 minutes.
The sample was then measured for Brookfiefd viscosity using a Brookfield RVT-DV Viscometer at 20 rpm. The viscosity of the neutralized dispersion is referred to as the Neutralized Viscosity.
Salt Sensitivity Sodium chloride was then added to the sample in solid form with stirring using an S-paddle at 300 rpm for 3-5 minutes. Salt additions of 2.0 g were made with the Brookfield viscosities being read between additions.
- 21~
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Polymer samples 5-9 were produced in accordance with the typical copolymerization process example and tests were conducted to characterize those polymers. These reactions show a combination of polymers that have lower viscosity upon neutralization and an increase in viscosity upon introduction of salt.
NeulraSized Viscosity Smp AA T- SMAX phmChain phm SolvtTempTS BV BV at BV BV
# BA link Trans 0.5 0.5 at 1.0 Wt% 1wt%NaCL1.0% wt%
Nazi 5 95 5 APE 0.25ODSH 0.3 CO 55 11 610 2,910 5,25016,300 6 95 5 APE 0.25ODSH 0.2 CO 55 11 640 1,960 3,43013,900 7 85 10 5 TMPDAE0.3ODSH 0.2 CO 45 11 10504500 6,40024,500 8 95 5 APE 0.25'Glutathiol0.27CO 55 11 13402210 7650 14,200 9 95 5 APE 0.25Glutathiot0.8 CO 55 11 30301490 6100 10,800 -h~-gwcamione Example 10 - 11 Polymer samples 10-11 were produced in accordance with the typical copolymerization process example in the presence of a steric stabilizer Hypermer B-246) and tests were conducted to characterize those polymers. These reactions show a combination of polymers that have lower viscosity upon neutralization and an increase in viscosity upon introduction of salt.
Neutralized Viscosity N ~ ~ ~ o m ~n 3 ~n 0 3 ~
G a ~ a o z ~ ~ ~ o ~ > > > >
r 3 a ~ .~ F ~ c- ~ m m m m ~- z ~, a E ~ x a a c. ~ ~
~
c ~
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r a ~ aoa~ o~ ~ c ~ ~.II ~- C
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a a I
Polymer samples 5-9 were produced in accordance with the typical copolymerization process example and tests were conducted to characterize those polymers. These reactions show a combination of polymers that have lower viscosity upon neutralization and an increase in viscosity upon introduction of salt.
NeulraSized Viscosity Smp AA T- SMAX phmChain phm SolvtTempTS BV BV at BV BV
# BA link Trans 0.5 0.5 at 1.0 Wt% 1wt%NaCL1.0% wt%
Nazi 5 95 5 APE 0.25ODSH 0.3 CO 55 11 610 2,910 5,25016,300 6 95 5 APE 0.25ODSH 0.2 CO 55 11 640 1,960 3,43013,900 7 85 10 5 TMPDAE0.3ODSH 0.2 CO 45 11 10504500 6,40024,500 8 95 5 APE 0.25'Glutathiol0.27CO 55 11 13402210 7650 14,200 9 95 5 APE 0.25Glutathiot0.8 CO 55 11 30301490 6100 10,800 -h~-gwcamione Example 10 - 11 Polymer samples 10-11 were produced in accordance with the typical copolymerization process example in the presence of a steric stabilizer Hypermer B-246) and tests were conducted to characterize those polymers. These reactions show a combination of polymers that have lower viscosity upon neutralization and an increase in viscosity upon introduction of salt.
Neutralized Viscosity N ~ ~ ~ o m ~n 3 ~n 0 3 ~
G a ~ a o z ~ ~ ~ o ~ > > > >
r 3 a ~ .~ F ~ c- ~ m m m m ~- z ~, a E ~ x a a c. ~ ~
~
10 85 10 5 TMPDAE0.3 ODSH0.2 I.5CO 55 17 870 3580 575019,100 11 85 10 5 TMPDAE0.3 ODSH0.2 3 CO 45 17 11503980 440019,400 Comparative polymer samples 1-2 were produced in accordance with the typical copolymerization process except that no hydrophobic monomers were incorporated into the polymerization and tests were conducted to characterize those polymers. These reactions show that the hydrophobic monomer or combination of hydrophobic monomers is essential to produce polymers that have lower viscosity upon neutralization and an increase in viscosity upon introduction of salt.
Neutralized Viscosity Exp AA T- SMA X phm ChainphmSolventTempTS BV BV at BV BV
0.5 1 # BA link Trans 0.5 1wt%NaCLat 1 wt% 1.0 wt%
wt% NaCI
1 1000 0 APE 0.25ODSH 0.5CO 55 11 72 22 120 36 2 1000 0 APE 0.25ODSH 0.75CO 55 11 34 12 44 17 ~ ~ ~ ~ ~ ~ ~ ~ ~
Comparative polymer samples 3-6 were produced in accordance with the typical copolymerization process except that a hydrophilic chain transfer agent were incorporated into the polymerization and tests were conducted to characterize those polymers. These reactions show that the hydrophobic chain transfer agent is essential to produce polymers that have lower viscosity upon neutralization and an increase in viscosity upon introduction of salt.
ExampleAA SMA X phm Chainphm SolventTemp TSBV BV at BV BV
# link Trans 0.5 0.5 at 1 wt! 1wt!NaCL1.0 1 wt% wt%
NaCI
3 95 5 APE 0.25*NAC0.5 **EtAc11 5517 10 28 27 4 95 5 APE 0.25NAC 0.75EtAc 11 5512 - 17 -95 5 APE 0.25NAC 0.75CO 11 558 - 11 -6 100 APE 0.27 EtAc 11 5515,400306 22,3004,600 .. ..",.,~ ~ "y.,.".....
**Ethy) Acetate 5 Emulsion Stabilization and Thickening in the Presence of Electrolyte A two phase emulsion was prepared. The polymer of Example 1 (0.40wt%) was dispersed in mineral oil (20 wt%). The mineral oil suspension was dispersed in water and neutralized with NaOH to a ph of 6.5. The Brookfield viscosity of the emulsion was measured and found to be 210 centipoise (cP). An addition of 1 wt% NaCI was made to the emulsion and the viscosity was measured and found to be 4040 cP. The sample was thenplaced in a 45°C
oven for two weeks. The stability and viscosity of the emulsion were then checked.
Minimal separation of the creamy*white emulsion occurred, and the viscosity did not change from 4040 cP.
Enhanced Thickening Viscosity in the Presence of SurFactant A gelled formulation was prepared with a surfactant. The polymer of Example 1 (1.5 wt%) was dispersed in water and stirred for 30 minutes.
Propylene glycol (10 wt%) and IGEPAL-CA 630 (1.5 wt%) was added to the solution and mixed well. The solution was pH adjusted to 4.35 with NaOH. The mixture gelled immediately and the Brookfield Viscosity was measured at 20 rpm.
The viscosity measured 64,500 cP.
While in accordance with the Patent Statutes the best mode and preferred embodiment have been set forth, the scope of the invention is not limited thereto but rather by the scope of the claims.
Neutralized Viscosity Exp AA T- SMA X phm ChainphmSolventTempTS BV BV at BV BV
0.5 1 # BA link Trans 0.5 1wt%NaCLat 1 wt% 1.0 wt%
wt% NaCI
1 1000 0 APE 0.25ODSH 0.5CO 55 11 72 22 120 36 2 1000 0 APE 0.25ODSH 0.75CO 55 11 34 12 44 17 ~ ~ ~ ~ ~ ~ ~ ~ ~
Comparative polymer samples 3-6 were produced in accordance with the typical copolymerization process except that a hydrophilic chain transfer agent were incorporated into the polymerization and tests were conducted to characterize those polymers. These reactions show that the hydrophobic chain transfer agent is essential to produce polymers that have lower viscosity upon neutralization and an increase in viscosity upon introduction of salt.
ExampleAA SMA X phm Chainphm SolventTemp TSBV BV at BV BV
# link Trans 0.5 0.5 at 1 wt! 1wt!NaCL1.0 1 wt% wt%
NaCI
3 95 5 APE 0.25*NAC0.5 **EtAc11 5517 10 28 27 4 95 5 APE 0.25NAC 0.75EtAc 11 5512 - 17 -95 5 APE 0.25NAC 0.75CO 11 558 - 11 -6 100 APE 0.27 EtAc 11 5515,400306 22,3004,600 .. ..",.,~ ~ "y.,.".....
**Ethy) Acetate 5 Emulsion Stabilization and Thickening in the Presence of Electrolyte A two phase emulsion was prepared. The polymer of Example 1 (0.40wt%) was dispersed in mineral oil (20 wt%). The mineral oil suspension was dispersed in water and neutralized with NaOH to a ph of 6.5. The Brookfield viscosity of the emulsion was measured and found to be 210 centipoise (cP). An addition of 1 wt% NaCI was made to the emulsion and the viscosity was measured and found to be 4040 cP. The sample was thenplaced in a 45°C
oven for two weeks. The stability and viscosity of the emulsion were then checked.
Minimal separation of the creamy*white emulsion occurred, and the viscosity did not change from 4040 cP.
Enhanced Thickening Viscosity in the Presence of SurFactant A gelled formulation was prepared with a surfactant. The polymer of Example 1 (1.5 wt%) was dispersed in water and stirred for 30 minutes.
Propylene glycol (10 wt%) and IGEPAL-CA 630 (1.5 wt%) was added to the solution and mixed well. The solution was pH adjusted to 4.35 with NaOH. The mixture gelled immediately and the Brookfield Viscosity was measured at 20 rpm.
The viscosity measured 64,500 cP.
While in accordance with the Patent Statutes the best mode and preferred embodiment have been set forth, the scope of the invention is not limited thereto but rather by the scope of the claims.
Claims (25)
1. A copolymer composition for increasing viscosity in an electrolyte-containing environment comprising:
said copolymer composition derived from at least one unsaturated carboxylic acid monomer wherein the amount of said unsaturated carboxylic acid monomer is from 60% to 98% by weight based upon the total weight of said unsaturated monomers and said hydrophobic monomers, at least one hydrophobic monomer;
a hydrophobic chain transfer agent comprising alkyl mercaptans, thioesters, amino acid-mercaptan-containing compounds or peptide fragemnts, or combinations thereof;
a cross-linking agent; and, optionally, a steric stabilizer.
said copolymer composition derived from at least one unsaturated carboxylic acid monomer wherein the amount of said unsaturated carboxylic acid monomer is from 60% to 98% by weight based upon the total weight of said unsaturated monomers and said hydrophobic monomers, at least one hydrophobic monomer;
a hydrophobic chain transfer agent comprising alkyl mercaptans, thioesters, amino acid-mercaptan-containing compounds or peptide fragemnts, or combinations thereof;
a cross-linking agent; and, optionally, a steric stabilizer.
2. A copolymer composition according to claim 1, wherein said unsaturated carboxylic acid monomer has from 3 to 12 carbon atoms.
3. A copolymer composition accordingly to claim 2, wherein said hydrophobic monomer has the formula:
¦ ¦
wherein R3 is H or methyl;
R4 is alkyl, amide, alkoxy or cyano derivative;
X is O or NH;
and mixtures thereof.
¦ ¦
wherein R3 is H or methyl;
R4 is alkyl, amide, alkoxy or cyano derivative;
X is O or NH;
and mixtures thereof.
4. A copolymer composition according to claim 3, wherein said cross-linking agent is an allyl ether of sucrose or pentaerythritol, diallyl esters, dimethallyl ethers, allyl or methallyl acrylates and acyrlamides, tetrallyl tin, tetravinyl silane, polyalkenyl urethanes, diacrylates and dimethacrylates, divinyl compounds, divinyl glycol, polyallyl phosphate, trimethoxypropylallyl ether, diallyloxy compounds, phosphate esters, and combinations thereof.
5. A copolymer composition according to claim 4, wherein said unsaturated carboxylic acid monomer is acrylic acid or methacrylic acid.
6. A copolymer composition according to claim 5, wherein said hydrophobic monomer is octadecyl methacrylate, hexadecyl methacrylate, behenyl methacrylate, steryl methacrylate, or combinations thereof.
7. A copolymer composition according to claim 6, wherein said cross-linking agent is an allyl ether of sucrose, an allyl ether of pentaerythritol, trimethylolpropane allyl ether, trimethoxypropylallyl ether, or divinyl glycol, or combinations thereof, and wherein said cross-linking agent is present in an amount from 0.01 to 5 parts by weight per 100 parts by weight of said unsaturated acid monomer and said hydrophobic monomer.
8. A copolymer composition according to claim 7, wherein said hydrophobic chain transfer agent is n-dodecyl mercaptan, t-dodecyl mercaptan, octyl decyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, butyl thioglycolate, isoctyl thiglycolate, dodecyl thioglycolate, dodecyl thioglycolate, butane thiol decanethiol, tridecane thiol, undecane thiol, 2,4-dimethylbenzene thiol, 2,5-dimethylbenzene thiol, perfluorodecanethiol, 1-napthalenethiol, 2,4-di-t-butyl thiophenol, or amino carboxylic acid-mercaptan containing compounds or peptide fragments containing from 2 to 15 amino acids where at least one amino acid is cysteine or homocysteine, and wherein said chain transfer agent has from 4 to . 30 carbon atoms, and wherein the amount of said hydrophobic chain transfer agent is from 0.05 to . 5 parts by weight per 100 parts by weight of said unsaturated acid monomers and said hydrophobic monomer.
9. The copolymer composition of claim 8, wherein said chain transfer agent is octadecyl mercaptan or dodecyl mercaptan and wherein said chain transfer agent is present in an amount from : 0.1 to 3 parts by weight based upon 100 total parts by weight of said unsaturated acid monomers and said hydrophobic monomers.
10. A copolymer composition according to claim 4 including said steric stablizer, wherein said steric stabilizer is a dimethicone copolyol, a dimethicone copolyol ester, or a dimethicone copolyol phthalate and said static stabilizer is present in an amount from _ . 0.1 to ' . 10 parts by weight per 100 parts by weight of said unsaturated acid monomers and said hydrophobic monomers.
11. A copolymer composition according to claim 1, further comprising at least one nonionic, cationic, anionic, amphoteric, or zwitterionic monomers, or combinations thereof.
12. A copolymer composition according to claim 8, further comprising at least one nonionic, cationic, anionic, amphoteric, or zwitterionic monomer, or combinations thereof, in an amount of from 0.1 to 10 parts by weight per 100 parts by weight of said unsaturated acid monomers and said hydrophobic monomers.
13. The copolymer composition according to claim 1, wherein said hydrophobic monomer is a complex hydrophobe having the formula:
wherein R5 is H or methyl;
X is O or NH;
R6 is C8-C24 alkyl, or alkylaryl, or the residue of a polycylic hydrocarbyl;
and n=1 to 750.
wherein R5 is H or methyl;
X is O or NH;
R6 is C8-C24 alkyl, or alkylaryl, or the residue of a polycylic hydrocarbyl;
and n=1 to 750.
14. A process far making the copolymer composition of claim 1, comprising precipitation or dispersion copolymerizing the monomeric mixture in the presence of a free-radical producing catalyst at a temperature between 20°C to . 135°C.
15. An aqueous composition comprising an electroyte-containing solution and an effective amount of an aqueous copolymer composition according to claim 1 to thicken said composition.
16. A personal care product containing the copolymer composition of claim 1.
17. A home-care product containing the copolymer composition of claim 1.
18. An industrial application product containing the copolymer composition of claim 1.
19. An agricultural application product containing the copolymer composition of any one of claims 1 to 15.
20. A therapeutic-containing composition adapted for use as a drug delivery system comprising the copolymer composition as defined in any one of claims 1 to 15.
21. An electrolyte composition containing the copolymer composition of any one of claims 1 to 15.
22. A process for preparing the copolymer composition of anyone of claims 1 to 15 having increased viscosity in a salt-containing environment comprising the steps of:
a) forming a mixture comprising at least one unsaturated carboxylic acid monomer, at least one hydrophobic monomer, a hydrophobic chain transfer agent comprising alkyl mercaptans, thioesters, or amino acid-mercaptan-containing compounds or peptide fragments, or combinations thereof, a cross-linking agent, and optionally, a steric stabilizer; and b) polymerizing said mixture to form said copolymer.
a) forming a mixture comprising at least one unsaturated carboxylic acid monomer, at least one hydrophobic monomer, a hydrophobic chain transfer agent comprising alkyl mercaptans, thioesters, or amino acid-mercaptan-containing compounds or peptide fragments, or combinations thereof, a cross-linking agent, and optionally, a steric stabilizer; and b) polymerizing said mixture to form said copolymer.
23. Use of the copolymer composition of any one of claims 1 to 15 increasing the viscosity of an electrolyte-containing solution.
24. The use of claim 23 wherein the viscosity of said electrolyte-containing solution is increased from 10% to 1000%.
25. The use of claim 22 wherein the viscosity of said electrolyte-containing solution is increased from 100% up to 350%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/694,917 | 2000-10-24 | ||
| US09/694,917 US6433061B1 (en) | 2000-10-24 | 2000-10-24 | Rheology modifying copolymer composition |
| PCT/US2001/032542 WO2002034793A2 (en) | 2000-10-24 | 2001-10-18 | Rheology modifying copolymer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2426128A1 true CA2426128A1 (en) | 2002-05-02 |
Family
ID=24790787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002426128A Abandoned CA2426128A1 (en) | 2000-10-24 | 2001-10-18 | Rheology modifying copolymer composition |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US6433061B1 (en) |
| EP (1) | EP1330477A2 (en) |
| JP (1) | JP2004512399A (en) |
| KR (1) | KR20030051735A (en) |
| CN (1) | CN1471545A (en) |
| AU (1) | AU2002213382A1 (en) |
| BR (1) | BR0114782A (en) |
| CA (1) | CA2426128A1 (en) |
| CZ (1) | CZ20031319A3 (en) |
| MX (1) | MXPA03003515A (en) |
| RU (1) | RU2003115881A (en) |
| WO (1) | WO2002034793A2 (en) |
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| US2798053A (en) | 1952-09-03 | 1957-07-02 | Goodrich Co B F | Carboxylic polymers |
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| CH606154A5 (en) | 1974-07-02 | 1978-11-15 | Goodrich Co B F | |
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| US4062817A (en) | 1977-04-04 | 1977-12-13 | The B.F. Goodrich Company | Water absorbent polymers comprising unsaturated carboxylic acid, acrylic ester containing alkyl group 10-30 carbon atoms, and another acrylic ester containing alkyl group 2-8 carbon atoms |
| US4066583A (en) | 1977-05-16 | 1978-01-03 | The B. F. Goodrich Company | Flexible water absorbent polymer compositions comprising (a) unsaturated carboxylic acid, acrylic ester containing alkyl group 10-30 carbon atoms, additional monomer plus (b) aliphatic diol |
| US4267103A (en) | 1978-12-07 | 1981-05-12 | The B. F. Goodrich Company | Solvent polymerization of carboxyl containing monomers |
| US4384096A (en) | 1979-08-27 | 1983-05-17 | The Dow Chemical Company | Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems |
| US4429097A (en) | 1982-09-16 | 1984-01-31 | Rohm And Haas Company | Alkyl poly(oxyalkylene) esters of acrylate oligomers and copolymers thereof for thickening purposes |
| US5292843A (en) | 1992-05-29 | 1994-03-08 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing macromonomers |
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| US5739196A (en) * | 1995-11-30 | 1998-04-14 | Union Carbide Chemicals & Plastics Technology Corporation | Latex compositions having wet adhesion and other improved rheological properties and methods of producing same |
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-
2000
- 2000-10-24 US US09/694,917 patent/US6433061B1/en not_active Expired - Fee Related
-
2001
- 2001-10-18 CA CA002426128A patent/CA2426128A1/en not_active Abandoned
- 2001-10-18 CN CNA018178995A patent/CN1471545A/en active Pending
- 2001-10-18 WO PCT/US2001/032542 patent/WO2002034793A2/en not_active Application Discontinuation
- 2001-10-18 AU AU2002213382A patent/AU2002213382A1/en not_active Abandoned
- 2001-10-18 CZ CZ20031319A patent/CZ20031319A3/en unknown
- 2001-10-18 KR KR10-2003-7005623A patent/KR20030051735A/en not_active Application Discontinuation
- 2001-10-18 EP EP01981760A patent/EP1330477A2/en not_active Withdrawn
- 2001-10-18 BR BR0114782-0A patent/BR0114782A/en not_active Application Discontinuation
- 2001-10-18 JP JP2002537779A patent/JP2004512399A/en not_active Withdrawn
- 2001-10-18 RU RU2003115881/04A patent/RU2003115881A/en not_active Application Discontinuation
- 2001-10-18 MX MXPA03003515A patent/MXPA03003515A/en unknown
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| Publication number | Publication date |
|---|---|
| EP1330477A2 (en) | 2003-07-30 |
| AU2002213382A1 (en) | 2002-05-06 |
| WO2002034793A3 (en) | 2002-10-03 |
| KR20030051735A (en) | 2003-06-25 |
| JP2004512399A (en) | 2004-04-22 |
| CN1471545A (en) | 2004-01-28 |
| MXPA03003515A (en) | 2003-08-07 |
| CZ20031319A3 (en) | 2003-09-17 |
| US6433061B1 (en) | 2002-08-13 |
| BR0114782A (en) | 2003-12-23 |
| RU2003115881A (en) | 2004-12-10 |
| WO2002034793A2 (en) | 2002-05-02 |
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| EEER | Examination request | ||
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