WO1998047937A1 - Polymeres amphoteres aux caracteristiques ioniques modifiables par ajustement du ph - Google Patents

Polymeres amphoteres aux caracteristiques ioniques modifiables par ajustement du ph Download PDF

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Publication number
WO1998047937A1
WO1998047937A1 PCT/US1998/008099 US9808099W WO9847937A1 WO 1998047937 A1 WO1998047937 A1 WO 1998047937A1 US 9808099 W US9808099 W US 9808099W WO 9847937 A1 WO9847937 A1 WO 9847937A1
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moiety
polymer
amphoteric polymer
moieties
reactant
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PCT/US1998/008099
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English (en)
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Joseph Thomas Ippoliti
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Joseph Thomas Ippoliti
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Priority to AU71475/98A priority Critical patent/AU7147598A/en
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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
    • 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
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • 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
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently

Definitions

  • the present invention is in the field of amphoteric polymers, and more particularly to amphoteric polymers having pendant cationic and anionic functional groups which are reversibly protonatable with changes in pH.
  • Hydrophilic polymers are water-compatible polymeric materials which contain polar segments that allow these materials to attract and absorb water. If there are enough of these polar segments present, the polymers will become soluble in water. On the other hand, if there are a fewer number of polar functionalities present, and/or the polymer chains are highly cross-linked, the polymers will absorb water, or swell, rather than be water soluble. Such swellable , systems are commonly referred to as “hydrogels" or “superabsorbant polymers”.
  • the polar segments within water compatible polymers may be comprised of polar functional groups (e.g. amide linkages) or may be ionic in nature, for example a carboxylate with a metal counterion.
  • water compatible polymers include diapers, feminine hygiene products, tapes for protecting fiber optic cables and sealants in building construction. They also can be used as drug delivery vehicles that release drugs on a time-dependent or an external stimuli-dependent basis (i.e. pH, ionic strength, concentration of a solute in a medium such as blood), artificial skin for burn victims and artificial muscle. These polymers can also be used as drug delivery vehicles that release drugs on a time-dependent or an external stimuli-dependent basis (i.e. pH, ionic strength, concentration of a solute in a medium such as blood), artificial skin for burn victims and artificial muscle. These polymers can also be used as a time-dependent or an external stimuli-dependent basis (i.e. pH, ionic strength, concentration of a solute in a medium such as blood), artificial skin for burn victims and artificial muscle. These polymers can also be used as a time-dependent or an external stimuli-dependent basis (i.e. pH, ionic strength, concentration of a solute in a medium such as blood), artificial
  • SUBSTITUTE SHETfRULE 26 applied in size-exclusion processes such as in biological filtration of water and in capillary gel electrophoresis.
  • the present invention advantageously provides amphoteric polymers whose ionic character can be controlled by adjusting pH. Moreover, the amphoteric polymers also possess ionic character over a wide range of pH values, and thus, the interactions between amphoteric polymers of the present invention and water involve both hydrogen bonding and ion-dipole forces. As a result, polymers of the present invention are extremely water compatible. "Water compatible" as used herein means that a polymer is substantially completely soluble in water in a pH range from 6 to 8, preferably 5 to 9, more preferably 2 to 1 1, or alternatively, if the polymer is water insoluble, that the polymer is capable of absorbing at least three times, preferably at least 10 times, its weight in water.
  • Polymers of the present invention can be provided with a wide range of physical properties. For example, they can be hard, rigid, brittle, resilient, elastic, rubbery, soft, flexible, or the like, as desired. Polymers of the present invention can also be provided with "self-healing" properties such that scratches or cracks formed in polymeric coatings of the invention tend to "heal" themselves.
  • the polymers are advantageously used in a wide range of applications, including uses as an adhesive, a water absorbing component of diapers, a water soluble protective coating, a water soluble antistatic treatment, a water or brine viscosifier, a drug delivery vehicle, a polyelectrolyte, an oil-field chemical, a brine drag reduction agent, and the like.
  • the present invention provides an amphoteric polymer comprising a plurality of pendant carboxylate moieties and a plurality of ammonium moieties.
  • each of the carboxylate and ammonium moieties is reversibly protonatable such that the ionic character of the moieties can be changed by adjusting pH.
  • the present invention provides a water compatible polyampholyte, comprising: (a) a plurality of pendant first functional groups, wherein each of said first functional groups independently exists as a deprotonated anion of an acid group when dispersed in water at a pH of about 7 or above and wherein said functional groups can be protonotated to form a nonionic form when dispersed in water at an acidic pH; and
  • each of said second functional groups independently exists as a protonated cation when dispersed in water at a pH of about 7 or below and wherein said second functional groups can be deprotonated to form a nonionic form when dispersed in water at a basic pH; and wherein the polymer includes a sufficient amount of the first and second functional groups such that the polymer is water compatible in a pH range from about 5 to about 9.
  • the present invention provides a method of making an amphoteric polymer, comprising the steps of
  • a ® is a positively charged, ionic moiety comprising a nitrogen atom covalently linked to four moieties with the proviso that no more than one of said four moieties is hydrogen and X 2 is a divalent linking group.
  • the present invention provides a method of making an amphoteric polymer, comprising the steps of:
  • Figure 1 is an illustration of a reaction scheme showing how one embodiment of an amphoteric polymer of the present invention is formed from a polymer having maleic anhydride functionality
  • Figure 2 is a specific application of the reaction scheme of Figure 1 ;
  • Figure 3 is an illustration of a reaction scheme showing how another embodiment of an amphoteric polymer of the present invention is formed from vinyl monomers;
  • Figure 4 is an illustration of a reaction scheme showing how to make the tertiary amine functional vinyl monomer of Figure 3;
  • Figure 5 is an illustration of a reaction scheme showing how another embodiment of an amphoteric polymer of the present invention is formed from (meth)acrylic acid and a vinyl monomer having tertiary amine functionality;
  • Figures 6A and 6B are an illustration of a two-step reaction scheme showing how another embodiment of an amphoteric polymer of the present invention is formed from maleic anhydride, a vinyl monomer having tertiary amine functionality, and an alcohol;
  • Figure 7 is an illustration of a reaction scheme showing how another embodiment of an amphoteric polymer of the present invention is formed from acrylic acid and 2-(dimethylamino)ethyl acrylate;
  • Figure 8 is an illustration of a reaction scheme showing how another embodiment of an amphoteric polymer of the present invention is formed from maleic anhydride and 2-(dimethylamino)ethyl acrylate;
  • Figure 9 is an illustration of a reaction scheme showing how another embodiment of an amphoteric polymer of the present invention is formed from maleic anhydride and 2-(dimethylamino)ethyl acrylate.
  • Amphoteric polymers of the present invention are uniquely characterized by pendant functional moieties whose ionic character is easily adjusted with changes in pH.
  • Such functionality includes a plurality of first pendant functional moieties, wherein each such first pendant functional moiety independently exists as a deprotonated anion of an acid group when the polymer is dispersed in water at a pH of about 7 or above and which can be protonated to form a nonionic acid group when the polymer is dispersed in water at an acidic pH.
  • SUBSTITUTE SHEET (RI ⁇ E 28)
  • Representative examples of such functionality include carboxylate, phosphonate, phosphate, sulfonate, sulfate, phosphate, and combinations thereof.
  • each moiety may further be complexed with a separate, cationic counterion other than hydrogen.
  • representative examples of such counterions include Na ® , Li ⁇ , K ⁇ , NH 4 ffi , combinations thereof, and the like.
  • use of such counterions is optional.
  • Embodiments of the present invention can be prepared in which a corresponding second pendant functional moiety serves as the first pendant functional moiety counterion and vice versa so that the use of separate counterions may be avoided, if desired.
  • the first pendant functional moiety may be protonated or deprotonated at will merely by adjusting the pH of the environment in which the amphoteric polymer is being used.
  • the first pendant functional moiety tends to be in an ionic, deprotonated form.
  • the first pendant functional moiety tends to exist in a nonionic, protonated form if there is a source of H ⁇ ions available.
  • the ionic character of the first pendant functional moiety is easily controlled merely by adjusting pH.
  • the functionality of the polymers of the present invention further includes a plurality of second pendant functional moieties, wherein each of such moieties independently exists as a protonated cation when the polymer is dispersed in water at a pH of about 7 or below and preferably can be deprotonated to a nonionic form when the polymer is dispersed in water at a basic pH.
  • Representative examples of such functionality include ammonium functionality, phosphonium functionality, sulfonium functionality, and combinations thereof.
  • ammonium refers to a moiety including a nitrogen atom linked to a plurality of moieties by four bonds when dispersed in water at a pH of 7, with the provisos that (1) one of the moieties comprises the polymer backbone which is linked to the nitrogen either directly through a single bond or indirectly through a divalent linking group, and (2) no more than one of the other moieties linked to the nitrogen is hydrogen.
  • sulfonium refers to a moiety including a sulfur atom linked to three other moieties when dispersed in water at a pH of about 7 with the provisos that (1) one of the moieties comprises the polymer backbone which is linked to the sulfur either directly through a single bond or indirectly through a divalent linking group, and (2) no more than one of the other moieties linked to the sulfur atom is hydrogen.
  • phosphonium refers to a moiety including a phosphorous atom linked to four other moieties when dispersed in water at a pH of about 7 with the provisos that (1) one of the moieties comprises the polymer backbone which is linked to the phosphorous either directly through a single bond or indirectly through a divalent linking group, and (2) no more than one of the other moieties linked to the sulfur atom is hydrogen.
  • ammonium, phosphonium, and sulfonium functionality may be represented by the following formulae, respectively:
  • R, and R 2 are each independently any suitable monovalent moiety subject to the provisos above. If desired, each may be straight, branched, or cyclic in structure. Further, pairs of the R, and R 2 substituents on any one moiety may be comembers of a ring structure linked to the nitrogen, sulfur, or phosphorus atom, as the case may be, through such pairs.
  • each of R, and R 2 may independently be selected from a cycloalkyl moiety, a branched alkyl moiety, a straight alkyl moiety, an alkaryl moiety, an aryl moiety, an alkoxy moiety, combinations of these, and the like.
  • each of R, and R 2 is independently an alkyl group of 1 to 20, preferably 1 to 4, and most preferably 1 to 2 carbon atoms. In many embodiments, any of R, and R 2 , is most conveniently -CH 3 .
  • each such second functional group of the present invention may further be complexed with a separate, anionic counterion.
  • a counterion designated herein as M ⁇
  • representative examples of such a counterion include a halogen atom, sulfates, carbonates, nitrates, perchlorates, combinations thereof, and the like.
  • use of such counterions is optional in that embodiments of the present invention can be prepared in which a corresponding pendant first functional group serves as the second functional group counterion and vice versa.
  • each second functional group includes one hydrogen atom, the second functional groups may be protonated or deprotonated at will merely by adjusting the pH of the environment in which the amphoteric polymer is being used.
  • the second functional group tends to be in an ionic, protonated form.
  • the second functional group tends to exist in a nonionic deprotonated form.
  • the ionic character of the second functional groups is easily controlled merely by adjusting pH.
  • the overall ionic character of the amphoteric polymers of the present invention may depend upon pH.
  • the second functional groups are ionic.
  • both the first and second functional groups are ionic, and the ionic strength of the polymers is at a maximum.
  • the first functional groups are ionic.
  • the polymers of the present invention exhibit ionic character over a wide range of pH values and thereby may be provided with excellent water compatibility characteristics over a wide pH range as well.
  • the polymers can incorporate a wide range of first and second pendant functional moieties with beneficial results.
  • the water soluble embodiments of the present invention would include a sufficient amount of such moieties such that the polymers are water compatible over a pH range including acidic, neutral, and basic pH values. Preferably, this would be a pH range of from about 5 to about 9, more preferably about 2 to about 11.
  • a pH range of from about 5 to about 9, more preferably about 2 to about 11.
  • independently providing polymers with an equivalent weight of to each functionality in the range from 170 to 900,000 grams/equivalent, preferably from 170 to 150,000 grams/equivalent, more preferably from about 170 to 1000 grams/equivalent would be suitable in the practice of the present invention.
  • the principles of the present invention can be applied to polymers having a wide range of molecular weights as well.
  • preferred polymers of the present invention may have a weight average molecular weight in the range from about 1000 to about 1.8 million, preferably from mabout 1000 to about 300,000.
  • the first pendant functional moiety comprises carboxylate functionality and the second pendant functional moiety comprises ammonium functionality.
  • Such amphoteric polymers comprise a plurality of first and second chain segments, wherein the first chain segments have the formula
  • each of X, and X 2 is independently a single bond or a divalent linking group
  • a ffi is a positively charged, ionic moiety comprising a nitrogen atom covalently linked to four moieties with the proviso that no more than one of said four moieties is hydrogen.
  • any divalent moiety which is capable of linking the carboxylate to the polymer backbone, in the case of X,, or A ® to the polymer backbone, in the case of X 2 may be used. Accordingly, any divalent linking group that can achieve such objectives would be suitable in the practice of the present invention.
  • such divalent linking group preferably has the formula:
  • X 3 is a divalent moiety having a molecular weight in the range from about 40 to about 2500 and Y 2 is selected from -O-, -NH-, -S- or -NR 3 -; wherein R 3 is a monovalent moiety other than hydrogen.
  • suitable divalent linking groups for use as X 3 include divalent groups that comprise an alkylene moiety, a polyether moiety, a perfluorinated polyether moiety, a polyester moiety, a polyurethane moiety, a polycarbonate moiety, a polyimide moiety, a polyamide moiety, an aryl moiety, an alkaryl moiety, an alkoxyaryl moiety, combinations thereof and the like.
  • the molecular weight and/or chemical structure of X 3 may be selected to provide the amphoteric polymer with certain kinds of properties as desired. For example, if it is desired for the amphoteric polymer to be able to form rigid or hard bodies, then X 3 may be a lower molecular weight divalent group or a larger divalent group with a rigid backbone. On the other hand, if it is desired for the amphoteric polymer to be able to form elastic, rubbery, or soft bodies, then X 3 may be a divalent group with a flexible backbone such as a polyether chain segment.
  • X is a single bond
  • X 2 has a structure according to Formula (6) wherein X 3 is an alkyl group of 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms, more preferably — CH 2 CH 2 — .
  • X may be a single bond
  • X 2 may be a polyether moiety having a molecular weight in the range from about 44 to about 2500, more preferably about 200 to about 900.
  • the ratio of the first pendant functional moieties to the second pendant functional moieties relative to each other may be selected within a wide range. However, if there are too few of the first pendant functional moieties, the polymer may not have sufficient ionic character for a desired application in basic environments. On the other hand, if there are too few of the second pendant functional moieties, the polymer may not have sufficient ionic character for a desired application in acidic environments. Accordingly, it is desirable if the molar ratio of the first functional groups to the second functional groups is in the range from 100: 1 to 1 : 100, preferably 20: 1 to 1 :20, more preferably about 1 :1.
  • Embodiments of the invention according to formulae (4) and (5) in which the ratio of first chain segments to second chain segments is 1 :1 are particularly advantageous.
  • separate counterions for the carboxylate and ammonium moieties are not required at such a ratio, because the carboxylate serves as the counterion for the ammonium and vice versa.
  • the preferred polymers of the present invention may be provided with built-in counterion capability so that the use of separate counterions may be avoided. Avoiding the presence of separate counterions is desirable in many applications.
  • Counterions, particularly metal counterions are often reactive in undesirable ways. For example, separate counterions can oxidize metals in close proximity to the polymer, counterions are subject to ion exchange, and counterions affect ion concentration.
  • preferred embodiments of the invention do not necessarily include separate counterions, such embodiments are particularly useful as electrolytes in applications in which the presence of counterions would otherwise cause problems.
  • polymers of the present invention can be used as electrolytes in a battery where counterions, if present, would tend to attack and damage battery electrodes.
  • Other examples of such applications include capillary electrophoresis.
  • first and second chain segments are in sufficiently close proximity to facilitate the ability of the carboxylate and ammonium moieties to act as counterions for each other.
  • at least a portion of the first and second chain segments are covalently linked to each other such that the polymer comprises a plurality of amphoteric chain segments of the formula
  • each amphoteric pair of a polymer such as the amphoteric pairs shown in Formulae (7) or (8), are spaced apart from other amphoteric pairs. Accordingly, it may be desirable if the polymer further incorporates backbone chain segments of at least two carbon atoms between pairs in order to achieve this objective. In preferred embodiments of the invention, such additional backbone chain segments are derived from ethylene such that the polymer comprises a plurality of chain segments of the formula
  • Each amphoteric pair included in a structure according to formula (9) is thus spaced apart from other pairs by a polymer backbone segment comprising the two carbon atoms derived from ethylene.
  • Amphoteric polymers of the present invention show tremendous compatibility with water. Consequently, polymers of the present invention with substantially linear backbones are very water soluble over a wide range of pH values and concentrations.
  • Other embodiments of polymers of the present invention optionally may be formed with branched structures such that the polymers are water insoluble while still showing tremendous ability to absorb large quantities of water, e.g., several times their weight in water. This makes such branched embodiments of the present invention particularly suitable in applications, e.g., in diapers, in which so-called "superabsorbent" characteristics are desirable.
  • An amphoteric polymer with a branched structure i.e., a water insoluble, yet water absorbing amphoteric polymer, can be made in several ways.
  • such a polymer is prepared by inco ⁇ orating a plurality of chain segments derived from N,N'-methylenebisacrylamide into the polymer.
  • the use of N,N'-methylenebisacrylamide to make superabsorbent polymers has been described in J. Chem. Ed., "Synthesis of Superabsorbent Polymers", vol. 74, pp. 95- 6.
  • such superabsorbent polymers are prepared by incorporating a multifunctional monomer into the polymer backbone such that the resultant backbone of the polymer is sufficiently branched so that the polymer absorbs water, but is water insoluble.
  • such multifunctional monomers include monomers comprising a plurality of carbon-carbon double bonds, preferably at least three carbon-carbon double bonds.
  • Representative examples of such multifunctional monomers include divinylbenzene, ethylene glycol diacrylate, butylene glycoldiacrylate, triallylamine, allylmethacrylate, 1,1,1,-trimethylolpropane triacrylate, tetraallyloxyethane, combinations of these, and the like.
  • a wide range of amounts of monomers such as N,N'- methylenebisacrylamide, or a monomer comprising a plurality of carbon-carbon double bonds, combinations thereof, or the like, may be incorporated into an amphoteric polymer with beneficial results.
  • the amount of such monomers incorporated into an amphoteric polymer will depend to a great extent upon the amount of water absorbent characteristics which are desired in the final polymer product as well as the application in which the polymer will be used.
  • using greater amounts of such monomer or monomers provides a polymer with greater water absorbing capabilities up to a practical limit beyond which using more monomer provides little added benefit.
  • amphoteric polymers of the present invention may be prepared using a variety of approaches. According to one approach, a polymer comprising one or more chain segments having maleic anhydride functionality of the formula
  • a first reactant is reacted with a second reactant comprising a tertiary amine moiety and a nucleophilic moiety.
  • the nucleophilic moiety undergoes a nucleophilic reaction with the maleic anhydride functionality of the polymer, thereby linking said second reactant to one of the carboxyl moieties of the maleic anhydride group while simultaneously forming a carboxylate.
  • a first reactant is a maleic anhydride functional polymer comprising a maleic anhydride chain segment 10 having two carboxyl groups cyclically linked to each other via an oxygen atom.
  • the polymer incorporating chain segment 10 may be any polymer inco ⁇ orating one or more of such maleic anhydride chain segments.
  • the first reactant including chain segment 10 is a vinyl copolymer obtained by copolymerizing vinyl monomers comprising maleic anhydride and optionally one or more other vinyl monomers.
  • a particularly preferred vinyl copolymer of the present invention is an alternating block copolymer of ethylene and maleic anhydride having a weight average molecular weight in the range from 1,000 to 1.8 million.
  • such copolymers have excellent spacing (two carbon atoms in the backbone provided by the ethylene) between anhydride groups while otherwise maximizing the anhydride content of such copolymers.
  • the use of such copolymers results in the production of amphoteric polymers characterized by a molar ratio of carboxylate to ammonium moieties of 1 : 1 so that separate counterions are not required.
  • the amphoteric polymers so produced comprise amphoteric pairs according to Formula (7) above.
  • the amphoteric polymers so produced are also extremely water compatible due to the resultant high content of carboxylate and ammonium moieties.
  • Second reactant 12 comprises divalent linking group X 3 , nucleophilic moiety Y,, and moiety A.
  • nucleophilic moieties suitable for use as Y include -OH, -NH 2 , -SH, and -NHR 3 , wherein R 3 is a monovalent moiety other than hydrogen.
  • R 3 is an alkyl group of 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms, more preferably -CH 3 .
  • the divalent linking group X 3 has been defined above with respect to Formula (6), and is preferably selected from an alkylene group of 1 to 20 carbon atoms or a polyether moiety having a molecular weight in the range from 44 to about 900.
  • the moiety A is a moiety comprising an amine group having a nitrogen atom linked to X 3 and to two monovalent substituents, wherein neither substituent is hydrogen or an acidic group.
  • moiety A is represented by the formula
  • each of R 4 and R 5 is independently a monovalent moiety other than hydrogen or an acid group.
  • each of R 4 and R 5 is independently an alkyl group of 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms, more preferably -CH 3 .
  • One preferred class of compounds suitable for use as second reactant 12 is represented by the formula
  • the first reactant inco ⁇ orating chain segment(s) 10 and second reactant 12 are reacted together at room temperature in a suitable nonaqueous, polar solvent, such as THF or ether, at a substantially neutral pH.
  • a suitable nonaqueous, polar solvent such as THF or ether
  • first reactant chain segment 10 includes a plurality of maleic anhydride chain segments
  • the intermediate reaction product will likewise include a corresponding plurality of chain segments 14.
  • the nucleophilic moiety reacts with one of the carboxyl moieties to form linkage Y 2 between the carboxyl group and the divalent linking group X 3 .
  • the nature of Y 2 depends upon what kind of nucleophilic moiety is used as Y,. For example, if Y, is OH, then Y 2 is -O-. If Y, is -SH, then Y 2 will be -S-.
  • each chain segment 10 As seen from the structure of chain segment 14, the other carboxyl group of the chain segment 10 forms -COOH.
  • the hydrogen on this -COOH group spontaneously shifts to the A moiety.
  • the -COOH becomes an ionic carboxylate group
  • the tertiary amine group A becomes the corresponding protonated ammonium group A ® .
  • Amphoteric polymer chain segment 16 results.
  • the resultant carboxylate and ammonium moieties form amphoteric pairs.
  • Each ionic moiety is thus capable of acting as a counterion for the other.
  • each chain segment 10 tends to react with only one second reactant 12 so that the reaction scheme provides a very high yield of amphoteric chain segments 16. Very few, if any, of the chain segments 10 will react with two second reactants 12 such that both carboxyl groups form linkages to the A groups.
  • first reactant 20 is a chain segment of a 50:50, alternating block, vinyl copolymer of ethylene and maleic acid anhydride.
  • Second reactant 22 corresponds to a compound of formula (12) in which Y, is -OH, and each of R 4 and R 5 is -CH 3 .
  • the maleic acid anhydride moiety of first reactant 20 has reacted with second reactant 22 to form a polymer comprising chain segment 24 having pendant -COOH and tertiary amine functionality.
  • the hydrogen on the COOH group spontaneously shifts to the tertiary amine moiety, and a polymer having amphoteric chain segment 26 is thereby produced.
  • such polymers are formed by copolymerizing vinyl monomers comprising a tertiary amine functional vinyl monomer, an acid functional vinyl monomer, and optionally one or more additional copolymerizable vinyl monomers (not shown) as desired.
  • the acid group of the acid functional monomer is preferably -COOH, but could also be the protonated form of sulfate, sulfonate, phosphate, phosphonate, or the like.
  • additional vinyl monomers include vinyl acetate, vinyl chloride, vinylidene chloride, divinyl benzene, styrene, a-methyl styrene, alkylated styrene, alkoxy styrene, alkyl(meth)acrylate, acrylonitrile, hydroxy functional (meth)acrylate, vinyl naphthalene, alkylated vinyl naphthalene, alkoxy vinyl naphthalene, (meth)acrylamide, (meth)acrylimide, N- vinyl pyrolidone, isobornyl (meth)acrylate, allyl (meth)acrylate, combinations of these, and the like.
  • such additional vinyl monomer(s) may include N,N'-methylenebisacrylamide, multifunctional vinyl monomers comprising at least two, preferably three carbon-carbon double bonds, combinations of these, and the like.
  • first reactant 30 may be any vinyl monomer comprising a tertiary amine moiety and a polymerizable carbon-carbon double bond.
  • A represents a moiety of the formula
  • R 4 and R 5 are each independently a monovalent moiety other than hydrogen, preferably an alkyl group of 1 to 4 carbon atoms, more preferably -CH 3 ;
  • X 3 is a divalent linking group according to the definition of X 3 given for Formula (6) above; and R is hydrogen or a lower alkyl group of 1 to 4 carbon atoms, preferably hydrogen or -CH 3 .
  • Second reactant 32 may be any vinyl monomer comprising acid functionality and a polymerizable carbon-carbon double bond.
  • second reactant is a (meth)acrylic acid type compound, wherein Rg is as defined above.
  • Other examples of compounds suitable for use as second reactant 32 include acrylic acid, p-vinyl benzoic acid, and the like.
  • First reactant 30, second reactant 32, and other vinyl monomers if any, may be reacted together within a wide range of concentrations relative to each other. Appropriate amounts can be selected in accordance with conventional practices to provide resultant amphoteric polymers having the molecular weight ranges and molar ratios between functional groups as described above.
  • the molar ratio of the first reactant 30 to the second reactant 32 is in the range from 1 : 100 to 100: 1 , preferably 1 : 10 to 10:1, more preferably about 1 :1.
  • the vinyl copolymers of the present invention of Figure 3 may be prepared using any suitable free radical polymerization technique including bulk, solution, emulsion, and suspension polymerization methods.
  • first reactant 30 and second reactant 32 are added to water.
  • second reactant 32 acrylic acid
  • first reactant 30 the methacrylated amine
  • Both reactants 30 and 32 are ionic and fully water soluble as a result, making it easy to now carry out the polymerization in water.
  • optional additives such as a chain-transfer agent, a free radical polymerization initiator, or the like, may be added to facilitate the polymerization.
  • the solution may be sealed in an inert atmosphere and then agitated at a temperature sufficient to activate the initiator.
  • Free radical initiators suitable for solution polymerization include those that are soluble in the reaction solvent, including, but not limited to, azo compounds, peroxides, and combinations of these.
  • useful peroxide initiators include those chosen from benzoyl peroxide, lauroyl perodice, di-t-butyl peroxide, and the like.
  • useful azo compound initiators include those chosen from the group consisting of 2,2'- azobis(2-methylbutyronitrile), and 2,2'azobis(isobutyronitrile).
  • a preferred initiator is 2,2'azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride commercially available under the trade designation VA-044 from Wako Chemical.
  • equimolar amounts of the vinyl monomers are copolymerized at elevated temperature in aqueous solution containing 1-10 mole percent, preferably 1 to 5 mole percent, initiator based upon the monomers to be copolymerized.
  • the resultant copolymer 38 comprises one or more carboxylate functional chain segments 34 and one or more ammonium functional chain segments 36 in the backbone of copolymer 38.
  • Figure 4 illustrates a particularly preferred, two-step reaction scheme for preparing first reactant 30 shown in Figure 3.
  • tertiary amine nucleophile 40 is reacted with (meth)acrylate functional acyl halide 42 to provide ammonium functional (meth)acrylate 44.
  • A is a moiety of the formula: R 4
  • R 4 and R 5 are as defined above with relation to Formula (14).
  • X 3 is a divalent linking group as defined above, preferably -CH 2 CH 2 - or a polyether moiety having a molecular weight in the range from about 44 to about 900.
  • Y is a nucleophilic moiety, preferably -OH.
  • Y 3 is a halogen atom, preferably chlorine.
  • Y 2 and Rg are as defined above in connection with Figure 1.
  • a ® is the protonated form of A.
  • the reaction takes place at room temperature in a solvent such as THF or ether, wherein the molar ratio of reactant 40 to reactant 42 is about 1:1.
  • the reaction is self-catalyzed, and yields of about 100% have been achieved.
  • the ammonium functional (meth)acrylate 44 is treated with an aqueous base, such as sodium hydroxide (NaOH), potassium carbonate (K 2 CO 3 ) or the like, in order to deprotonate the ammonium moiety to produce reaction product 46, a tertiary amine functional (meth)acrylate.
  • Reaction product 46 is then extracted into an organic solvent, such as ether, and the solvent subsequently removed to recover reaction product 46, thereby removing any added counterions and providing a tertiary amine functional (meth)acrylate 46 suitable for use as first reactant 30 in Figure 3.
  • Amphoteric polymers of the present invention may also be prepared by polymerizing a monomer having tertiary amine functionality and a polymerizable carbon-carbon double bond with a monomer comprising acid functionality and a polymerizable carbon-carbon double bond vie free radical polymerization.
  • the molar ratio of these monomers relative to each other is in the range from 1 : 100 to 100: 1 , preferably 1 : 10 to 10:1, more preferably about 1 :1.
  • the carboxylate moiety of the one monomer as well as the tertiary amine moiety of the other monomer become pendant from the resultant polymer backbone.
  • a representative example of this approach is illustrate schematically in Figure 5.
  • a first reactant 50, (meth)acrylic acid, and a second reactant 52, a (meth)acrylate functional tertiary amine are copolymerized to form copolymer 58 comprising carboxylate functional chain segment 54 and ammonium functional chain segment 56 in the backbone of copolymer 58.
  • (meth)acrylic acid and the (meth)acrylate functional tertiary amine are merely representative of the types of monomers that can be copolymerized to form copolymer 58.
  • Other examples of compounds suitable for use as first reactant 50 include imidazoles.
  • Copolymer 58 may be prepared using any suitable free radical polymerization technique including bulk, solution, emulsion, and suspension polymerization methods, as described above with relation to Figure 3. Water is a preferred solvent for carrying out the reaction.
  • the carboxyl group of first reactant 50 corresponds to the pendant -COOH moiety of chain segment 54.
  • the hydrogen on this -COOH group spontaneously shifts to the tertiary amine moiety of chain segment 56.
  • the -COOH becomes an anionic carboxylate group
  • the tertiary amine moiety becomes the corresponding cationic ammonium group.
  • Amphoteric polymer 58 results.
  • amphoteric polymers of the present invention may also be prepared by a two-step reaction scheme.
  • the first step involves copolymerizing a (meth)acrylate functional tertiary amine and a maleic anhydride monomer
  • the second step involves reacting the resultant intermediate product with an alcohol.
  • This approach is illustrated schematically in Figures 6A and 6B.
  • a first reactant 60, maleic anhydride is copolymerized with a second reactant 62, a (meth)acrylate functional tertiary amine, to form intermediate copolymer 64 comprising anhydride functional chain segment 66 and ammonium functional chain segment 65 in the backbone of intermediate copolymer 64.
  • maleic anhydride and the (meth)acrylate functional tertiary amine are merely representative of the types of monomers that can be copolymerized to form intermediate copolymer 64.
  • the reaction of Figure 6 A may be carried out using any suitable free radical polymerization technique including bulk, solution, emulsion, and suspension polymerization methods, as described above with relation to Figures 3 and 5.
  • the intermediate copolymer 64 is reacted with an alcohol 67, e.g., ethanol, to form polymer product 68.
  • an alcohol 67 e.g., ethanol
  • other alcohols may be used instead, such as propanol, butanol, and the like.
  • the alcohol group of the alcohol functions as a nucleophilic moiety that undergoes a nucleophilic reaction with the anhydride group, linking to one of the carboxylate moieties while the other carboxylate moiety becomes pendant from the polymer backbone.
  • Alcohol 67 may also have multiple hydroxyl groups, i.e, alcohol may be a diol or triol, in which case, resultant polymer product 68 would comprise pendant hydroxyl functionality, and thus, would be crosslinkable.
  • Example 1 The present invention will now be further described with reference to the following examples: Example 1
  • N,N-dimethylethanol amine (8.5 g) was added to a solution of low molecular weight 50/50 ethylene/maleic anhydride copolymer (3.0 g) in tetrahydrofuran (150mL). The reaction was stirred under N 2 at 25°C for 21 hours. The tetrahydrofuran was removed by rotoevaporating under house vacuum with the use of a 40°C water bath. The residue was washed with two 275 mL aliquots of diethyl ether. The diethyl ether was decanted and the product was placed into a vacuum over at 25°C under house vacuum for 17 hours.
  • Example 2 Example 2
  • N,N-dimethylethanol amine (11.5 g) was added to a solution of high molecular weight 50/50 ethylene/maleic anhydride copolymer (5.0 g) in tetrahydrofuran (200 mL). The reaction was stirred under N 2 at 25°C for 23 hours. More N,N-dimethylethanol amine (23.8 g) was added to the reaction mixture. The reaction was stirred under N 2 at 25°C for an additional 21 hours. The tetrahydrofuran was decanted and the precipitate was washed with one aliquot of tetrahydrofuran (200 mL) followed by two 175 mL aliquots of diethyl ether. The product was placed into a vacuum oven at 25°C under house vacuum for 24 hours.
  • the polymer was prepared as follows. Distilled water (866 mL) was placed into a 2.0 L split reactor flask equipped with a magnetic stirbar. The flask was stirred under vacuum for one hour in order to remove dissolved oxygen from the water. After one hour, the flask was removed from the vacuum and opened to a positive nitrogen atmosphere. Acrylic acid (144.12 g, 2.0 mol) and 2- (Dimethylamino) ethyl acrylate (286.38 g, 2.0 mol) were added to the water by quickly pouring from graduated cylinders. The contents of the flask were then stirred under vacuum for 30 minutes.
  • VA-044 (8.66 g, 0.03 mol) was dissolved into 43 mL distilled water in a 250 mL round bottom flask equipped with a magnetic stirbar. The flask was stirred under vacuum for 30 minutes to deoxygenate.
  • the polymer was prepared as follows. A 100 mL round-bottom flask equipped with a magnetic stirbar was flame-dried and cooled under nitrogen. 2.00 g (0.0204 mol) of malaic anhydride were placed into the flask and the flask purged with nitrogen. 40 mL of THF were added to the flask via cannulation. 1.20 mL (0.0204 mol) ethanol followed by 3.10 mL (0.0204 mol) of 2-(dimethylamino)ethyl acrylate were then added to the flask, both via disposable syringe. The resulting yellow solution was allowed to stir overnight at room temperature, under positive nitrogen pressure.
  • the polymer was prepared as follows. A 250 mL round-bottom flask equipped with a magnetic stirbar was flame-dried and cooled under nitrogen. 2.00 g
  • VA-044 0.00031 mol was dissolved in 0.5 mL distilled water in a 3.0 mL reaction vial equipped with a magnetic stirbar. The vial was stirred for 30 minutes under vacuum to deoxygenate.
  • a solution of N,N-methylenebisacrylamide (BIS) was prepared by adding 4.18 g of BIS to another oven-dried round bottom flask equipped with a magnetic stir bar. The flask was stirred for 20 minutes under vacuum to deoxygenate.
  • BIS N,N-methylenebisacrylamide
  • the water-containing 2 L round-bottom flask was removed from vacuum and opened to a positive nitrogen atmosphere. 167.2 g of acrylic acid and 332.7 g of 2-(dimethylamino)ethyl acrylate was added to the flask via syringe. The resulting solution was stirrred under vacuum for 30 minutes. The flask was then
  • SUBSTITUTE SHEET (RULE 26 removed from under vacuum and opened to a positive nitrogen atmosphere.
  • the BIS solution, followed by the VA-044 solution were then added to the flask via syringe.
  • the flask was then immersed into a 55° C oil bath, while the contents of the flask were continually stirred. The contents of the flask reacted to form a gel, which was removed from the flask and dried in a vacuum oven.
  • VA-044 was dissolved in about 30.0 mL deionized water in an oven-dried round bottom flask equipped with a magnetic stirbar. The flask was stirred for 20 minutes under vacuum to deoxygenate. The water-containing 2 L round-bottom flask was removed from vacuum and opened to a positive nitrogen atmosphere. 167.2 g of acrylic acid and 332.7 g of 2-(dimethylamino)ethyl acrylate was added to the flask via syringe. The resulting solution was stirrred under vacuum for 30 minutes. The flask was then removed from under vacuum and opened to a positive nitrogen atmosphere. The VA-044 solution was then added to the flask via syringe. The flask was then immersed into a 55° C oil bath, while the contents of the flask were continually stirred. The contents of the flask reacted to form a gel, which was removed from the flask and dried in a vacuum oven.

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Abstract

L'invention porte sur un polymère amphotère comprenant une pluralité de fractions de carboxylate pendantes et une pluralité de fractions d'ammonium. Selon des réalisations préférées, chacune des fractions de carboxylate et d'ammonium peuvent être protonées de manière réversible de sorte que le caractère ionique des fractions puisse être modifié par ajustement du pH.
PCT/US1998/008099 1997-04-23 1998-04-22 Polymeres amphoteres aux caracteristiques ioniques modifiables par ajustement du ph WO1998047937A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010125341A1 (fr) * 2009-04-28 2010-11-04 Unilever Plc Copolymère ramifié amphiphile, ses procédés de préparation, émulsions, emu et utilisations
US20140039229A1 (en) * 2010-08-23 2014-02-06 Flowchem, Ltd. Drag Reducing Compositions and Methods of Manufacture and Use
EP2719712A1 (fr) * 2012-10-11 2014-04-16 Samsung SDI Co., Ltd. Polymère, électrode pour batterie secondaire au lithium comprenant le polymère et batterie secondaire au lithium utilisant l'électrode
CN110945110A (zh) * 2017-07-24 2020-03-31 联合碳化公司 混合电荷聚合物
WO2021009274A1 (fr) 2019-07-18 2021-01-21 Sabic Global Technologies B.V. Copolymère d'éthylène et composé de paire d'ions

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Publication number Priority date Publication date Assignee Title
US4704324A (en) * 1985-04-03 1987-11-03 The Dow Chemical Company Semi-permeable membranes prepared via reaction of cationic groups with nucleophilic groups

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4704324A (en) * 1985-04-03 1987-11-03 The Dow Chemical Company Semi-permeable membranes prepared via reaction of cationic groups with nucleophilic groups
US4797187A (en) * 1985-10-22 1989-01-10 The Dow Chemical Company Semi-permeable membranes prepared via reaction of cationic groups with nucleophilic groups

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010125341A1 (fr) * 2009-04-28 2010-11-04 Unilever Plc Copolymère ramifié amphiphile, ses procédés de préparation, émulsions, emu et utilisations
US20140039229A1 (en) * 2010-08-23 2014-02-06 Flowchem, Ltd. Drag Reducing Compositions and Methods of Manufacture and Use
US9416331B2 (en) * 2010-08-23 2016-08-16 Flowchem, Ltd. Drag reducing compositions and methods of manufacture and use
EP2719712A1 (fr) * 2012-10-11 2014-04-16 Samsung SDI Co., Ltd. Polymère, électrode pour batterie secondaire au lithium comprenant le polymère et batterie secondaire au lithium utilisant l'électrode
CN103724523A (zh) * 2012-10-11 2014-04-16 三星Sdi株式会社 聚合物化合物、电极粘结剂组合物、电极和锂二次电池
US9318744B2 (en) 2012-10-11 2016-04-19 Samsung Sdi Co., Ltd. Polymer electrode for lithium secondary battery including the polymer and lithium second battery employing the electrode
CN110945110A (zh) * 2017-07-24 2020-03-31 联合碳化公司 混合电荷聚合物
US20200207896A1 (en) * 2017-07-24 2020-07-02 Rohm And Haas Company Mixed-charge polymers
WO2021009274A1 (fr) 2019-07-18 2021-01-21 Sabic Global Technologies B.V. Copolymère d'éthylène et composé de paire d'ions
CN114269797A (zh) * 2019-07-18 2022-04-01 Sabic环球技术有限责任公司 乙烯和离子对化合物的共聚物

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