EP0968237A1 - Leitfähige heterocyclische pfropfcopolymere und dabei angewandte macromere - Google Patents

Leitfähige heterocyclische pfropfcopolymere und dabei angewandte macromere

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Publication number
EP0968237A1
EP0968237A1 EP98912086A EP98912086A EP0968237A1 EP 0968237 A1 EP0968237 A1 EP 0968237A1 EP 98912086 A EP98912086 A EP 98912086A EP 98912086 A EP98912086 A EP 98912086A EP 0968237 A1 EP0968237 A1 EP 0968237A1
Authority
EP
European Patent Office
Prior art keywords
graft copolymer
maeromer
group
moiety
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98912086A
Other languages
English (en)
French (fr)
Inventor
Michael J. Zajaczkowski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Adhesives Research Inc
Original Assignee
Adhesives Research Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/821,724 external-priority patent/US5929172A/en
Priority claimed from US08/821,725 external-priority patent/US5929182A/en
Application filed by Adhesives Research Inc filed Critical Adhesives Research Inc
Publication of EP0968237A1 publication Critical patent/EP0968237A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes

Definitions

  • the present invention is directed to a pressure sensitive adhesive comprised of a polymerized acrylic or methacrylic acid ester backbone having grafted thereto pendant sulfur, nitrogen or oxygen-containing heterocyclic moieties, as well as novel heterocyclic macromers used therein.
  • Loss of adhesive tack is also recognized as a potential problem with respect to electrically- conductive pressure sensitive adhesives in U.S. Patent No. 2,670,306.
  • the use of powdered graphite is stated to be preferred over carbon black to minimize the degree of tack loss.
  • U.S. Patent No. 3,475,213 discloses an electrically-conductive adhesive tape which comprises a pressure sensitive adhesive and electrically-conductive particles distributed as a monolayer in the adhesive layer.
  • U.S. Patent No. 2,808,352 discloses an electrically conductive adhesive tape wherein the adhesive base is impregnated with finely divided silver particles.
  • U.S. Patent No. 4,367,745 discloses a conformable electrically conductive composition composed of a plurality of deformable, non-polar microspheres around which are dispersed electrically conductive particles.
  • U.S. Patent No. 4,548,862 is directed to a flexible tape having bridges of electrically conductive particles extending through the adhesive layer.
  • U.S. Patent No. 4,588,762 discloses a pressure sensitive adhesive composition consisting of both a viscoelastic polymeric adhesive phase and an electrically conductive aqueous phase containing a water receptive polymer, a humectant, and an electrolyte.
  • a graft copolymer comprised of the reaction product of:
  • At least one A monomer comprising a monomeric acrylic or methacrylic acid ester of a non-tertiary alcohol, said alcohol having from 1 to 30 carbon atoms with the average number of carbon atoms being in the range of from about 4 to 15,
  • a graft polymeric moiety C defined by the formula X-(Y) m -Z-R, wherein X is a moiety copolymerizable with monomers A and B or is capable of attachment to copolymerized monomers A and B, Y is a divalent linking group, R is a terminal group, m is 0 or 1, and Z is the
  • R 6 is hydrogen, alkyl, aryl, alkylaryl or arylalkyl
  • R ⁇ and R 2 may be the same or different and are hydrogen, linear or branched C ⁇ - j ⁇ alkyl, aryl, alkylaryl, arylalkyl, hydroxycarbonyl , alkoxycarbonyl, or amide radical, or R- and R 2 together form a closed ring structure, with R ⁇ and R 2 together forming a chain selected from the group consisting of an optionally substituted C 3 _ 4 alkylene radical and -0-T-O- wherein T is an optionally substituted C 2 _ 3 alkylene radical, and n is 10 to 5000; and
  • a heterocyclic macromer I having the formula X-(Y) m -Z-R wherein X is an unsaturated polymerizable moiety, Y is a divalent linking group, R is a terminal group and Z is
  • Q is an oxygen or sulfur atom or -Nf-
  • R 6 is hydrogen, alkyl, aryl, arylalkyl, or arylalkyl
  • R and R 2 may be the same or different and are hydrogen, linear or branched C- ⁇ _ 10 alkyl, aryl, alkylaryl, arylalkyl, hydroxycarbonyl, alkoxycarbonyl or amide radical, or R-L and R 2 together form a closed ring structure, with R ⁇ and R 2 together forming a chain selected from the group consisting of an optionally substituted C 3 _ 4 alkylene radical and O- T-0 wherein T is an optionally substituted C 2 _ 3 alkylene radical, and n is 10 to 5000.
  • graft copolymer comprised of the reaction product of:
  • At least one A monomer comprising a monomeric acrylic or methacrylic acid ester of a non-tertiary alcohol, said alcohol having from 1 to 30 carbon atoms with the average number of carbon atoms being in the range of from about 4 to 15,
  • R 6 I wherein Q is an oxygen or sulfur atom or -N- wherein R 6 is hydrogen, alkyl, aryl, alkylaryl or arylalkyl; and R and R 2 may be the same or different and are hydrogen, linear or branched C- ⁇
  • R- ⁇ and R 2 together form a closed ring structure, with R 1 and R 2 together forming a chain selected from the group consisting of an optionally substituted C 3 _ 4 alkylene radical and O-
  • T-0 wherein T is an optionally substituted C 2 _ 3 alkylene radical, P is selected from the group consisting of C 1-2 alkylene, an oxygen atom or a - CH 2 -0- linkage, R is a terminal group, X is a moiety copolymerizable with monomers A and B or is capable of attachment to copolymerized monomers A and B, Y is a divalent linking group, n- and n 2 each range from 0 to 5000 and n ] _+n 2 is 10 to 5000; and
  • Q is an oxygen or sulfur atom or -N- wherein R 6 is hydrogen, alkyl, aryl, alkylaryl or arylalkyl; and R and R 2 may be the same or different and are hydrogen, linear or branched C ⁇ 10 alkyl, aryl, alkylaryl, arylalkyl, hydroxycarbonyl, alkoxycarbonyl, or amide radical, or R- ⁇ and R 2 together form a closed ring structure, with R and R 2 together forming a chain selected from the group consisting of an optionally substituted C 3 _ 4 alkylene radical and O- T-0 wherein T is an optionally substituted C 2 _ 3 alkylene radical, P is selected from the group consisting of C 1-2 alkylene, an oxygen atom or a - CH 2 -0- linkage, R is a terminal group, X is a moiety copolymerizable with monomers A and B or is capable of attachment to copolymerized monomers A and B, Y is
  • the electrically-conductive graft copolymer of the present invention is comprised of copolymerized monomers A and B to form a backbone polymer having a sulfur, nitrogen or oxygen- containing heterocyclic moiety C grafted thereto, and optionally a water-soluble or water- dispersible graft polymeric moiety D.
  • Monomer A is a monomeric acrylic or methacrylic acid ester of a non-tertiary alcohol having from 1 to 30 carbon atoms with the average number of carbon atoms possessed by the acrylic-or methacrylic acid esters present as the A monomer(s) being in the range of about 4 to 15.
  • Exemplary A monomers include but are not limited to esters of acrylic acid or methacrylic acid with non-tertiary alcohols such as 1-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-l-butanol, 1-methyl-1-pentanol, 2-methyl-l-pentanol, 3-methyl-l-pentanol, 2-ethyl-l-butanol, 3,5,5- trimethyl-1-hexanol, 3-heptanol, 2-octanol, 1- decanol, 1-dodecanol, etc., as well as mixtures thereof.
  • Such monomers are known to those skilled in the art.
  • Exemplary A monomers include but are not limited to methyl (meth) aerylate, ethyl (meth) aerylate, propyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth) aerylate, isooctyl (meth) aerylate, and isobornyl (meth)acrylate.
  • one or more polymerizable B monomers may be incorporated in the copolymer which B monomer(s) is copolymerizable with the A monomer. If the T g of the B monomer present is equal to or greater than 20°C, then less than 20% by weight of the B monomer should be present if it is desired that the copolymer exhibit pressure sensitive adhesive properties.
  • Exemplary optional B monomers include vinyl monomers having at least one nitrogen atom.
  • Such monomers include but are not limited to N-mono-substituted acrylamides such as acrylamide, methacry1amide, N- methylacrylamide, N-ethylacrylamide, N- methylolacrylamide, N-hydroxyethylacrylamide, and diacetone acrylamide; N, N-disubstituted acrylamides such as N,N-dimethylacrylamide, N,N- diethylacrylamide , N-ethy1-N-aminoethy1 acrylamide, N-ethy1-N-hydroxyethylacrylamide, N,N- dimethylolacrylamide, and N , N - dihydroxyethylacrylamide, etc.
  • N-mono-substituted acrylamides such as acrylamide, methacry1amide, N- methylacrylamide, N-ethylacrylamide, N- methylolacrylamide, N-hydroxyethylacrylamide, and diacetone
  • Other optional B monomers may include, for example, various vinyl monomers such as acrylic and methacrylic acid, itaconic acid, methoxyethyl acrylate or methacrylate, ethyoxyethyl aerylate or methacrylate, acrylonitrile, methacrylonitrile, glycerol acrylate or methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinyl pyrrolidone and vinyl caprolactam (each of which also exhibit a T of >20°C) .
  • various vinyl monomers such as acrylic and methacrylic acid, itaconic acid, methoxyethyl acrylate or methacrylate, ethyoxyethyl aerylate or methacrylate, acrylonitrile, methacrylonitrile, glycerol acrylate or methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinyl pyrrol
  • the heterocyclic graft moiety C is defined by the formula X-(Y) m -Z-R, wherein X is a moiety copolymerizable with monomers A and B or is capable of attachment to copolymerized monomers A and B, R is a terminal group, Y is a divalent linking group and m is 0 or 1.
  • the Z moiety comprises the heterocyclic portion of the graft moiety.
  • the X moiety is an unsaturated polymerizable moiety the composition of which is not critical.
  • Other exemplary X moieties include but are not limited to methacryloyl, maleoyl, itaconoyl, crotonoyl, unsaturated urethane moiety, methacrylamido and moieties of the formula
  • the X moiety may comprise an a ine or alcohol moiety (such as a monohydroxyl or monoa ine moiety) which permits attachment of the maeromer to a suitable functionality on previously- polymerized monomers A and B.
  • the hydroxyl moiety can serve as a terminal reactive group by reaction with suitable moieties on the polymer backbone resulting from the use of monomers such as isocyanate-substituted (meth) acrylic acid, (meth) acrylic acid anhydride, etc.
  • the divalent linking group Y may be selected from a variety of acceptable moieties, with a preferred divalent linking group Y being
  • Additional Y linking groups which may be employed in connection with the present invention include but are not limited to the following moieties:
  • Divalent macromonomeric moieties may also be employed as the linking group.
  • exemplary divalent macromeric moieties include (but are not limited to) a polypropylene or polyethylene oxide radical, a polyethyloxazoline radical such as a radical of poly(2-ethyl-2- oxazoline) , polyacrylic acid radical, polyvinyl alcohol radical, polyvinylpyrrolidone radical, polyvinyl caprolactam radical, polymethylvinyl ether radical or mixtures thereof.
  • the presence of the Y linking group is optional in the event the Z moiety includes a functionality which enables the Z moiety to react with the X moiety.
  • Z may in one embodiment be defined as the heterocyclic R-.
  • R 6 is hydrogen, alkyl, aryl, alkylaryl or arylalkyl
  • R ⁇ and R 2 may be the same or different and are hydrogen, linear or branched alkyl, aryl, alkylaryl, arylalkyl, hydroxycarbony1, alkoxycarbonyl, or amide radical, or R and R 2 together form a closed ring structure, with R and R 2 together forming a chain selected from the group consisting of an optionally substituted C 3 _ 4 alkylene radical and - O-T-O- wherein T is an optionally substituted C 2 _ 3 alkylene radical, and n ranges from 10 to 5000.
  • R and R 2 are both hydrogen and Q is a sulfur atom.
  • the graft moiety X-Y-Z-R may be defined bv the formula:
  • X, Q, R, R ⁇ and R 2 are as defined above, P is selected from the group consisting of C 1 _ alkylene, an oxygen atom or a -CH 2 -0- linkage, Y is a divalent linking group, n 1 and n 2 each range from 0 to 5000 and n x + n 2 is 10 to 5000.
  • alkyl and alkoxy radicals have from 1 to 10 carbon atoms.
  • the alkylene radicals may be substituted with C j ⁇ -, alkyl or alkoxy radicals.
  • the R terminal group is preferably hydrogen, C 1 _ 5 alkyl or phenyl. It is, however, within the scope of the present invention for the R terminal group to contain a reactive group which permits subsequent crosslinking (either ionic or covalent) ; i.e., the R terminal group may be either mono- or difunctional.
  • the copolymer of the present invention may optionally also include a water-soluble or water- dispersible graft polymeric moiety D.
  • the maeromer D forms polymeric sideehains on the graft copolymer.
  • the maeromer D is hydrophilic by nature (i.e., the maeromer is water-soluble or water-dispersible) .
  • the maeromer D may be represented by the formula X-(Y) -Z-R wherein X is a moiety copolymerizable with monomers A and B or, in the alternative, capable of attachment to polymerized monomers A and B, Y is a divalent linking group, Z is a water-soluble or water-dispersible homo- or polymeric moiety essentially unreactive at copolymerization conditions, R is a terminal group, and p is 0 or 1.
  • the X and Y moieties may be selected using the same criteria discussed above in connection with the X and Y moieties present in the heterocyclic graft polymeric moiety.
  • the Z moiety of maeromer D is preferably selected from the group consisting of (but not limited to) a polypropylene or polyethylene oxide radical, a polyethyloxazoline radical such as a radical of poly(2-ethyl-2-oxazoline) , polyacrylic acid radical, polyvinyl alcohol radical, polyvinylpyrrolidone radical, polyvinyl caprolactam radical, polymethylvinyl ether radical or mixtures thereof.
  • Exemplary D macromers formed from such radicals include but are not limited to ethoxylated or propoxylated hydroxy(C 1 _ 5 ) alkyl meth (acrylate) and polymethylvinyl ether mono (meth) acrylate.
  • the molecular weight of the maeromer used in the present invention is not critical but will generally range from about 300 to about 50,000, and preferably from about 300 to 3,000.
  • the hydrophilic maeromer D is more preferably represented by the formula:
  • R- L 0 wherein R is hydrogen or C 1 _ 5 alkyl and R is a terminal group.
  • m is 2 or 3 and n is 5 to 30, and R is OH or C- ⁇ g alkyl.
  • the Z moiety is preferably comprised solely of one or more hydrophilic monomer radicals to ensure that the resulting maeromer is water- soluble or water-dispersible.
  • the Z moiety may also be a copolymer of hydrophilic and hydrophobic monomers, with any copolymerized hydrophobic portion being present in an amount insufficient to render the resulting maeromer water-insoluble or non-water-dispersible.
  • any non-hydrophilic portion employed in such a copolymer is present in an amount of less than 50 percent by weight based on the weight of the maeromer, and preferably less than 30 percent by weight.
  • the maeromer D may employ a variety of terminal groups R. While the terminal group may typically be OH or C 1-5 alkyl, it may be desirable to select a terminal group based on the functional character of the terminal group.
  • suitable terminal groups include but are not limited to (1) acid/ionic groups such as carboxyl, phosphate or sulfate groups, (2) hydrophobic groups such as C 1-5 alkyl, phenyl or substituted phenyl, and (3) hydrophilic groups such as hydroxyl or amine groups.
  • ionic end groups may be used to provide pH- dependent solubility characteristics for the copolymer.
  • Hydrophobic terminal groups may be used to reduce the water solubility of the copolymer.
  • Other physical properties or characteristics of the copolymer may be modified by selection of suitable terminal groups.
  • ionic terminal groups may be used to provide a desired degree of cross-linking; for example, by neutralizing acid moieties with metal hydroxides.
  • the copolymer may be covalently or ionically crosslinked in a conventional manner.
  • Suitable covalent crosslinking agents are well-known in the art. Covalent crosslinking may be achieved by incorporating into the polymerization mixture (for internal crosslinking) a polyfunctional ethylenically unsaturated compound in an amount sufficient to provide the desired crosslinking. External crosslinking agents may also be employed by admixture to the copolymer polymerization product.
  • Exemplary internal crosslinking agents suitable for addition to the reaction mixture include but are not limited to di- or tri-esters of (meth) acrylic acid, di- or poly-alkylene glycol (meth)acrylates, alkylene bis (meth) acrylamides and n- (isobutoxymethy1) acrylamide.
  • Exemplary external crosslinking agents which may be added to the polymerization product to provide the desired crosslinking include but are not limited to aziridines, titanates, melamine resins, etc.
  • the crosslinking agent, if employed, is added to the reaction mixture or to the polymerization product in an amount of from 0.02 to about 2 percent by weight, preferably from about 0.05 to 1 percent by weight.
  • the graft copolymer may be ionically- crosslinked in a conventional manner. See, for example, the teachings of U.S. Patent Nos. 3,264,272; 3,969,434; and 4,002,581 each herein incorporated by reference in their entirety.
  • the desired ionic crosslinking can occur by providing on at least a portion of the monomers A and B and/or the graft moieties C and D functional groups which are capable of being neutralized by a mono-, di- or trivalent metal ion.
  • Exemplary functional groups are selected from the group consisting of carboxyl, sulfate, phosphate, anhydride and mixtures thereof.
  • At least one of the copolymerizable B monomers may comprise an ionically-crosslinkable monomer such as an alpha, beta-ethylenically unsaturated carboxylic acid group having from 3-8 carbon atoms, such as acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, and dicarboxylic acids.
  • an ionically-crosslinkable monomer such as an alpha, beta-ethylenically unsaturated carboxylic acid group having from 3-8 carbon atoms, such as acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, and dicarboxylic acids.
  • Alpha,beta- monoethylenically unsaturated anhydrides of carboxylic acid such as maleic anhydride can also be employed.
  • from about 3 to 10 percent by weight of the total reactants A, B, C and D may comprise acrylic or (meth) acrylic acid
  • the D maeromer may be rendered ionically-crosslinkable by incorporation of an acidic/ionic terminal group such as carboxyl, sulfate, phosphate, anhydride or mixtures thereof.
  • the ionically-crosslinked graft copolymer of the present invention may be produced by reaction of the copolymer with an ionizable metal compound in order to neutralize the appropriate functionalities (e.g. , acid functionalities) on either the base monomers or on the maeromer.
  • an ionizable metal compound e.g., from about 2 to about 50 weight percent of the base monomers or the maeromer contain functionalities which may be neutralized by reaction with an ionizable metal compound.
  • Metal ions which may be employed in the formation of the ionically-crosslinked graft copolymer include but are not limited to mono-, di- and trivalent ions of the metals of Groups I, II, III, IV and VIII.
  • Suitable monovalent metal ions include sodium, potassium, lithium, cesium, silver, mercury and copper.
  • Suitable divalent metal ions include beryllium, magnesium, calcium, strontium, berium, copper, cadmium, mercury, tin, lead, iron, cobalt, nickel and zinc.
  • Suitable trivalent metal ions include aluminum, chromium, iron and yttrium. The preferred metal ions are alkali metal ions.
  • the ionic crosslinking reaction (i.e., the neutralization of the appropriate neutralizable functionalities) may be carried out by blending the graft copolymer with a solution of the crosslinking metal compounds in an amount sufficient to neutralize the neutralizable functionalities to the desired extent.
  • Preferred metal compounds for use in providing the necessary neutralization include but are not limited to alkali and alkaline earth metal hydroxides. Also suitable are alkali metal salts or alkaline earth metal salts based on an organic acid, such as sodium acetate, calcium acetate, magnesium acetate, zinc formate, and zinc acetate.
  • one or more polymerizable hydrophilic or hydrophobic B monomers may be incorporated in the copolymer.
  • a hydrophilic B monomer in addition to a hydrophilic graft polymer moiety D to enhance the water-soluble or dispersible character of the conductive copolymer.
  • the copolymer serves as a conductive pressure sensitive adhesive to adhere a biomedical device such as an electrode to a person's skin. This will enable the adhesive to be easily removed from the person's skin by contact of the adhesive with sufficient amount of water. This may be important in the event the skin to which the adhesive is applied is sensitive (e.g., as may be encountered in a neonatal or geriatric environment) .
  • the B monomer if hydrophilic
  • a hydrophobic B monomer in an amount that renders the polymer composition reduces the extent or degree of water sensitivity of the polymer.
  • the A monomer is present in an amount of from 30 to 70 percent by weight
  • the B monomer is present in an amount of from 3 to 30 percent by weight
  • the C graft moiety is present in an amount of from 20 to 60 percent by weight
  • the D maeromer is present in an amount ranging from 0 to 40 percent by weight, based on the total weight of the respective components A, B, C and D in the composition.
  • the A monomer is preferably present in an amount of from 30 to 75 percent by weight
  • the B monomer is hydrophilic and is preferably present in an amount of from 3 to 15 percent by weight
  • the graft moiety C is preferably present in an amount of from 20 to 60 percent by weight
  • the maeromer D is preferably present in an amount of from 15 to 40 percent by weight.
  • tackifiers include polyethylene glycol, polypropylene glycol, and suitable polyoxyethylene-based compounds. Suitable polyoxyethylene-based tackifiers are disclosed at column 6 of U.S. Patent No. 4,413,080, herein incorporated by reference in its entirety. Such tackifiers, if present, may be employed in an amount of up to about 50 percent by weight, based on the total weight of the composition.
  • heterocyclic moiety defined by the formula X-(Y) m -Z-R may be prepared by initially forming the heterocyclic monomer by the following synthesis (exemplified by use of the sulfur heterocycle) :
  • heterocyclic macromeric moiety II may be prepared in a similar manner whereby the following compound 2 is substituted for compound 1 of the above reaction scheme:
  • X, Y and Q are as defined previously.
  • mixtures of compounds 1 and 2 may be employed in the reaction mixture.
  • the graft moiety C and maeromer D may be attached to the polymer backbone by conventional techniques such as (1) copolymerization with the respective monomers of the backbone polymer or (2) attachment to a preformed backbone polymer via a suitable functional group subsequent to formation of same by copolymerization of monomers A and B.
  • the graft copolymer of the present invention may be formed from copolymerized components A, B, C and optionally D, wherein
  • monomer A is a monomeric acrylic or methacrylic acid ester of a non-tertiary alcohol, said alcohol having from 1 to 30 carbon atoms with the average number of carbon atoms being in the range of about 4 to 15,
  • monomer B is a monomer copolymerizable with said monomer A, and (3) graft moieties C and optionally D having the general formula X-Y-Z-R as defined above.
  • the graft moieties C and D may be prepared and copolymerized with one or more A and B monomers which form the backbone polymer such as acrylic acid, acrylamide, methacrylic acid, methacrylamide and alkyl acrylates where the alkyl groups contain from 1 to 14 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, 2-ethylhexyl and other octyl, nonyl and decyl acrylates) .
  • a and B monomers which form the backbone polymer
  • a and B monomers which form the backbone polymer such as acrylic acid, acrylamide, methacrylic acid, methacrylamide and alkyl acrylates where the alkyl groups contain from 1 to 14 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl
  • suitable copolymerization temperatures range from about 20°C to 150°C for periods of time of from 2 to 24 hours until the desired degree of conversion occurs.
  • the solvent is removed and a graft copolymer results.
  • the coated copolymer may be treated with a suitable material to yield a copolymer having a highly conductive doped state in a conventional manner.
  • the copolymer may be dipped in a 3 mg/ml solution of ferric chloride for a period of time sufficient to yield a conductive doped copolymer.
  • the resulting graft copolymer may need to be used in solution or emulsion form. That is, if the molecular weight of the graft is sufficiently high, the resultant graft copolymer may be applied to a backing material or substrate in emulsion or solution form, with the water or solvent being removed upon application to the substrate.
  • exemplary backing materials include but are not limited to flexible or inflexible backing materials conventionally employed in the area of pressure sensitive adhesives such as creped paper, kraft paper, fabrics (knits, non-wovens, wovens) , foil and synthetic polymer films such as polyethylene, polypropylene, polyvinyl chloride, poly (ethylene terephthalate) and cellulose acetate, as well as glass, ceramics, metallized polymeric films and other compatible sheet materials.
  • Such materials may be coated in any conventional manner with the adhesive composition of the present invention, such as by roll coating, spray coating, extrusion coating, co-extrusion coating, hot melt coating by use of conventional coating devices.
  • composition of the present invention may be applied as a solution and the solvent subsequently removed to leave a tacky adhesive residue on the backing material.
  • the coated backing material may take many forms, such as tapes, patches, strips, biomedical electrodes, etc. , with the choice and form of backing material being ultimately determined by the end use contemplated.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
EP98912086A 1997-03-20 1998-03-20 Leitfähige heterocyclische pfropfcopolymere und dabei angewandte macromere Withdrawn EP0968237A1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US821725 1986-01-23
US08/821,724 US5929172A (en) 1997-03-20 1997-03-20 Conductive heterocyclic graft copolymer
US08/821,725 US5929182A (en) 1997-03-20 1997-03-20 Heterocyclic macromers
US821724 1997-03-20
PCT/US1998/006028 WO1998041550A1 (en) 1997-03-20 1998-03-20 Conductive heterocyclic graft copolymer and heterocyclic macromer used therein

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EP0968237A1 true EP0968237A1 (de) 2000-01-05

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KR20000076307A (ko) 2000-12-26
CA2283456A1 (en) 1998-09-24
JP2001516390A (ja) 2001-09-25

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