Polyester comprising branched diols, methods of making, and adhesives comprising the polyester

Abstract

A polyester copolymer comprising the reaction product of a first diol and second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short chain diol having from 2 to 20 carbon atoms; a difunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; a third diol, wherein the third diol comprises a branched hydrocarbyl group., a method of making the a polyester copolymer, adhesives comprising the polyester copolymer, dermal patches comprising the adhesive, and medical devices comprising the adhesive.

Description

POLYESTER COMPRISING BRANCHED DIOLS, METHODS OF MAKING, AND ADHESIVES COMPRISING THE POLYESTERCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] NoneFIELD OF THE INVENTION

[0002] The present invention relates, generally, to polyester copolymers, methods of making the polyester copolymers, adhesives comprising the polyester copolymers, and dermal patches and medical devices comprising the polyester copolymer adhesives. BACKGROUND OF THE INVENTION

[0003] Pressure sensitive adhesives (PSAs) are used in a wide range of medical applications including wound coverings, wound closures, ostomy mounts, surgical drapes, transdermal drug delivery, and attachment of medical devices to the body. These PSAs must combine strong adhesive and cohesive properties for good bonding to the skin and atraumatic removal with no residue. Of particular importance are long wear times, biocompatibility, long term stability, and non-irritability. Typical polymers used in medical applications are acrylics, thermoplastic elastomers like styrene-butadiene-styrene and styrene-isoprene-styrene block co-polymers blended with tacky resins, polysiloxanes, and hydrogels like polyvinylpyrrolidone or crosslinked carboxymethyl cellulose-polyisobutylene.

[0004] Acrylic polymers have strong adhesive properties but can cause damage upon removal and often contain monomers that lead to sensitization or irritation. Thermoplastic elastomers can also damage skin during removal, and they can be uncomfortable for longterm wear due to poor breathability. Polysiloxanes are gentle on skin, especially the skin of newborns and the elderly, but they have drawbacks in moisture management, poor adhesive strength, and cost. Hydrogels dry out quickly, are uncomfortable to wear, and can be difficult to process.

[0005] Thus, there is a need for a one-part, easily processable adhesive for medical applications that adheres strongly to skin for the duration of the required application, is easily and painlessly removed, is breathable and is repositionable.BRIEF SUMMARY OF THE INVENTION

[0006] The present invention is directed to a polyester copolymer, comprising: the reaction product of a first diol and second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short chain diol having from 2 to 20 carbon atoms; a difunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, ananhydride, or a diester; a third diol, wherein the third diol comprises a branched hydrocarbyl group.

[0007] The present invention is further directed to a method of making a polyester copolymer, comprising the steps of combining: a first diol and second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short chain diol having from 2 to 20 carbon atoms; a difunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; a third diol, wherein the third diol comprises a branched hydrocarbyl or hydrocarbyloxy group; and a catalyst to form a reaction mixture, and exposing the reaction mixture to conditions sufficient to cause a reaction and form the polyester copolymer.

[0008] The present invention is still further directed to a pressure sensitive adhesive comprising the polyester copolymer composition of the invention.

[0009] The present invention is still further directed to a dermal patch comprising the pressure sensitive adhesive according to the invention, wherein the patch is a transdermal drug delivery patch or a wound care patch or any other adhesive system used to temporarily secure a medical or veterinary device on respectively huma or animal body.

[0010] The present invention is still further directed to a medical device comprising the pressure sensitive adhesive according to the invention.

[0011] The present invention is finally directed to a polyester copolymer, comprising: random units having the formulas [-OR4O-], [-OR5O-], [-C(O)R6C(O)-], [-OR7O-], wherein R4is hydrocarbylene having from 2 to 20 carbon atoms, alternately 2 to 5 carbon atoms, alternatively from 2 to 4 carbon atoms, R5is a branched hydrocarbylene, branched hydrocarbyloxy-substituted hydrocarbylene, or branched ether-substituted hydrocarbylene having from 4 to 20 carbon atoms, R6is hydrocarbylene having from 4 to 12 carbon atoms, wherein R7is oligomeric, copolymeric, or polymeric hydrocarbylene or alkylene glycol having a Mw greater than 400 g / mol, alternatively from 400 g / mol to 3000 g / mol, and where the polyester copolymer is hydroxy, carboxy, or carboxylate terminated.BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Fig. 1 is a graph of loss modulus and storage modulus versus angular frequency for Example 1 .

[0013] Fig. 2 is a graph of loss modulus and storage modulus versus angular frequency for Example 2.

[0014] Fig. 3 is a graph of loss modulus and storage modulus versus angular frequency for Example 3.

[0015] Fig. 4 is a graph of loss modulus and storage modulus versus angular frequency for Example 5.

[0016] Fig. 5 is a graph of loss modulus and storage modulus versus angular frequency for Example 6.

[0017] Fig. 6 is a graph of loss modulus and storage modulus versus angular frequency for Example 8.

[0018] Fig. 7 is a graph of loss modulus and storage modulus versus angular frequency for Example 9.

[0019] Fig. 8 is a graph of loss modulus and storage modulus versus angular frequency for Example 10.

[0020] Fig. 9 is a graph of loss modulus and storage modulus versus angular frequency for Example 11 .

[0021] Fig. 10 is a graph of loss modulus and storage modulus versus angular frequency for Example 12.

[0022] Fig. 11 is a graph of loss modulus and storage modulus versus angular frequency for Example 13.

[0023] Fig. 12 is a graph of loss modulus and storage modulus versus angular frequency for Example 16.

[0024] Fig. 13 is a graph of loss modulus and storage modulus versus angular frequency for Example 17.

[0025] Fig. 14 is a graph of loss modulus and storage modulus versus angular frequency for Example 18.

[0026] Fig. 15 is a graph of loss modulus and storage modulus versus angular frequency for Example 19.

[0027] Fig. 16 is a graph of loss modulus and storage modulus versus angular frequency for Example 21.

[0028] Fig. 17 is a graph of loss modulus and storage modulus versus angular frequency for Example 22.DETAILED DESCRIPTION OF THE INVENTION

[0029] As used herein, the article "a" refers to one as well as more than one and does not necessarily limit its referent noun to the grammatical category of singular number.

[0030] As used herein, the terms “about” and “at or about”, when used to modify an amount or value, refers to an approximation of an amount or value that is more or less than the precise amount or value recited in the claims or described herein. The precise value ofthe approximation is determined by what one of skill in the art would recognize as an appropriate approximation to the precise value. As used herein, the term conveys that similar values, not precisely recited in the claims or described herein, can bring about results or effects that are equivalent to those recited in the claims or described herein, for which one of skill in the art would acknowledge as acceptably brought about by the similar values.

[0031] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation of these, refer to a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not limited to only the listed elements but may include other elements not expressly listed or inherent. Further, unless expressly stated to the contrary, “or” refers to an inclusive, not an exclusive, or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0032] As used herein, the clause “the polyester copolymer comprises” or “the polyester copolymer comprises” or similar, means that the polyester copolymer is produced from the material described following this clause. That is, the material reacts with the one or more other materials to produce the polyester copolymer.

[0033] As used herein, the terms "consisting essentially of', and "consisting of' or any other variation of these, may refer either to a non-exclusive inclusion or to an exclusive inclusion. When these terms refer to a more exclusive inclusion, these terms limit the scope of a claim to those recited materials or steps that materially affect the novel elements of the recited invention. When these terms refer to a wholly exclusive inclusion, these terms exclude any element, step or component not expressly recited in the claim.

[0034] As used herein, terms that describe molecules or polymers follow the terminology in the IUPAC Compendium of Chemical Terminology version 2.15 (International Union of Pure and Applied Chemistry) of September 7, 2009.

[0035] As used herein, the term "alkyl” refers to linear, branched, or cyclic hydrocarbon structures and combinations of there. Alkyl does not include aromatic structures. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Branched alkyl groups include for example s-and t-butyl, and isopropyl groups. Examples of cyclic hydrocarbon groups include cyclopropyl, cyclopentyl, cyclohexyl, cyclobutyl, and cyclooctyl groups.

[0036] As used herein, the term ’’alkoxy” or “alkoxyl” refers to alkyl groups attached to an oxygen atom by a single bond. The other bond of the oxygen atom is connected to a carbon atom. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, and cyclohexyloxy.

[0037] As used herein, the term “aromatic” refers to a chemical entity comprising at least one unsaturated ring of atoms that are stabilized by an interaction of the bonds forming the ring. Such chemical entities are typified by benzene and naphthalene.

[0038] As used herein, the term “phenyl” refers to a chemical entity having the formula - CQH5 derived from benzene by removal of one hydrogen atom. The carbon atom lacking the hydrogen atom is used to form a bond to another chemical entity.

[0039] As used herein, the term “phenylene” refers to a chemical entity having the formula C6H4derived from benzene by removal of two hydrogen atoms. The carbon atoms lacking the hydrogen atom is used to form bonds to another chemical entity or part of a larger molecule.

[0040] Any range set forth herein expressly includes its endpoints unless explicitly stated otherwise. Setting forth an amount, concentration, or other value or parameter as a range specifically discloses all possible ranges formed from any possible upper range limit and any possible lower range limit, regardless of whether such pairs of upper and lower range limits are expressly disclosed herein. Compounds, processes, and articles described herein are not limited to specific values disclosed in defining a range in the description.

[0041] The disclosure herein of any variation in terms of materials, chemical entities, methods, steps, values, and / or ranges, etc. — whether identified as preferred or not — of the processes, compounds and articles described herein specifically intends to include any possible combination of materials, methods, steps, values, ranges, etc. For the purpose of providing photographic and sufficient support for the claims, any disclosed combination is a preferred variant of the processes, compounds, and articles described herein.

[0042] In this description, if there are nomenclature errors or typographical errors regarding the chemical name any chemical species described herein, the chemical structure takes precedence over the chemical name. And, if there are errors in the chemical structures of any chemical species described herein, the chemical structure of the chemical species that one of skill in the art understands the description to intend prevails.

[0043] A polyester copolymer, comprising: the reaction product ofa first diol and second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short chain diol having from 2 to 20 carbon atoms; a difunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; a third diol, wherein the third diol comprises a branched hydrocarbyl group.The First Diol

[0044] The first diol can be many of the diols, or mixture of diols, known in the art for use in making polyester polymers that are different from the second and third diol. In various embodiments, the dihydroxy-terminated diol is chosen from poly(alkylene oxide)diols (such as polyethylene oxide, polypropylene oxide, or polybutylene oxide, diols), linear aliphatic polyester, aliphatic polycarbonates, linear polyether polysiloxane diols, branched polyether polysiloxane diols, linear aliphatic polyolefins, linear polybutadiene, linear polyisobutylene, polyadipates, and mixtures thereof. In another embodiment, the first diol may comprise polytetrahydrofuran as the first diol.

[0045] The first diol can also be a hydroxyl-terminated oligomer such as, but not limited to, an aliphatic hydrocarbon diol having over 20 carbon atoms, alternatively 20 to 4000, alternatively 1000 to 3000 carbon atoms.

[0046] In one embodiment, the first diol comprises a linear or branched chain hydroxyterminated polydimethylsiloxane, linear or branched chain polyether polydimethylsiloxane with 5 to 50, alternatively 5 to 20, alternatively 7 to 12 polymer units of polydimethylsiloxane endcapped with 5 to 50 units, alternatively 5 to 20, alternatively 7 to 12 polymer units of polyether (polyethyleneoxide or polypropyleneoxide with terminal hydroxy groups). The polyalkylene glycol end-capped polydimethylsiloxane has a molecular weight from 400 to 3000 g / mol. In one further embodiment, the polysiloxane portion of the polyetherpolysiloxane is at least 30 % (w / w). One skilled in the art would know how to select a first diol base on this description. Examples of the first diol are available commercially.

[0047] In various embodiments, the weight average molecular weight of the linear polyetherpolysiloxane diol is from about 500 to about 10,000, about 1000 to about 9500, about 1500 to about 9000, about 2000 to about 8500, about 2500 to about 8000, about 3000 to about 7500, about 3500 to about 7000, about 4000 to about 6500, about 4500 to about 6000, about 5000 to about 5500, about 800 to about 4000, about 1000 to about 4000, about 1500 to about 3500, about 2000 to about 3000, or about 2000 to about 2500, Daltons. Typically, the higher the weight average molecular weight, the more problems with miscibility in the polymerizationreaction can be observed. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0048] Alternatively, the polyetherpolysiloxane moiety may be at least about 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95, weight percent of the linear polyether polysiloxane diol. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0049] In still other embodiments, the polyetherpolysiloxane diol has the formula:wherein c is from about 1 to about 30; d is from about 0 to about 20; and g is from about 3 to about 50 and wherein R12and R13are each independently chosen from C1-C4 aliphatic groups. For example, c may be 1 or any number up to about 30. D may be about 0 or any number up to about 20. G may be 3 or any number up to about 50. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0050] In still other embodiments, the reaction product is further defined as the reaction product of branched diol containing the at least one short chain branching group; the dicarboxylic acid; and an aliphatic diol chosen from 1 ,2-ethanediol; 1 ,3-propanediol; 1 ,4- butanediol; 1 ,5-pentanediol; 1 ,6-hexanediol; 2-methyl-1 ,3-propanediol; 2,2-dimethy-1 ,3- propanediol; 1 ,2-dihydroxy cyclohexane; 1 ,3- di hydroxy cyclohexane; 1 ,4-dihydroxy cyclohexane; 1 ,4-butenediol; diethyleneglycol; and mixtures thereof. In related embodiments, the copolymer has a molar ratio of units derived from the aliphatic diol to units derived from the dicarboxylic acid of from about 0.01 :1 to about 0.1 :1 , 0.1 :1 to about 0.8:1 , about 0.2:1 , about 0.3:1 , about 0.4:1 , about 0.5:1 , about 0.6:1 , about 0.7:1 , about 0.8:1 , about 0.9:1 , or about 1 :1. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0051] In yet another embodiment, the linear aliphatic polyesters may be polylactic acids, polyhgydroyalkanoates, polycaprolactones, and mixtures thereof.The Second Diol

[0052] The second diol is a short chain diol having from 2 to 20, alternatively 2 to 10, alternatively 2 to 8, alternatively 2-6, carbon atoms. The second diol is linear. The second diol can be any short chain diol known in the prior art for use in making polyester copolymers having from 2 to 20 carbon atoms. Examples of the short chain diol include, but are not limited to, 1 ,2-ethanediol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,7- heptanediol, 1 ,8-octanediol, 1 ,9-nonanediol, and 1 ,10-decanediol. In one embodiment, the second diol is 1 ,4-butanediol. Examples of the second diol are available commercially. In one embodiment, the second diol is a mixture of diols described.Difunctional Compound

[0053] The difunctional compound comprises a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester of a dicarboxylic acid. The difunctional compound may be any known in the art for use in making polyester copolymers. In one embodiment, the difunctional compound is a dicarboxylic acid such as an aliphatic dicarboxylic acid or an alkyl diester of an aliphatic dicarboxylic acid. In another embodiment, the difunctional compound is an aromatic dicarboxylic acid or ester or an aromatic dicarboxylic acid. In various embodiments, the difunctional compound is chosen from the dicarboxylic acids terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phthalic acid, phthalic anhydride, cyclohexanedicarboxylic acid, biphenyl dicarboxylic acid, any of the series of C4-C10 aliphatic dicarboxylic acids, a spiroacetal diacid, a combination thereof or a 1 to 5 carbon atom, alternatively 1 to 2 carbon atom, alternatively a one carbon atom alkyl diester of one of the foregoing carboxylic acids. In one embodiment, the difunctional compound is the methyl diester of terephthalic acid. In another embodiment, the dicarboxylic acid is isophthalic acid or the methyl diester of isophthalic acid. In another embodiment, the dicarboxylic acid is naphthalenedicarboxylic acid or the methyl diester of naphthalenedicarboxylic acid. In another embodiment, the dicarboxylic acid is phthalic acid, phthalic anhydride, or methyl diester of phthalic acid. In another embodiment, the dicarboxylic acid is cyclohexanedicarboxylic acid or a methyl diester of cyclohexanedicarboxylic acid. In another embodiment, the dicarboxylic acid or diester is biphenyl dicarboxylic acid or its methyl diester. In another embodiment, the dicarboxylic acid is chosen from C4-C10 aliphatic dicarboxylic acids. For example, aliphatic dicarboxylic acids 0 may be, but are not limited to, those that have 4, 5, 6, 7, 8, 9, or 10 carbon atoms or their methyl diesters. In another embodiment, the dicarboxylic acid is a mixture of aromatic and aliphatic dicaboxylic acids or diesters. In yet another embodiment, the dicarboxylic acid is a spiroacetal diacid or its methyl diester. One skilled in the art would know how to procure ormake the difunctional compound according to the invention. Many of representative difunctional acids are available commercially.

[0054] Without intending to be bound by any particular theory, it is believed that the choice of the difunctional compound such as dicarboxylic acid or their alkyl esters influences the presence of crystalline segments in the backbone of the copolymer which, in turn, influences the cohesive strength of the copolymer and the final composition.Third Diol

[0055] The third diol comprises a branched hydrocarbyl group, alternatively a branched hydrocarbyl group having from 4 to 20 carbon atoms, alternatively 4 to 8 carbon atoms, alternatively from 6 to 10 carbon atoms, alternatively 7 to 9 carbon atoms. Examples of hydrocarbyl include, branched alkyl, such as 1-methylethyl, 1 -methylpropyl, 2-methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, 1 -methylbutyl, 1 -ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1 ,2, -dimethylpropyl, 2,2-dimethylpropyl, 1 -methylhexyl, 2-methylhexyl, 1-ethylhexyl, 2- ethylhexyl, 1-methylheptyl, alkyl-substituted (i.e., branched) octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; aryl, such as phenyl and naphthyl; alkaryl, such as tolyl and xylyl; aralkyl such as benzyl and phenylethyl; branched alkenyl, such as 1 -methylethenyl, 1- methylpropenyl, 2-methylbutenyl, 1 -ethylhexenyl, 2-ethylhexenyl.

[0056] In certain embodiments, the branched hydrocarbyl group is covalently bonded at a carbon atom, through an oxygen linking group, or through -R’-O-, where R’ is hydrocarbylene having from 1 to 3 carbon atoms, to a carbon chain having at least two, alternatively two or three, alternatively 2 hydroxyl groups and having from 2 to 18 carbon atoms, alternatively 3 to 10 carbon atoms, alternatively 3 to 5 carbon atoms. The carbon chain may have further branching or may be linear.

[0057] In one embodiment, the third diol is according to formula I: --0H(I) wherein R1 is hydrogen, hydrocarbyl, or ether, alternatively hydrogen or hydrocarbyl,alternatively hydrogen, R2 is hydrocarbyl or ether, alternatively hydrocarbyl or ether, R3 is hydrocarbylene.

[0058] When R1 is hydrocarbyl, or ether, R1 has 1 to 12 carbon atoms (C1-C12), alternatively 2 to 8 carbon atoms. R2 may have from 1 to 12 carbon atoms (C1-C12), alternatively 2 to 8 carbon atoms. R3 may have from 1 to 5 carbon atoms, alternatively 1 to 3 carbon atoms, alternatively 1 carbon atom.

[0059] Examples of hydrocarbyl for R1 having from 1 to 12 atoms include, but are not limited to, linear alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and branched alkyl, such as 1 -methylethyl, 1 -methylpropyl, 2-methylpropyl, 2- methylpropyl, 1 ,1 -dimethylethyl, 1 -methylbutyl, 1 -ethyl propyl, 2-methylbutyl, 3-methylbutyl, 1 ,2, -dimethylpropyl, 2,2-dimethylpropyl, 1 -methylhexyl, 2-methylhexyl, 1-ethylhexyl, 2- ethylhexyl, 1-methylheptyl, alkyl-substituted (i.e., branched) octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; aryl, such as phenyl and naphthyl; alkaryl, such as tolyl and xylyl; aralkyl such as benzyl and phenylethyl; branched alkenyl, such as 1 -methylethenyl, 1- methylpropenyl, 2-methylbutenyl, 1 -ethylhexenyl, 2-ethylhexenyl.

[0060] Examples of ether for R1 include, but are not limited to, the hydrocarbyl groups described above for R1 bonded including an oxygen linking group, or through -R’-O-, where R’ is hydrocarbylene having from 1 to 3 carbon atoms.

[0061] Examples of hydrocarbyl and ether for R2 include those described for R1 above.

[0062] In one embodiment, R1 is hydrogen and R2 is ether, alternatively hydrogen and ether, where the ether is hydrocarbylenehydrocarbyloxy, alternatively ethylhexyloxymethylene.

[0063] Examples of the third diol include, but are not limited to, methylethylglycerin, methylpropylglycering, methylbutylglycerin, methylpentylglycerin, methylhexylglycering, methylheptylglycering, methyloctylglycerin, methylnonylglycerin, methyldecylglycering, methyldodecylglycerin, ethylethylglycerin, ethylpropylglycering, ethylbutylglycerin, ethylpentylglycerin, ethylhexylglycering, ethylheptylglycering, ethyloctylglycerin, ethylnonylglycerin, ethyldecylglycering, ethyldodecylglycerin2-methyl-2-propyl-1 ,3- propanediol, 2-phenyl-1 ,3-propanediol, 1 ,2-dodecanediol, dimerized fatty acid diols (for example, Pripol™ 2030, Pripol™ 2033 and Pripol™ 2043 from Cargill) and mixtures thereof. In one embodiment, the third diol is ethylhexylglycerin.

[0064] The third diol may be a mixture of diols meeting the description of the third diol. Many materials meeting the description of third diol are available commercially. One skilled in the ar would know how to acquire materials meeting the description of the third diol.Polyol

[0065] In one embodiment, the polyester copolymer may further comprise a polyol, wherein the polyol is a linear oligomer, polymer, or copolymer comprising at least three hydroxyl groups. The polyol introduces branching sites for the polyester copolymer backbone. Any polyol known in the prior art for use in producing polyester copolymers may be used. Examples of polyols include copolymers of alkylene glycol and a polyol monomer such as glycerin or similar reactant having three or more hydroxyl groups. One skilled in the art would understand how to select a polyol to include in the production of the polyester copolymer.End-Capping Agent

[0066] In one embodiment, the polyester copolymer further comprises an end-capping agent. The end-capping agent may be a linear or branched mono-alcohol or combination thereof, preferably a secondary or primary alcohol or combination thereof, more preferably a primary alcohol or combination thereof. Examples of optional end-capping agents include, but are not limited to, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, lauryl alcohol, 1-tridecanol, myristyl alcohol, 1 -pentadecanol, cetyl alcohol, 1 -heptadecanol, stearyl alcohol, oleyl alcohol, saturated and unsaturated fatty alcohols, ethoxylated alcohols, ethoxylated polydimethylsiloxanes such as Silsurf A008-UP and Silsurf A004-UP from Siltech, and combinations thereof. One skilled in the art would understand how to pick an optional endcapping agent for use in producing a polyester copolymer according to the invention. Many of these materials are available commercially.Triol

[0067] In one embodiment, the polyester copolymer further comprises a triol. The triol comprises from 3 to 100, alternatively from 3 to 20, alternatively from 3 to 10 carbon atoms. The triol comprises at least three, alternatively three hydroxyl groups. In one embodiment, the triol is a hydrocarbon having 3 hydrogens substituted with hydroxyl groups, alternatively a alkane substituted with 3 hydroxyl groups, where examples of alkane include, but are not limited to methane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, 1 -methylethane, 1 -methylpropane, 2-methylpropane, 2-methylpropane, 1 ,1- dimethylethane, 1-methylbutane, 1 -ethylpropane, 2-methylbutane, 3-methylbutane, 1 ,2,- dimethylpropane, 2,2-dimethylpropane, 1 -methylhexane, 2-methylhexane, 1 -ethylhexane, 2- ethylhexane, 1 -methylheptane, alkyl-substituted, dodecane, tridecane, and tetradecane;cycloalkane, such as cyclopentane, cyclohexane, and methylcyclohexane; aromatic, such as benzene and toluene. Examples of the triol include, but are not limited to, glycerol, trimethylolethane, trimethylolpropane (or 2-Ethyl-2-(hydroxymethyl)propane-1 ,3-diol), trimethylolbutane, trimethylolpentane, pentaerythritol, trimethylolhexane, trimethylolheptane, trimethyloloctane, trimethyloldecane, trimethyloldodecanetris(hydroxyethyl) isocyanurate, dipentaerythritol, tripentaerythritol, maltitol, sorbitol, xylitol, erythritol, 1 ,2,6-hexanetriol, polyether glycols, polyester glycols, trimethylolpropane allyl ether / trimethylolethane allyl ether, dimethylolpropionic acid, 2,2-dimethylolbutryic acid, 5-(2-hydroxyethoxy) isophathalic acid, 5- acetoxyisophthalic acid, 3,5-bis(2-hydroxyethoxy)benzoic acid. In one embodiment, the triol is glycerol or trimethylolpropane. One skilled in the art would understand how to pick a triol for use in producing a polyester copolymer according to the invention. The triols of the invention are available commercially.

[0068] A method of making a polyester copolymer, comprising the following steps: combining a first diol and second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short chain diol having from 2 to 20 carbon atoms; a difunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; a third diol, wherein the third diol comprises a branched hydrocarbyl or hydrocarbyloxy group; optionally, an end-capping agent; and a catalyst to form a reaction mixture, exposing the reaction mixture to conditions sufficient to cause a reaction and form the polyester copolymer.

[0069] In the method of making the polyester copolymer, the first diol, second diol, third diol, and difunctional compound are as described above for the polyester copolymer. The catalyst may be any catalyst known in the art for making polyesters. In one embodiment, the catalyst may be a titanium-based, tin-based, zinc-based or zirconium-based catalyst.Examples of suitable catalysts known in the art are titanium (IV) isopropoxide, titanium (IV) isobutoxide, or titanium (IV) n-butoxide, titanium (IV) acetylacetonate, zirconium (IV) n- butoxide, tin 2-ethylhexanoate, organotin oxides such as dibutyltin oxide, dibutyltin diacetate, zinc acetate and combinations thereof. In one embodiment, the catalyst is a titanium alkanoate, such as titanium (IV) isopropoxide, titanium (IV) isobutoxide, or titanium (IV) n-butoxide. In another embodiment, the catalyst is n-butyl titanate. Many catalysts form making polyesters are commercially available.

[0070] The combining of the first diol, second diol, third diol, and difunctional compound and catalyst to form a reaction mixture are done according to methods known in the art. The reaction mixture is exposed to conditions sufficient to cause a reaction and form the polyester copolymer. Conditions sufficient to form the polyester copolymer are those conditions known in the art. Reactors known in the art for making polyesters may be used to make the polyester copolymer of the invention and to practice the method of making a polyester copolymer of the invention.

[0071] A pressure sensitive adhesive comprising the polyester copolymer described above. A pressure sensitive adhesive made according to the method of the invention.

[0072] A dermal patch comprising the pressure sensitive adhesive described above, wherein the patch is a transdermal drug delivery patch or a wound care patch. The dermal patch may be made by methods know in the art. For example, the dermal patch may be made by forming a film on a backing sheet made of materials known in the art.

[0073] A medical device comprising the pressure sensitive adhesive. The pressure sensitive adhesive can be used to adhere the medical device to the body. The pressure sensitive adhesive can be made by methods known the art. For example, a film made in the shape of the device can be made and adhered to the medical device.

[0074] A polyester copolymer, comprising: random units having the formulas[-OR4O-], [-OR5O-], [-C(O)R6C(O)-], [-OR7O-], wherein R4is hydrocarbylene having from 2 to 20 carbon atoms, alternately 2 to 5 carbon atoms, alternatively from 2 to 4 carbon atoms, R5is a branched hydrocarbylene, branched hydrocarbyloxy-substituted hydrocarbylene, or branched ether-substituted hydrocarbylene having from 4 to 20 carbon atoms, R6is hydrocarbylene having from 2 to 12 carbon atoms, wherein R7is oligomeric, copolymeric, or polymeric hydrocarbylene or alkylene glycol having a Mw greater than 400 g / mol, alternatively from 400 to 3000 g / mol, and where the polyester copolymer is hydroxy, carboxy, or carboxylate terminated.

[0075] R4is hydrocarbylene having from 2 to 20 carbon atoms. Examples of the hydrocarbylene include, but are not limited to, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene and branched alkylene, such as 1 -methylethylene, 1 -methylpropylene, 2-methylpropylene, 2-methylpropylene, 1 ,1- dimethylethylene, 1 -methylbutylene, 1 -ethylpropylene, 2-methylbutyl, 3-methylbutylene, 1 ,2,- dimethylpropylene, 2,2-dimethylpropylene, 1 -methylhexylene, 2-methylhexylene, 1-ethylhexylene, 2-ethylhexylene, 1 -methylheptylene, alkyl-substituted (i.e., branched) octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, and tetradecylene; cycloalkylene, such as cyclopentylene, cyclohexylene, and methylcyclohexylene; aryl, such as phenylene and naphthylene; alkarylene, such as tolylene and xylylene; aralkylene such as benzylene and phenylethylene; branched alkenylene, such as 1-methylethenylene, 1- methylpropenylene, 2-methylbutenylene, 1-ethylhexenylene, 2-ethylhexenylene.

[0076] R5is a branched hydrocarbylene, branched hydrocarbyloxy-substituted hydrocarbylene, or branched ether-substituted hydrocarbylene having from 4 to 20 carbon atoms. Examples of the branched hydrocarbylene are as described from R4. Examples of hydrocarbyloxy-substituted hydrocarbylene include hydrocarbylene as described for R5substituted with one or more hydrocarbyloxy groups. Examples of hydrocarbyloxy include, but are not limited to, alkyloxy, such as methoxy, ethoxy methylethoxy, ethylethoxy, methylpropoxy, ethylpropoxy, propylpropoxy, methylbutoxy, ethylbutoxy, propylbutoxy, ethylhexoxy. In one embodiment, R5is ethylhexyloxymethylethylene, [-CH2C(H)(CH2OCH(CH2CH3)((CH2)4CH3))-].

[0077] R6is hydrocarbylene having from 4 to 12 carbon atoms. Examples of hydrocarbylene R6include, but are not limited to, 1 ,3- and 1 ,4-phenylene, naphthalene, , cyclohexylene, biphenylene, any of the series of C4-C10 aliphatic hydrocarbylene, a spiro groups, a combination thereof. In one embodiment, the difunctional compound is phenylene.

[0078] R7is an oligomeric, copolymeric, or polymeric hydrocarbylene or alkylene glycol having a Mw greater than 400 g / mol, alternatively from 400 to 3000 g / mol. Examples include, but are not limited to, polyethyleneoxide, polypropyleneoxide, polyethylenepropyleneoxide.

[0079] In one embodiment, the polyester copolymer further comprises a unit having the structure of polyalkyleneglycol end-capped diorganopolysiloxane having a molecular weight from 400 to 3000 g / mol per unit or a polyether. This unit is derived from the polyalklenoxide polysiloxane described above.

[0080] In one embodiment, the polyester copolymer further comprises a linear polyol unit according to the formula [-OR8(O-)O-], wherein R8is trivalent hydrocarbyl having from 4 to 3000 carbon atoms. Examples of trivalent hydrocarbyl groups include, but are not limited to, trivalent butane, pentane, hexane, heptane, and their isomers. In one embodiment, R7is 2- ethyl-2-methylenepropylene.

[0081] One particularly important application for the polyester copolymer of the present invention is in a transdermal or local drug delivery system or in a topical medicated patch forlocal administration of a drug to a substrate, such as cutaneous or mucosal tissues. The system includes an active agent and the polyester copolymer of the present invention functioning as a pressure sensitive adhesive. The active agent and its relationship to the polyester copolymer in the context of the system are described in detail below. As those skilled in the art appreciate, the system is structural and can be in many forms including, but not limited to, patches, films, multi-layer dressings, reservoir systems, and combinations thereof. The active agent is in the system for controlled transdermal delivery to a substrate. It is also possible, but not required, for the system to include a backing layer for supporting the polyester copolymer, and / or a release liner for protecting the polyester copolymer and / or the active agent prior to the controlled transdermal delivery of the active agent to the substrate. One preferred application of the transdermal drug delivery system of the present invention is to treat a user, or patient, with the active agent. As a result, the substrate is typically the skin of the user and, in this preferred application, the user applies and wears the system on their skin.

[0082] The active agent can be any component suitable for transdermal delivery to a substrate. Suitable active agents include, but are not limited to, those active agents disclosed and so described in U.S. Pat. No. 5,474,783 to Miranda et al., the disclosure of which is incorporated by reference herein in its entirety. These active agents include, but are not limited to, cardioactive medications, androgenic steroids, estrogens, hormones, progestational agents, drugs having an action on the central nervous system, nutritional agents, anti-inflammatory agents, antihistamines, respiratory agents, sympathomimetics, miotics, cholinergic agonists, antimuscarinic or muscarinic cholinergic blocking agents, mydriatics, psychic energizers, anti-infectives, dermatological agents, humoral agents, antispasmodics, antidepressant drugs, antidiabetic, anorectic drugs, anti- allergenics, tranquilizers, antipsychotics, decongestants, antipyretics, antimigraine agents, drugs for treating nausea and vomiting, anti-malarials, anti-ulcerative agents, peptides, drugs for Parkinson's disease, drugs for spasticity, drugs for acute muscle spasms, anti-estrogen, anti-hormone agents, pain relief agents, local anesthetics, drugs for dermatological treatments, therapeutic agents, and combinations thereof.

[0083] More specific examples of the active agents outlined above that are suitable for implementation as the active agent in the present invention include: cardioactive medications, illustratively, organic nitrates such as nitroglycerin, isosorbide dinitrate and, isosorbide mononitrates; quinidine sulfate; procainamide; thiazides such asbendroflumethiazide, chlorothiazide, and hydrochlorothiazide; nifedipine; nicardipine; adrenergic blocking agents, such as timolol, and propranolol; verapamil; diltiazem; captopril; clonidine and prazosin; androgenic steroids, such as testosterone, methyltestosterone and fluoxymesterone; estrogens, such as, conjugated estrogens, esterified estrogens, quinestrol, estropipate, 17-(3 estradiol, 17-(3 estradiol valerate, equilin, mestranol, estrone, estriol, 17-(3 ethinyl estradiol, and diethylstilbestrol; Progestational agents, such as progesterone, 19-norprogesterone, norethindrone, norethindrone acetate, melengestrol, chlormadinone, ethisterone, medroxyprogesterone acetate, hydroxyprogesterone caproate, ethynodiol diacetate, norethynodrel, 17-alpha- hydroxyprogesterone, dydrogesterone, dimethisterone, ethinylestrenol, norgestrel, demegestone, promegestone, and megestrol acetate; drugs having an action on the central nervous system, for example sedatives, hypnotics, antianxiety agents, analgesics and anesthetics, such as chloral, buprenorphine, naloxone, haloperidol, fluphenazine, pentobarbital, phenobarbital, secobarbital, codeine, lidocaine, tetracaine, dyclonine, dibucaine, cocaine, procaine, mepivacaine, bupivacaine, etidocaine, prilocaine, benzocaine, fentanyl, and nicotine; Nutritional agents, such as vitamins (e.g. niacinamide), essential amino acids and essential fats; Anti-inflammatory agents, such as hydrocortisone, cortisone, dexamethasone, fluocinolone, triamcinolone, medrysone, prednisolone, flurandrenolide, prednisone, halcinonide, methylprednisolone, fludrocortisone, corticosterone, paramethasone, betamethasone, ibuprofen, naproxen, fenoprofen, fenbufen, flurbiprofen, acetaminophen, indoprofen, ketoprofen, suprofen, indomethacin, piroxicam, aspirin, salicylic acid, diflunisal, methyl salicylate, phenylbutazone, sulindac, mefenamic acid, meclofenamate sodium, naproxen, and the like; external analgesics, such as camphor, menthol, capsicum extract, frankincense, green tea, juniper tea, and caffeine; antihistamines, such as diphenhydramine, dimenhydrinate, perphenazine, triprolidine, pyrilamine, chlorcyclizine, promethazine, carbinoxamine, tripelennamine, brompheniramine, hydroxyzine, cyclizine, meclizine, terfenadine, and chlorpheniramine; respiratory agents, such as theophylline and Beta-adrenergic agonists such as albuterol, terbutaline, metaproterenol, ritodrine, carbuterol, fenoterol, quinterenol, rimiterol, solmefamol, soterenol, and tretoquinol; sympathomimetics such as dopamine, norepinephrine, phenylpropanolamine, phenylephrine, pseudoephedrine, amphetamine, propylhexedrine and epinephrine; miotics such as pilocarpine, and the like; cholinergic agonists, such as choline, acetylcholine, methacholine, carbachol, bethanechol, pilocarpine, muscarine, and arecoline; antimuscarinic or muscarinic cholinergic blocking agents, such as atropine, scopolamine, homatropine, methscopolamine, homatropinemethylbromide, methantheline, cyclopentolate, tropicamide, propantheline, anisotropine, dicyclomine, and eucatropine; mydriatics, such as atropine, cyclopentolate, homatropine, scopolamine, tropicamide, eucatropine and hydroxyamphetamine; psychic energizers, such as 3-(2-aminopropy)indole, 3-(2- 5 aminobutyl)indole, and the like; anti-infectives, such as antibiotics, including penicillin, tetracycline, chloramphenicol, sulfacetamide, sulfadiazine, sulfamethoxazole and sulfisoxazole; antivirals, including idoxuridine; antibacterials, such as erythromycin and io clarithromycin; anti-fungals, such as ketoconazole, and other anti- infectives including nitrofurazone, cyclopirox, terbafine, witch hazel, and the like; dermatological agents, such as retinoids; vitamins C and E; benzoyl peroxide (BPO) (also commonly referred to as 15 dibenzoyl peroxide) and dapsone; humoral agents, such as the prostaglandins, natural and synthetic, for example PGE1 , PGE 2-alpha, and PGF 2-alpha, and the PGE1 analog misoprostol; antispasmodics, such as atropine, methantheline, papaverine, cinnamedrine, and methscopolamine; antidepressant drugs, such as paroxetine, phenelzine, tranylcypromine, imipramine, amitriptyline, trimipramine, doxepin, desipramine, nortriptyline, protriptyline, amoxapine, maprotiline, and trazodone; anti-diabetics, such as insulin, and anticancer drugs such as tamoxifen and methotrexate; anorectic drugs, such as, dextroamphetamine, methamphetamine, phenylpropanolamine, fenfluramine, diethylpropion, mazindol, and phentermine; anti-allergenics, such as antazoline, methapyrilene, chlorpheniramine, pyrilamine and pheniramine; tranquilizers, such as reserpine, chlorpromazine, and antianxiety benzodiazepines such as alprazolam, chlordiazepoxide, clorazepate, halazepam, oxazepam, prazepam, clonazepam, flurazepam, triazolam, lorazepam and diazepam; antipsychotics, such as thiopropazate, chlorpromazine, triflupromazine, mesoridazine, piperacetazine, thioridazine, acetophenazine, fluphenazine, perphenazine, trifluoperazine, chlorprothixene, thiothixene, haloperidol, bromperidol, loxapine, and molindone; decongestants, such as phenylephrine, ephedrine, naphazoline, tetrahydrozoline; antipyretics, such as aspirin, salicylamide, and the like; antimigraine agents, such as dihydroergotamine and pizotyline; drugs for treating nausea and vomiting, such as chlorpromazine, perphenazine, prochlorperazine, promethazine, thiethylperazine, triflupromazine, and trimeprazine; anti-malarials, such as the 4- aminoquinolines, alphaminoquinolines, chloroquine, and pyrimethamine; anti-ulcerative agents, such as misoprostol, omeprazole, and enprostil; peptides, such as growth releasing factor; drugs for Parkinson's disease, spasticity, and acute muscle spasms such as levodopa, carbidopa, amantadine, apomorphine, bromocriptine, selegiline (deprenyl), trihexyphenidyl hydrochloride, benztropine mesylate, procyclidine hydrochloride, baclofen,diazepam, and dantrolene; and anti-estrogen or hormone agents, such as tamoxifen or human chorionic gonadotropin.

[0084] In one embodiment, the active agent is selected from the group of ketoprofen, estradiol, clonidine, and combinations thereof.

[0085] As indicated above, the particular active agent is not limited to those recited above. Other examples of suitable active agents for use in the systems will be apparent to those skilled in the art (See, for example, pages 149-217 of Yie Chien's US 8,614,278 B2 treatise entitled "Novel Drug Delivery Systems" which is Volume 14 of Drugs and the Pharmaceutical Sciences, Marcel Dekker, Inc., New York, N.Y. 10016 (1982)). As those skilled in the art appreciate, the active agents can be present in the system in different forms, depending on which form yields optimum delivery characteristic, such as the release rate and the total amount released as described below. For example, in the case of drugs, the drug can be in its free base or acid form, or in the form of salts, esters, or any other pharmacologically acceptable derivatives, or even as components of molecular complexes.

[0086] Furthermore, relative to the active agent, it is to be recognized that the active agent is most typically disposed in the polyester copolymer. However, it is also to be understood that the active agent and the polyester copolymer may coexist in the system in discrete layers. That is, in certain embodiments, the active agent is not disposed, or directly incorporated, into the polyester copolymer. Of course, the transdermal drug delivery system can also contain other agents known to accelerate the delivery of the active agent through the skin or other substrate. These other agents are also referred to in the art as skinpenetration or permeation enhancers, accelerants, adjuvants, and sorption promoters, and are collectively referred herein simply as io "enhancers". These enhancers includes those with diverse mechanisms of action including those which have the function of improving the solubility and diffusibility of the active agent within the polyester copolymer and those which improve percutaneous absorption, for example, by changing the ability of the stratum corneum to retain moisture, softening the skin, improving the skin's permeability, acting as penetration assistants or hair-follicle openers or changing the state of the skin including the boundary layer. Some of these enhancers have more than one mechanism of action, but in essence they serve to enhance the delivery of the active agent to the substrate.

[0087] Some examples of enhancers are polyhydric alcohols such as dipropylene glycol, propylene glycol, and polyethylene glycol which enhance solubility of the active agent, oils such as olive oil, squalene, and lanolin; fatty ethers such as cetyl ether and oleyl ether; fatty acid esters such as isopropyl myristate which enhance diffusibility of the active agent; ureaand urea derivatives such as allantoin which affect the ability of keratin to retain moisture; polar solvents such as dimethyldecylphosphoxide, methyloctylsulfoxide, dimethyllaurylamide, dodecylpyrrolidone, isosorbitol, dimethylacetonide, dimethylsulfoxide, decylmethylsulfoxide, and dimethylformamide which affect keratin permeability; salicylic acid which softens the keratin; amino acids which are penetration assistants; benzyl nicotinate which is a hair follicle opener; and higher molecular weight aliphatic surfactants such as lauryl sulfate salts which change the surface state of the substrate, e.g. skin, and the active agents administered. Other agents include oleic and linoleic acids, ascorbic acid, pan-thenol, butylated hydroxytoluene, tocopherol, tocopheryl acetate, tocopheryl linoleate, propyl oleate, and isopropyl palmitate.

[0088] Other applications of the polyester copolymer of the present invention include medical device skin and prosthesis adhesion e.g., limb prosthesis, wig, medical device assembly adhesive, adhesive for in vitro diagnostics, tape adhesive, adhesive film, adhesive for surgical drapes, electrically conductive adhesive, adhesive for ostomy devices, adhesive for incontinence devices, such as urisheath, pouch, adhesive for securing catheters, and adhesive for dressings used in wound care, scar care, negative pressure wound therapy, border dressings, and intravenous (IV) dressings.

[0089] Other applications of the polyester copolymer of the present invention include adhesive and patch for dermo-cosmetic applications, facial mask, skin moisturizing, wrinkle treatment, make up, color cosmetic, fixation of hair, disguises.

[0090] In certain embodiments of the invention, an additive such as a plasticizer or tackifying agent may be incorporated into the system, typically into the composition, to improve the adhesive characteristics of the polyester copolymer. A tackifying agent is particularly useful in those embodiments in which the active agent does not plasticize the polyester polymer. Suitable tackifying agents are those known in the art including: (1) aliphatic hydrocarbons; (2) mixed aliphatic and aromatic hydrocarbons; (3) aromatic hydrocarbons; (4) substituted aromatic hydrocarbons; (5) hydrogenated esters; (6) polyterpenes; and (7) hydrogenated wood rosins. The tackifying agent employed is typically compatible with the other components in the composition.

[0091] In certain embodiments, the polyester copolymer can include a filler for mechanical reinforcement, rheology profile modification, thermal conductivity, electrical conductivity, or a combination thereof. In certain embodiments, the filler may include, but is not limited to, microspheres, expandable materials, containing liquids or gases, silica, cellulosiccellulosics, polysaccharides, conductive fillers, metallic fibers, graphitic, conductive materials such ascarbon nanotubes and silver nanowires, and combinations thereof. Tackifiers, plasticizers, and / or filler particles are known in the art, and they are used at dosages known in the art.

[0092] The adhesive composition can be a pressure sensitive adhesive.

[0093] The adhesive composition may be designed to be applied to any substrate. For example, the substrate may be human or animal skin. Alternatively, the substrate may be a medical device or implement. For example, the substrate may be, but is not limited to, plastic, polymeric, fabric, nonwoven, paint, wood, metal, ceramic.

[0094] Examples of suitable tackifying agents are silicone fluids (e.g., Q7-9120 Silicone Fluid, available from Dow Corning Corporation, Midland, Mich.), silicone resins (e.g., Q2- 7466 INT, available from Dow Corning Corporation, Midland, Mich.), or mineral oil. Silicone fluids and silicone resins are useful for blends comprising polysiloxane as a major component. In other embodiments, where a synthetic rubber, for example, is a major component, mineral oil is a useful tackifying agent. Notably some active agents, such as vasodilator nitroglycerin, function as plasticizers in the composition because they are soluble to a certain degree in the components of the composition. For active agents which are not readily soluble in the components, a co-solvent for the active agent and other components can be added. Co-solvents, such as lecithin, retinol derivatives, tocopherol, dipropylene glycol, triacetin, propylene glycol, saturated and unsaturated fatty acids, mineral oil, silicone fluid, alcohols, butyl benzyl phthalate, and the like are useful in the practice of the instant invention depending on the solubility of the active agent in the composition.

[0095] Certain aspects of the invention follow:

[0096] Aspect 1 . A polyester copolymer, comprising: the reaction product of a first diol and second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short chain diol having from 2 to 20 carbon atoms; a difunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; a third diol, wherein the third diol comprises a branched hydrocarbyl group.

[0097] Aspect 2. The polyester copolymer according to Aspect 1 , wherein the polyester copolymer comprises a polyol.

[0098] Aspect 3. The polyester copolymer according to Aspect 2, wherein the polyol is oligomeric, polymeric, copolymeric, or copolymeric.

[0099] Aspect 4. The polyester copolymer according to any one of Aspect 2 or 3, wherein the polyol is linear.

[0100] Aspect 5. The polyester copolymer according to any one of the preceding Aspects, further comprising a triol monomer.

[0101] Aspect 6. The polyester copolymer according to any one of the preceding Aspects, wherein the first diol is an oligomeric polyether.

[0102] Aspect 7. The polyester copolymer according to any one of Aspects 1 -5, wherein the first diol has polysiloxane and polyalkylene glycol segments.

[0103] Aspect 8. The polyester copolymer according to Aspect 7, wherein the first diol is a polysiloxane terminated with polyalkylene glycol segments.

[0104] Aspect 9. The polyester copolymer according to any one of the preceding Aspects, wherein the second diol has from 2 to 8 carbon atoms, alternatively from 3 to 8, alternatively from 2 to 6, alternatively 3 to 6, carbon atoms.

[0105] Aspect 10. The polyester copolymer according to any one of the preceding Aspects, wherein the difunctional compound is a phthalate.

[0106] Aspect 11 . The polyester copolymer according to any one of the preceding Aspects, wherein the third diol is according to formula I:(I) wherein R1 is hydrogen, hydrocarbyl, hydrocarbyloxy, or ether having 1 to 12 carbon atoms (C1-C12), and R2 is hydrocarbyl, hydrocarbyloxy, or ether having 1 to 12 carbon atoms (CICI 2), R3 is hydrocarbylene having from 1 to 5 carbon atoms.

[0107] Aspect 12. A method of making a polyester copolymer, comprising the following steps: combining a first diol and second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short chain diol having from 2 to 20 carbon atoms; a difunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; a third diol, wherein the third diol comprises a branched hydrocarbyl or hydrocarbyloxy group; and a catalyst to form a reaction mixture, exposing the reaction mixture to conditions sufficient to cause a reaction and form the polyester copolymer.

[0108] Aspect 13. A pressure sensitive adhesive comprising the polyester copolymer composition according to any one of Aspects 1-11.

[0109] Aspect 14. A pressure sensitive adhesive according to Aspect 13, wherein the pressure sensitive adhesive is made according to the method of claim 12.

[0110] Aspect 15. A dermal patch comprising the pressure sensitive adhesive according to one of Aspects 13 or 14, wherein the patch is a transdermal drug delivery patch or a wound care patch.

[0111] Aspect 16. A medical device comprising the pressure sensitive adhesive according to one of Aspects 13 or 14.

[0112] Aspect 17. A polyester copolymer, comprising: random units having the formulas [-OR4O-], [-OR5O-], [-C(O)R6C(O)-], [-OR7O-], wherein R4is hydrocarbylene having from 2 to 20 carbon atoms, alternately 2 to 5 carbon atoms, alternatively from 2 to 4 carbon atoms, R5is a branched hydrocarbylene, branched hydrocarbyloxy-substituted hydrocarbylene, or branched ether-substituted hydrocarbylene having from 4 to 20 carbon atoms, R6is hydrocarbylene having from 2 to 12, alternatively 4 to 12, carbon atoms, wherein R7is oligomeric, copolymeric, or polymeric hydrocarbylene or alkylene glycol having a Mw greater than 400 g / mol, alternatively from 400 to 6000 g / mol, alternatively from 400 to 3000 g / mol, and where the polyester copolymer is hydroxy, carboxy, or carboxylate terminated.

[0113] Aspect 18. The polyester copolymer according to Aspect 17, further comprising a unit having the structure of polyalkyleneglycol end-capped diorganopolysiloxane having a moleculare weight from 400 to 3000 g / mol per unit or a polyether.

[0114] Aspect 19. The polyester copolymer according to one of Aspects 17 or 18, further comprising a linear polyol unit according to the formula [-OR7(O-)O-], wherein R7is trivalent hydrocarbyl having from 2 to 3000, alternatively 4 to 3000, carbon atoms.

[0115] Aspect 20. A polyester copolymer, comprising: a first diol and second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short chain diol having from 2 to 20 carbon atoms; a difunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; a third diol, wherein the third diol comprises a branched hydrocarbyl group.

[0116] The polyester copolymer of the invention can be used where pressure sensitive adhesives are used in healthcare applications with improved skin properties. The polyester copolymer may be used as a pressure sensitive adhesive in patches and medical devices for securing the patch or device to keratinaceous and mucosal substrates.EXAMPLES

[0117] The following examples are presented to better illustrate the method of the present invention but are not to be considered as limiting the invention, which is delineated in theappended claims. Unless otherwise noted, all parts and percentages reported in the examples are by weight. The following table describes the abbreviations used in the examples:

[0118] All copolymerization reactions were conducted in a 2 L Buchi autoclave fitted with a triple ribbon helical impeller, Vigreux column, glass condenser, vacuum line, and separate nitrogen inlet.

[0119] Polymer composition was determined by analysis with1H NMR spectroscopy. The integrals were normalized to the peak for the aromatic terephthalate protons, and the mol% of terephthalate was assumed to be 50%. Molecular weight, average molecular weight, and dispersity were determined by GPC analysis with calibration according to the UV absorption at 250 nm.

[0120] The peel adhesion in N (newtons) is measured using Tensile Testing equipment (e.g. Instron). The sample is prepared by heating the adhesives, coating them on the appropriate substrate, and pressing them to the desired thickness. The coated substrate is then cut in 2.5 cm strips (1 inch), and a polycarbonate film is laminated to the surface. Test parameters: 180° peel release test, test speed = 10.0 mm / s, distance = 90.0 mm. Each sample was run in triplicate and the average force (N) was reported. Any observed characteristics were noted.

[0121] Parallel plate rheology was recorded on a TA Instruments Discovery HR-1 at a sample measurement temperature of 30 °C.Table 1. Abbreviations used herein.

[0122] Dimethylterephthalate (DMT), 1 ,4-butanediol (BDO), polypropylene glycol (PPG2000 and PPG4000), polytetramethylene ether glycol (PTMEG2000), polybutyleneterephthalate (PBT Mn 38,000), PPG-PEG-PPG, trimethylolpropane (TMP), 2-ethyl-1 ,3-hexanediol, lauryl alcohol, Ethanox 330, and Tyzor® (n-butyl titanate) were purchased from Sigma Aldrich. Ethylhexyl glycerin was obtained from Ambeed. 1 ,2-Hexanediol; 1 ,2-dodecanediol; 2-methyl-2-propylpropane-1 ,3-diol; and PTMEG2900 were purchased from TCI America. HTPB commercial grade was procured from Island Pyrochemicals. Silsurf Di-1010, Silsurf Di-2012, Silsurf A008- UP, and Silsurf Di-151 were purchased or received as samples from Siltech.Polyethyleneterephthalate was purchased from Goodfellow. Glycerol from P&G was obtained through Univar. Ethylene glycol was purchased from Fisher Scientific.For reactions starting from DMT and BDO:

[0123] All of the reaction components except for the catalyst were added to the reactor. The reactor was evacuated and backfilled with nitrogen three times. The reaction mass was heated to a jacket temperature of 180 °C with stirring at 60 RPM. The Tyzor® catalyst was injected once the reactor reached an internal temperature of 80 °C. The jacket temperature was then raised to 210 °C for about 2.5 hours with concomitant distillation of methanol. Once butanediol began to azeoptrope with the methanol - corresponding to a drop in temperature at the bottom of the distillation column - the jacket temperature was raised to 240 °C, and the pressure in the reactor was reduced to about 80 torr. After about 1 h, the jacket temperature was raised to 250 °C. After another hour, the jacket temperature was raised to 260 °C, and the pressure was reduced to about 20 torr. The vacuum was raised over the next 2-6 hours until the pressure in the reactor was about 0.5 torr. The reaction was stirred at this temperature and pressure until the torque reached a plateau of 10 to 110 Ncm for about 30 minutes. At this time, the reactor was cooled to room temperature and jacketed with nitrogen. The resulting polymer was manually removed from the vessel. For polymers substituting ethylene glycol (EG) for BDO, the same basic procedures were followed, except that 1 ,2-ethandiol was collected in the distillate instead of BDO.

[0124] For reactions starting from PBT or PET pre-polymer:All reaction components except for the catalyst were added to the reactor. The reactor was evacuated and backfilled with nitrogen three times. The reaction mass was heated to a jacket temperature of 180 °C with stirring at 60 RPM. The Tyzor® catalyst was injected once the reactor reached an internal temperature of 80 °C. The jacket temperature was then raised to 210 °C until the internal temperature reached a plateau. At this time, the jacket temperature was raised to 240 °C, and the pressure in the reactor was reduced to about 80 torr. The jacket temperature was then raised to 250 °C after 10 minutes, and then to 260 °C after another 10 minutes. The vacuum was gradually increased to 0.5 torr over a 2-6 hour period while keeping the distillation of 1 ,4-butanediol (for PBT) 1 ,2-ethanediol (for PET), relatively constant. The reaction was then held at this temperature and pressure until the torque rose to a maximum value of 10-110 Ncm for about 30 minutes. At this time, the reactor was cooled toroom temperature and jacketed with nitrogen. The resulting polymer was manually removed from the vessel.

[0125] In the following Examples, Examples 1 , 4, 8, 12, 14, and 15 are comparative examples.

[0126] Example 1 - this example was too hard and rubbery and had little adhesion. DMT 100.9 g (0.520 mol); BDO 36.3 g (0.403 mol); Silsurf Di-1010 (0.133 mol); 1 ,2- hexanediol 78.0 g (0.660 mol); Ethanox 330 1.2 g (0.002 mol); Tyzor® 1.6 g (0.005 mol).

[0127] Example 2 - this sample was hard and rubbery and had little adhesion.DMT 100.9 g (0.519 mol); BDO 36.4 g (0.403 mol); PTMEG 239.1 g (0.120 mol); EHG 78.0 g (0.382 mol); Ethanox 330 1 .2 g (0.002 mol); Tyzor® 1 .6 g (0.005 mol)

[0128] Example 3 (3205) - this sample had good adhesion but tore easily and demonstrated cohesive failure with some residue on skin and polycarbonate.DMT 100.8 g (0.519 mol); BDO 36.4 g (0.404 mol); Silsurf Di-1010 239.6 g (0.133 mol); EHG 78.4 g (0.384 mol); Ethanox 330 1 .2 (0.002 mol); Tyzor® 1 .6 g (0.005 mol)

[0129] Example 4 (3207) - no viscoelastic properties.DMT 100.9 g (0.520 mol); BDO 114 g (1.265 mol); PPG2000 239.3 g (0.120 mol); Ethanox 330 1 .2 g (0.002 mol); Tyzor® 1 .6 g (0.005 mol).

[0130] Example 5 (3210) - this sample was very adhesive but lacked cohesive strength.DMT 100.9 g (0.520 mol); BDO 36.3 g (0.402 mol); Silsurf Di-1010 239.7 g (0.133 mol); 2-ethyl-1 ,3-hexanediol 119.7 g (1.006 mol); Ethanox 330 1.2 g (0.002 mol); Tyzor® 1 .6 g (0.005 mol)

[0131] Example 6 (3215) - this sample was too rubbery.DMT 100.9 g (0.520 mol); BDO 47.9 g (0.533 mol); Silsurf Di-1010 239.4 g (0.133 mol); EHG 39.0 g (0.191 mol); Ethanox 330 1.2 g (0.002 mol); Tyzor® 1.6 g (0.005 mol)

[0132] Example 7 (3216) - this sample was crosslinked and swelled in the presence of solvent.DMT 100.9 g (0.520 mol); BDO 36.3 g (0.403 mol); Silsurf Di-2012 386.0 g (0.133 mol); EHG 77.9 g (0.381 mol); Ethanox 330 1.2 g (0.002 mol); Tyzor® 1.6 g (0.005 mol).

[0133] Example 8 (3220) - this sample was adhesive but lacked cohesive strength. DMT - 123.5 g (0.003 mol); PPG200060.0 g (0.030 mol); PTMEG2000 180.0 g (0.090 mol); EHG 78.1 g (0.382 mol); Ethanox 330 1.2 g (0.002 mol); Tyzor® 1.6 g (0.005 mol).

[0134] Example 9 (3221 ) - this sample was adhesive but lacked cohesive strength. DMT 100.7 g (0.519 mol); BDO 36.2 g (0.402 mmol); PEG-PPG-PEG (Mn 1900) 2000 239.2 g (0.126 mol); EHG 70.0 g (0.126 mol); Ethanox 330 1 .2 g (0.002 mol); Tyzor® 1.6 g (0.005 mol).

[0135] Example 10 (3228) - this sample was adhesive but lacked cohesive strength. DMT 100.9 g (0.520 mol); BDO 36.2 g (0.401 mol); PTMEG 239.8 g (0.120 mol); 2- ethyl-1 ,3-hexanediol 110.0 g (0.753 mol); Ethanox 330 1.2 g (0.002 mol); Tyzor® 1.6 g (0.005 mol).

[0136] Example 11 (3230) - this sample was sticky and had good cohesive strength. DMT 100.9 g (0.520 mol); BDO 36.1 g (0.400 mol); Silsurf Di-1010 225.0 g (0.125 mol); PTMEG 225.0 g (0.113 mol); EHG 26.0 g (0.127 mol); Ethanox 330 1 .2 g (0.002 mol); Tyzor® 1 .6 g (0.005 mol)

[0137] Example 12 (3234) - this sample was less sticky than 11 and had good cohesive strength. DMT 100.9 g (0.520 mol); BDO 36.0 g (0.399 mol); Silsurf Di-1010 135.1 g (0.075 mol); PTMEG2000 317.0 g (0.159 mol); Ethanox 330 1 .2 g (0.002 mol), Tyzor® 1 .6 g (0.005 mol).

[0138] Example 13 (3237) - this sample showed a good balance of adhesion and cohesive strength. DMT 101.0 g (0.520 mol); BDO 36.4 g (0.404 mol); Silsurf Di-1010 71.7 g (0.040 mol); PTMEG2000 167.5 g (0.084 mol); EHG 53.6 g (0.262 mol); Ethanox 330 1 .2 g (0.002 mol); Tyzor® 1 .6 g (0.005 mol).

[0139] Example 14 (3239) - this sample had no adhesive properties.DMT 100.8 g (0.519 mol); BDO 72.1 g (0.800 mol); Silsurf Di-1010 119.6 g (0.066 mol); PTMEG2000 120.2 g (0.060 mol); Ethanox 330 1 .2 g (0.002 mol); Tyzor® 1 .6 g (0.005 mol).

[0140] Example 15 (3240) - this sample had no adhesives properties.DMT 100.9 g (0.520 mol); BDO 72.2 g (0.801 mol); Silsurf Di-1010 240.0 g (0.133 mol); Ethanox 330 1 .2 g (0.002 mol); Tyzor® 1 .6 g (0.005 mol).

[0141] Example 16 (3244) - this sample showed a good balance of adhesion and cohesive strength. DMT 100.9 g (0.520 mol); BDO 36.0 g (0.399 mol); Silsurf Di-1010 135.1 g (0.075 mol); PTMEG2000 314.9 g (0.157 mol); EHG 34.0 g (0.166 mol); Ethanox 330 1 .2 g (0.002 mol); Tyzor® 1 .6 g (0.005 mol).

[0142] Example 17 (3253) - this was a replicate of Example 16 starting from PBT. PBT 90.0 g (0.002 mol); Silsurf Di-1010 156.4 g (0.087 mol); PTMEG2000 293.6 g (0.147 mol); EHG 34.0 g (0.166 mol); Ethanox 1 .2 g (0.002 mol); Tyzor® 0.8 g (0.002 mol).

[0143] Example 18 (3257) - this sample showed a good balance of adhesion and cohesive strength. PBT 127.6 g (0.003 mol); PPG2000 60.0 g (0.030 mol); PTMEG 180.0 g (0.090 mol); EHG 78.0 g (0.382 mol); TMP 3.0 g (0.022 mol); Ethanox 330 1 .2 g (0.002 mol); Tyzor® 0.8 g (0.002 mol).

[0144] Example 19 (3261 ) - this sample showed a good balance of adhesion and cohesive strength. PBT 127.6 g (0.003 mol); PPG2000 60.0 g (0.030 mol); PTMEG 180.0 g (0.090 mol); EHG 78.8 g (0.386 mol); TMP 2.0 g (0.015 mol); Ethanox 330 1 .2 g (0.002 mol); Tyzor® 1 .6 g (0.005 mol).

[0145] Example 20 (3266) - this sample was crosslinked and swelled in the presence of solvent. PBT 127.7 g (0.003 mol); HTPB 80.7 g (0.029 mol); PTMEG2000 180.0 g (0.090 mol); EHG 78.0 (0.382 mol); Ethanox 330 1.2 g (0.002 mol); Tyzor® 1.6 g (0.005 mol).

[0146] Example 21(3267) - this sample showed a good balance of adhesion and cohesive strength.PBT 127.7 g (0.003 mol); PPG2000 120.0 g (0.060 mol); PTMEG2000 120.2 g (0.060 mol); EHG 78.0 g (0.382 mol); TMP 2.5 g (0.019 mol); Ethanox 330 1 .2 g (0.002 mol); Tyzor® 1 .6 g (0.005 mol).

[0147] Example 22 (3274) - this sample showed a good balance of adhesion and cohesive strength. PBT 127.6 g (0.003 mol), PPG2000 120.0 g (0.060 mol), PTMEG2000 120.2 g (0.060 mol), EHG 78.0 g (0.293 mol), TMP 2.5 g (0.019 mol),Silsurf A008-UP 1 1 .2 g (0.017 mol), Ethanox 330 1 .2 g (0.002 mol), Tyzor® 1 .6 g (0.005 mol).

[0148] Example 23 (3277) - this sample showed a good balance of adhesion and cohesive strength. PBT 127.6 g (0.003 mol), Silsurf Di-151 180.0 g (0.075 mol), PTMEG2000 60.0 g (0.030 mol), EHG 78.0 g (0.382 mol), TMP 2.5 g (0.019 mol), Ethanox 330 1 .2 g (0.002 mol), Tyzor® 1 .6 g (0.005 mol).

[0149] Example 24 (CO1279) - this sample showed a good balance of adhesion and cohesive strength.

[0150] PET 218 g (0.007 mol), PPG2000 216 g (0.108 mol), PTMEG2900 216 g (0.074 mol), EHG 139.8 g (0.684 mol), glycerol 5.23 g (0.056 mol), Ethanox 330 2.2 g (0.003 mol), Tyzor® 2.8 g (0.008 mol).

[0151] Example 25 (CS0301) - this sample showed good adhesion and low cohesive strength.

[0152] PBT 226.8 g (0.006 mol), PPG2000 213.2 g (0.107 mol), PTMEG2000 213.2 g (0.107 mol), 1 ,2-dodecanediol 137.5 g (0.679 mol), glycerol 4.41 g (0.048 mol), Ethanox 330 2.16 g (0.003 mol), Tyzor® 2.8 g (0.008 mol).

[0153] Example 26 (CQ3981) - this sample showed good adhesion and good cohesive strength.

[0154] PBT 127.6 g (0.0034 mol), PPG2000 120 g (0.06 mol), PTMEG2000 120 g (0.06 mol), EHG 78 g (0.382 mol), TMP 2.5 g (0.019 mol), lauryl alcohol 3.2 g (0.017 mol), Ethanox 330 1.2 g (0.002 mol), Tyzor® 1.6 g (0.005 mol).

[0155] Example 27 (CS0307) - this sample showed good adhesion and good cohesive strength.

[0156] PBT 127.6 g (0.003 mol), PPG2000 120 g (0.06 mol), PTMEG2000 120 g (0.06 mol), 2-methyl-2-propylpropane-1 ,3-diol 50.5 g (0.382 mol), glycerol 2.5 g (0.027 mol), Ethanox 330 2.16 g (0.003 mol), Tyzor® 2.8 g (0.008 mol).

[0157] Example 28 (CO1281) - this sample showed good adhesion and low cohesive strength.

[0158] DMT 200.2 g (1.031 mol), ethylene glycol 50.2 g (0.81 mol), PPG2000202.1 g (0.101 mol), PTMEG2000202.1 g (0.104 mol), EHG 135.85 g (0.665 mol), glycerol 5.2 g (0.056 mol), Ethanox 330 2.16 g (0.003 mol), Tyzor® 2.8 g (0.008 mol).

[0159] Example 29 (CO1283) - this sample showed low tack and good cohesive strength.

[0160] PBT 226 g (0.006 mol), PPG2000 212.5 g (0.106 mol), PTMEG2000 212.6 g (0.106 mol), ethylhexylglycerin 69.1 g (0.338 mol), Pripol™ 2033, a dimerized fatty acid diol 69.0 g (0.128 mol), glycerol 5.6 g (0.061 mol), Ethanox 330 2.16 g (0.003 mol), Tyzor® 3.25 g (0.010 mol).

[0161] Table 2 describes characteristics of the polyester copolymers of Example 1 through Example 29, as determined by1H NMR spectroscopy and GPC. Weight percent hard segment is calculated from the combined weight percent of terephthalic acid and second diol. Weight percent soft segment is calculated from the combined weight percent of first diol or diols. The weight percent of diol refers to the weight percent of third diol. Weight percent values are calculated by integration of1H NMR spectroscopy peaks. The Mw, Mn, and D were determined by GPC.

[0162] Table 2. Characteristics of Polyester Copolymers of ExamplesSample was crosslinked. It was either insoluble, or the data that was obtained is unreliable due to poor solubility.** Determined by1H NMR spectroscopy in CDCI3. Table 3 demonstrates the broad range of desirable peel properties that may accessed through polyester polymer formulation design, compared to the Comparative Example.Table 3. Peel Properties‘Denotes extensive cohesive failureParallel plate rheology analyses at 30 °C for selected examples:Table 4. Favorable adhesive properties of top-perforaming samples as defined by rheological characteristics.

Claims

That which is claimed is:1 . A polyester copolymer, comprising: the reaction product of a first diol and second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short chain diol having from 2 to 20 carbon atoms; a difunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; a third diol, wherein the third diol comprises a branched hydrocarbyl group.

2. The polyester copolymer according to any one of the preceding claims, wherein the polyester copolymer further comprises a polyol.

3. The polyester copolymer according to claim 2, wherein the polyol is oligomeric, polymeric, copolymeric, or copolymeric.

4. The polyester copolymer according to any one of claims 2 or 3, wherein the polyol is linear.

5. The polyester copolymer according to any one of the preceding claims, further comprising a triol monomer.

6. The polyester copolymer according to any one of the preceding claims, wherein the first diol is an oligomeric polyether.

7. The polyester copolymer according to any one of claims 1-5, wherein the first diol has polysiloxane and polyalkylene glycol segments.

8. The polyester copolymer according to claim 7, wherein the first diol is a polysiloxane terminated with polyalkylene glycol segments.

9. The polyester copolymer according to any one of the preceding claims, wherein the second diol has from 2 to 8 carbon atoms.

10. The polyester copolymer according to any one of the preceding claims, wherein the difunctional compound is a phthalate.11 . The polyester copolymer according to any one of the preceding claims, wherein the third diol is according to formula I:(I) wherein R1 is hydrogen, hydrocarbyl, hydrocarbyloxy, or ether having1 to 12 carbon atoms (C1-C12), and R2 is hydrocarbyl, hydrocarbyloxy, or ether having 1 to 12 carbon atoms (C1-C12), R3 is hydrocarbylene having from 1 to 5 carbon atoms.

12. A method of making a polyester copolymer, comprising the following steps: combining a first diol and second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short chain diol having from 2 to 20 carbon atoms; a difunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; a third diol, wherein the third diol comprises a branched hydrocarbyl or hydrocarbyloxy group; and a catalyst to form a reaction mixture, exposing the reaction mixture to conditions sufficient to cause a reaction and form the polyester copolymer.

13. A pressure sensitive adhesive comprising the polyester copolymer composition according to any one of claims 1-11.

14. A pressure sensitive adhesive according to claim 13, wherein the pressure sensitive adhesive is made according to the method of claim 12.

15. A dermal patch comprising the pressure sensitive adhesive according to one of claims 13 or 14, wherein the patch is a transdermal drug delivery patch or a wound care patch.

16. A medical device comprising the pressure sensitive adhesive according to one of claims 13 or 14.

17. A polyester copolymer, comprising: random units having the formulas[-OR4O-], [-0R50-], [-C(O)R6C(O)-], [-OR7O-], wherein R4is hydrocarbylene having from 2 to 20 carbon atoms, alternately 2 to 5 carbon atoms, alternatively from 2 to 4 carbon atoms, R5is a branched hydrocarbylene, branched hydrocarbyloxy-substituted hydrocarbylene, or branched ether-substituted hydrocarbylene having from 4 to 20 carbon atoms, R6is hydrocarbylene having from 4 to 12 carbon atoms, wherein R7is oligomeric, copolymeric, or polymeric hydrocarbylene or alkylene glycol having a molecular weight (Mw) greater than 400 g / mol.

18. The polyester copolymer according to claim 17, further comprising a unit having the structure of polyalkyleneglycol end-capped diorganopolysiloxane having a molecular weight from 400 to 3000 g / mol per unit or a polyether.

19. The polyester copolymer according to one of claims 17 or 18, further comprising a linear polyol unit according to the formula [-OR7(O-)O-], wherein R7is trivalent hydrocarby having from 4 to 3000 carbon atoms.

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