Polyesters comprising branched diols, methods of making, and adhesives comprising the same

Abstract

A polyester copolymer, a method for preparing the polyester copolymer, an adhesive comprising the polyester copolymer, a skin patch comprising the adhesive, and a medical device comprising the adhesive are disclosed. The polyester copolymer comprises the following reaction products: a first diol and a second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short-chain diol having 2 to 20 carbon atoms; a bifunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; and a third diol, wherein the third diol comprises a branched hydrocarbon group.

Description

Cross-reference to related applications

[0001] none Technical Field

[0002] The present invention generally relates to polyester copolymers, methods for preparing such polyester copolymers, adhesives comprising such polyester copolymers, and skin patches and medical devices comprising such polyester copolymer adhesives. Background Technology

[0003] Pressure-sensitive adhesives (PSAs) are used in a wide range of medical applications, including wound dressings, wound closures, stoma implants, surgical dressings, transdermal drug delivery, and attachment of medical devices to the body. These PSAs must combine strong adhesive properties with cohesive properties for good skin adhesion and non-invasive removal without residue. Long-lasting wear, biocompatibility, long-term stability, and non-irritation are particularly important. Typical polymers used in medical applications include acrylics, thermoplastic elastomers such as styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers blended with adhesive resins, polysiloxanes, and hydrogels such as polyvinylpyrrolidone or cross-linked carboxymethyl cellulose-polyisobutylene.

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

[0005] Therefore, there is a need for a single-component, easily processable adhesive for medical applications that adheres firmly to the skin for the duration of the desired application, is easy and painless to remove, is breathable, and can be repositioned. Summary of the Invention

[0006] This invention relates to a polyester copolymer comprising:

[0007] The following reaction products are: a first diol and a second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short-chain diol having 2 to 20 carbon atoms; a bifunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; and a third diol, wherein the third diol contains a branched hydrocarbon group.

[0008] The present invention further relates to a method for preparing a polyester copolymer, the method comprising the steps of: combining the following to form a reaction mixture: a first diol and a second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short-chain diol having 2 to 20 carbon atoms; a bifunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; a third diol, wherein the third diol contains a branched hydrocarbon group or a hydroxyl group; and a catalyst; and exposing the reaction mixture to conditions sufficient to induce a reaction and form the polyester copolymer.

[0009] The present invention further relates to a pressure-sensitive adhesive comprising the polyester copolymer composition of the present invention.

[0010] The invention further relates to a skin patch comprising a 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 for temporarily securing a medical or veterinary device to a human or animal body, respectively.

[0011] The present invention further relates to a medical device comprising a pressure-sensitive adhesive according to the present invention.

[0012] Finally, this invention relates to a polyester copolymer comprising:

[0013] Having the formula [-OR 4 O-]、[-OR 5 O-]、[-C(O)R 6 C(O)-]、[-OR 7 Random elements of O-], where R 4 It is a hydrocarbon group having 2 to 20 carbon atoms, or alternatively 2 to 5 carbon atoms, or alternatively 2 to 4 carbon atoms, R 5 It is a branched hydrocarbon group having 4 to 20 carbon atoms, a branched hydrocarbon group substituted with an alkyl group or a branched hydrocarbon group substituted with an ether, R 6 It is a hydrocarbon subgroup with 4 to 12 carbon atoms, where R 7 It is an oligomeric, copolymeric, or polymeric alkylene or alkylene glycol having a Mw of greater than 400 g / mol, or alternatively from 400 g / mol to 3000 g / mol, wherein the polyester copolymer is hydroxyl, carboxyl, or carboxylic acid ester-terminated. Attached Figure Description

[0014] Figure 1 This is a graph of the loss modulus and energy storage modulus of Example 1 relative to the angular frequency.

[0015] Figure 2 This is a graph of the loss modulus and energy storage modulus relative to the angular frequency for Example 2.

[0016] Figure 3 This is a graph of the loss modulus and energy storage modulus of Example 3 relative to the angular frequency.

[0017] Figure 4 This is a graph of the loss modulus and energy storage modulus of Example 5 relative to the angular frequency.

[0018] Figure 5 This is a graph of the loss modulus and energy storage modulus relative to the angular frequency for Example 6.

[0019] Figure 6 This is a graph of the loss modulus and energy storage modulus relative to the angular frequency for Example 8.

[0020] Figure 7 This is a graph of the loss modulus and energy storage modulus relative to the angular frequency for Example 9.

[0021] Figure 8 This is a graph of the loss modulus and energy storage modulus of Example 10 relative to the angular frequency.

[0022] Figure 9 This is a graph of the loss modulus and energy storage modulus of Example 11 relative to the angular frequency.

[0023] Figure 10 This is a graph of the loss modulus and energy storage modulus of Example 12 relative to the angular frequency.

[0024] Figure 11 This is a graph of the loss modulus and energy storage modulus of Example 13 relative to the angular frequency.

[0025] Figure 12 This is a graph of the loss modulus and energy storage modulus of Example 16 relative to the angular frequency.

[0026] Figure 13 This is a graph of the loss modulus and energy storage modulus of Example 17 relative to the angular frequency.

[0027] Figure 14 This is a graph of the loss modulus and energy storage modulus of Example 18 relative to the angular frequency.

[0028] Figure 15 This is a graph of the loss modulus and energy storage modulus of Example 19 relative to the angular frequency.

[0029] Figure 16 This is a graph of the loss modulus and energy storage modulus of Example 21 relative to the angular frequency.

[0030] Figure 17 This is a graph of the loss modulus and energy storage modulus of Example 22 relative to the angular frequency. Detailed Implementation

[0031] As used in this article, the article “a” refers to one or more than one and does not necessarily restrict the noun it refers to to the singular grammatical category.

[0032] As used herein, when referring to quantities or values, the terms "about" and "at or about" mean an approximate value of a quantity or value that is greater than or less than the exact quantity or value listed in the claims or described herein. The exact value of an approximation is determined based on a value that would be recognized by a person skilled in the art as an appropriate approximation of that exact value. As used herein, the term indicates that similar values ​​not precisely listed in the claims or precisely described herein can cause results or effects equivalent to those values ​​listed in the claims or described herein, with which a person skilled in the art would acknowledge that these similar values ​​are acceptablely caused.

[0033] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variation thereof refer to non-exclusive inclusion. For example, a process, method, article of manufacture, or apparatus that includes a list of elements is not limited to the listed elements but may include other elements not explicitly listed or inherent to the process. Furthermore, unless explicitly stated to the contrary, “or” refers to inclusive “or,” not exclusive “or.” For example, condition A or B is satisfied by any of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0034] As used herein, the clause “polyester copolymer comprises” or “polyester copolymer comprises” or similar clauses mean that the polyester copolymer is produced from the material described following the clause. That is, the material is reacted with one or more other materials to produce the polyester copolymer.

[0035] As used herein, the terms “consistently composed of” and “component of” or any other variations thereof may refer to a non-exclusive inclusion or an exclusive inclusion. When these terms refer to a more exclusive inclusion, they limit the scope of the claims to those materials or steps that substantially affect the novel element of the invention. When these terms refer to a completely exclusive inclusion, they exclude any element, step, or component not expressly recited in the claims.

[0036] As used herein, the terminology used to describe molecules or polymers follows the terminology in IUPAC Chemical Terminology Summary Version 2.15 (International Union of Pure and Applied Chemistry) dated 7 September 2009.

[0037] As used herein, the term "alkyl" refers to a straight-chain, branched, or cyclic hydrocarbon structure, and combinations thereof. Alkyl groups do not include aromatic structures. Examples of straight-chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl. Branched alkyl groups include, for example, sec-butyl and tert-butyl, and isopropyl. Examples of cyclic hydrocarbon groups include cyclopropyl, cyclopentyl, cyclohexyl, cyclobutyl, and cyclooctyl.

[0038] As used herein, the term "alkoxy (alkoxyl)" refers to an alkyl group attached to an oxygen atom by a single bond. The oxygen atom is then bonded to a carbon atom. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropoxy, and cyclohexyloxy.

[0039] As used herein, the term "aromatic" refers to a chemical entity containing at least one unsaturated atomic ring, which is stabilized by the interactions of the bonds forming the ring. Benzene and naphthalene are typical examples of such chemical entities.

[0040] As used herein, the term "phenyl" refers to a chemical entity of the formula -C6H5 derived from benzene by removing a hydrogen atom. The carbon atom lacking the hydrogen atom is used to form a bond with another chemical entity.

[0041] As used herein, the term "phenylene" refers to a chemical entity of the formula C6H4 derived from benzene by removing two hydrogen atoms. The carbon atom lacking the hydrogen atom is used to form a bond with another chemical entity or part of a larger molecule.

[0042] Unless otherwise expressly stated, any range described herein explicitly includes its endpoints. Describing a quantity, concentration, or other value or parameter as a range specifically discloses all possible ranges formed by any possible upper and lower limits, regardless of whether such pairs as upper and lower limits are explicitly disclosed herein. The compounds, methods, and articles described herein are not limited to the specific values ​​disclosed when the range is defined in the specification.

[0043] The disclosure herein is particularly intended to include any possible combinations of materials, methods, steps, values, and / or ranges (whether or not determined to be preferred) of the methods, compounds, and articles described herein. For the purpose of providing detailed, accurate, and sufficient support for the claims, any disclosed combinations are preferred variations of the methods, compounds, and articles described herein.

[0044] In this specification, if there are any errors in the naming or typographical errors of the chemical names of any chemical species described herein, the chemical structure takes precedence over the chemical name. Furthermore, if there are any errors in the chemical structure of any chemical species described herein, the chemical structure of the chemical species as understood by a person skilled in the art to be intended in this specification shall prevail.

[0045] A polyester copolymer comprising:

[0046] The following reaction products:

[0047] The first diol and the second diol, wherein the first diol is an oligomer, polymer or copolymer, and the second diol is a short-chain diol having 2 to 20 carbon atoms;

[0048] A bifunctional compound, including a dicarboxylic acid, a dicarboxylic acid halide, an acid anhydride, or a diester;

[0049] The third diol comprises a branched hydrocarbon group.

[0050] First Diol

[0051] The first diol can be any of the many diols or mixtures of diols known in the art for preparing polyester polymers, different from the second and third diols. In various embodiments, the dihydroxy-terminated diol is selected from poly(alkyleneoxy)diols (such as polyethyleneoxydiol, polypropyleneoxydiol, or polybutyleneoxydiol), linear aliphatic polyesters, aliphatic polycarbonates, linear polyether polysiloxane diols, branched polyether polysiloxane diols, linear aliphatic polyolefins, linear polybutadiene, linear polyisobutylene, polyadipate, and mixtures thereof. In another embodiment, the first diol may comprise polytetrahydrofuran as the first diol.

[0052] The first diol can also be a hydroxyl-terminated oligomer, such as, but not limited to, aliphatic hydrocarbon diols having more than 20 carbon atoms, or alternatively 20 to 4000, or alternatively 1000 to 3000 carbon atoms.

[0053] In one embodiment, the first diol comprises a linear or branched hydroxyl-terminated polydimethylsiloxane having 5 to 50, alternatively 5 to 20, or alternatively 7 to 12 polyether polymer units (polyethylidene or polypropyleneoxy) terminally terminal. The polyalkylene glycol-terminated polydimethylsiloxane has a molecular weight of 400 to 3000 g / mol. In another embodiment, the polysiloxane portion of the polyether polysiloxane is at least 30% (w / w). Those skilled in the art will know how to select the first diol based on this specification. Examples of the first diol are commercially available.

[0054] In various embodiments, the weight-average molecular weight of the linear polyether polysiloxane diol is about 500 to about 10,000, about 1,000 to about 9,500, about 1,500 to about 9,000, about 2,000 to about 8,500, about 2,500 to about 8,000, about 3,000 to about 7,500, about 3,500 to about 7,000, about 4,000 to about 6,500, about 4,500 to about 6,000, about 5,000 to about 5,500, about 800 to about 4,000, about 1,000 to about 4,000, about 1,500 to about 3,500, about 2,000 to about 3,000, or about 2,000 to about 2,500 Daltons. Typically, the higher the weight-average molecular weight, the more miscibility problems can be observed in the polymerization reaction. In various non-limiting embodiments, all values ​​and ranges (both integers and fractions) including those set forth above are hereby expressly contemplated for use herein.

[0055] Alternatively, the polyether polysiloxane portion may be at least about 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% by weight of linear polyether polysiloxane diol. In various non-limiting embodiments, all values ​​and ranges (both integers and fractions) including those set forth above are hereby expressly contemplated for use herein.

[0056] In other embodiments, the polyether polysiloxane diol has the following formula:

[0057]

[0058] Where c is about 1 to about 30; d is about 0 to about 20; and g is about 3 to about 50, and where R 12 and R 13Each is independently selected from C1-C4 aliphatic groups. For example, c can be 1 or any number up to about 30. D can be about 0 or any number up to about 20. G can be 3 or any number up to about 50. In various non-limiting embodiments, the values ​​set forth above and all values ​​between those values ​​and their ranges (both integers and fractions) are hereby expressly contemplated for use herein.

[0059] In other embodiments, the reaction product is further defined as the following: a branched diol containing at least one short-chain branched group; a dicarboxylic acid; and an aliphatic diol selected from 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,2-dihydroxycyclohexane, 1,3-dihydroxycyclohexane, 1,4-dihydroxycyclohexane, 1,4-butenyldiol, diethylene glycol, and mixtures thereof. In relevant embodiments, the copolymer has a molar ratio of units derived from aliphatic diols to units derived from dicarboxylic acids of 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 (both integers and fractions) including those set forth above are hereby expressly contemplated for use herein.

[0060] In yet another embodiment, the linear aliphatic polyester may be polylactic acid, polyhydroxyalkanoate, polycaprolactone, and mixtures thereof.

[0061] Second diol

[0062] The second diol is a short-chain diol having 2 to 20, alternatively 2 to 10, alternatively 2 to 8, or alternatively 2 to 6 carbon atoms. The second diol is linear. The second diol can be any short-chain diol known in the art for preparing polyester copolymers having 2 to 20 carbon atoms. Examples of short-chain diols include, but are not limited to, 1,2-ethylene glycol, 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 commercially available. In one embodiment, the second diol is a mixture of said diols.

[0063] Bifunctional compounds

[0064] Bifunctional compounds include dicarboxylic acids, dicarboxyl halides, acid anhydrides, or diesters of dicarboxylic acids. The bifunctional compound can be any bifunctional compound known in the art for preparing polyester copolymers. In one embodiment, the bifunctional compound is a dicarboxylic acid, such as an aliphatic dicarboxylic acid or an alkyl diester of an aliphatic dicarboxylic acid. In another embodiment, the bifunctional compound is an aromatic dicarboxylic acid or an ester of an aromatic dicarboxylic acid. In various embodiments, the bifunctional compound is selected from dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phthalic acid, phthalic anhydride, cyclohexanedicarboxylic acid, biphenyl dicarboxylic acid, and C4-C... 10 The dicarboxylic acid is any one of the aliphatic dicarboxylic acids, spiroacetal diacid, or a combination thereof, or an alkyl diester containing 1 to 5 carbon atoms, alternatively 1 to 2 carbon atoms, or alternatively 1 carbon atom of one carbon atom of any of the aforementioned carboxylic acids. In one embodiment, the dicarboxylic acid is a methyl diester of terephthalic acid. In another embodiment, the dicarboxylic acid is isophthalic acid or a methyl diester of isophthalic acid. In another embodiment, the dicarboxylic acid is naphthalic acid or a methyl diester of naphthalic acid. In another embodiment, the dicarboxylic acid is phthalic acid, phthalic anhydride, or a 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 a methyl diester thereof. In another embodiment, the dicarboxylic acid is selected from C4-C. 10 Aliphatic dicarboxylic acids. For example, aliphatic dicarboxylic acids can be, but are not limited to, those having 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 dicarboxylic acids or diesters. In yet another embodiment, the dicarboxylic acid is spiroacetal dicitonic acid or its methyl diester. Those skilled in the art will know how to obtain or prepare the bifunctional compounds according to the invention. Many of the representative bifunctional acids are commercially available.

[0065] Although not intended to be bound by any particular theory, it is believed that the choice of bifunctional compounds, such as dicarboxylic acids or their alkyl esters, affects the presence of crystalline segments in the copolymer backbone, which in turn affects the cohesive strength of the copolymer and the final composition.

[0066] Tertiary Diol

[0067] The third diol contains a branched hydrocarbon group, which may alternatively have 4 to 20 carbon atoms, or alternatively 4 to 8 carbon atoms, or alternatively 6 to 10 carbon atoms, or alternatively 7 to 9 carbon atoms. Examples of hydrocarbon groups include branched alkyl groups 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 groups such as cyclopentyl, cyclohexyl, and methylcyclohexyl; aryl groups such as phenyl and naphthyl; alkylaryl groups such as tolyl and xylyl; aralkyl groups such as benzyl and phenethyl; and branched alkenyl groups such as 1-methylvinyl, 1-methylpropenyl, 2-methylbutenyl, 1-ethylhexenyl, and 2-ethylhexenyl.

[0068] In some embodiments, the branched hydrocarbon group is covalently bonded at carbon atoms to a carbon chain having at least two, alternatively two or three, alternatively two hydroxyl groups and having 2 to 18, alternatively 3 to 10, or alternatively 3 to 5 carbon atoms, via an oxygen-linking group or via -R'-O- (where R' is a hydrocarbon group having 1 to 3 carbon atoms). The carbon chain may have additional branches or may be straight-chain.

[0069] In one embodiment, the third diol is prepared according to formula I:

[0070] (I) ,

[0071] Where R1 is hydrogen, hydrocarbon or ether, or alternatively hydrogen or hydrocarbon, or alternatively hydrogen; R2 is hydrocarbon or ether, or alternatively hydrocarbon or ether; and R3 is a hydrocarbon-like group.

[0072] When R1 is a hydrocarbon group or an ether, R1 has 1 to 12 carbon atoms (C1-C12), or alternatively 2 to 8 carbon atoms. R2 can have 1 to 12 carbon atoms (C1-C12), or alternatively 2 to 8 carbon atoms. R3 can have 1 to 5 carbon atoms, or alternatively 1 to 3 carbon atoms, or alternatively 1 carbon atom.

[0073] Examples of hydrocarbon groups having 1 to 12 atoms for R1 include, but are not limited to, straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl; and branched-chain alkyl groups 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; alkylaryl, such as tolyl and xylyl; aralkyl, such as benzoyl and phenethyl; branched alkenyl, such as 1-methylvinyl, 1-methylpropenyl, 2-methylbutenyl, 1-ethylhexenyl, and 2-ethylhexenyl.

[0074] Examples of ethers for R1 include, but are not limited to, those containing an oxygen-linking group or a hydrocarbon group bonded by -R'-O- (where R' is a hydrocarbon subgroup having 1 to 3 carbon atoms) as described above for R1.

[0075] Examples of hydrocarbon groups and ethers used for R2 include those described above for R1.

[0076] In one embodiment, R1 is hydrogen and R2 is an ether, or alternatively, hydrogen and ether, wherein the ether is an alkylene group or alternatively, an ethylhexyloxymethylene group.

[0077] Examples of third diols include, but are not limited to, methyl ethyl glycerol, methyl propyl glycerol, methyl butyl glycerol, methyl pentyl glycerol, methyl hexyl glycerol, methyl heptayl glycerol, methyl octyl glycerol, methyl nonyl glycerol, methyl decyl glycerol, methyl dodecyl glycerol, ethyl ethyl glycerol, ethyl propyl glycerol, ethyl butyl glycerol, ethyl pentyl glycerol, ethyl heptayl glycerol, ethyl octyl glycerol, ethyl nonyl glycerol, ethyl decyl glycerol, ethyl dodecyl glycerol, 2-methyl-2-propyl-1,3-propanediol, 2-phenyl-1,3-propanediol, 1,2-dodecanediol, dimer fatty acid diols (e.g., Pripol™ 2030, Pripol™ 2033, and Pripol™ 2043 from Cargill), and mixtures thereof. In one embodiment, the third diol is ethyl hexyl glycerol.

[0078] The third diol can be a mixture of diols that satisfy the description of a third diol. Many materials that satisfy the description of a third diol are commercially available. Those skilled in the art will know how to obtain materials that satisfy the description of a third diol.

[0079] polyols

[0080] In one embodiment, the polyester copolymer may further comprise a polyol, wherein the polyol is a linear oligomer, polymer, or copolymer containing at least three hydroxyl groups. The polyol introduces branching sites into the polyester copolymer backbone. Any polyol known in the art for the production of polyester copolymers can be used. Examples of polyols include copolymers of alkylene glycols and polyol monomers (such as glycerol) or similar reactants having three or more hydroxyl groups. Those skilled in the art will understand how to select polyols for inclusion in the production of polyester copolymers.

[0081] End capping agent

[0082] In one embodiment, the polyester copolymer further comprises an end-capping agent. The end-capping agent can be a linear or branched monohydric alcohol or a combination thereof, preferably a secondary or primary alcohol or a combination thereof, more preferably a primary alcohol or a 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-tetranol, 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. Those skilled in the art will understand how to select optional end-capping agents for the production of the polyester copolymer according to the invention. Many of these materials are commercially available.

[0083] Triols

[0084] In one embodiment, the polyester copolymer further comprises a triol. The triol comprises 3 to 100, alternatively 3 to 20, alternatively 3 to 10 carbon atoms. The triol comprises at least three, alternatively three hydroxyl groups. In one embodiment, the triol is a hydrocarbon having three hydrogen atoms substituted with hydroxyl groups, or alternatively, an alkane substituted with three hydroxyl groups, wherein examples of alkanes 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; cycloalkanes such as cyclopentane, cyclohexane, and methylcyclohexane; and aromatics such as benzene and toluene. Examples of triols include, but are not limited to, glycerol, trimethylolethane, trimethylolpropane (or 2-ethyl-2-(hydroxymethyl)propane-1,3-diol), trimethylolbutane, trimethylolpentane, pentaerythritol, trimethylolhexane, trimethylolheptanane, trimethyloloctane, trimethyloldecane, trimethyloldodecanetri(hydroxyethyl)isocyanurate, dipentaerythritol, tripentaerythritol, maltitol, sorbitol, xylitol, erythritol, 1,2,6-hexanetriol, polyether glycol, polyester glycol, trimethylolpropane allyl ether / trimethylolethane allyl ether, dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 5-(2-hydroxyethoxy)isophthalic acid, 5-acetoxyisophthalic acid, and 3,5-bis(2-hydroxyethoxy)benzoic acid. In one embodiment, the triol is glycerol or trimethylolpropane. Those skilled in the art will understand how to select triols for use in the production of polyester copolymers according to the present invention. The triols of the present invention are commercially available.

[0085] A method for preparing a polyester copolymer, the method comprising the following steps:

[0086] Combine the following to form a reaction mixture:

[0087] The first diol and the second diol, wherein the first diol is an oligomer, polymer or copolymer, and the second diol is a short-chain diol having 2 to 20 carbon atoms;

[0088] A bifunctional compound, including a dicarboxylic acid, a dicarboxylic acid halide, an acid anhydride, or a diester;

[0089] The third diol contains a branched hydrocarbon group or a hydrocarbon oxygen group;

[0090] Optionally, an end-capping agent; and

[0091] catalyst;

[0092] The reaction mixture is exposed to conditions sufficient to induce a reaction and form the polyester copolymer.

[0093] In this method for preparing polyester copolymers, the first diol, second diol, third diol, and bifunctional compound are as described above for polyester copolymers. The catalyst can be any catalyst known in the art for preparing polyesters. In one embodiment, the catalyst can be a titanium-based, tin-based, zinc-based, or zirconium-based catalyst. Examples of suitable catalysts known in the art are titanium isopropoxide (IV), titanium isobutoxide (IV), or titanium n-butoxide (IV), titanium acetylacetonate (IV), zirconium n-butoxide (IV), tin 2-ethylhexanoate, organotin oxides such as dibutyltin oxide, dibutyltin diacetate, zinc acetate, and combinations thereof. In one embodiment, the catalyst is titanium alkanoate, such as titanium isopropoxide (IV), titanium isobutoxide (IV), or titanium n-butoxide (IV). In another embodiment, the catalyst is n-butyl titanate. Many catalysts for preparing polyesters are commercially available.

[0094] The combination of the first diol, second diol, third diol, and a bifunctional compound, along with a catalyst, to form a reaction mixture is carried out according to methods known in the art. The reaction mixture is exposed to conditions sufficient to induce a reaction and form a polyester copolymer. These conditions sufficient to form the polyester copolymer are those known in the art. The polyester copolymers of the present invention can be prepared and the method for preparing the polyester copolymers of the present invention can be practiced using reactors known in the art for preparing polyesters.

[0095] A pressure-sensitive adhesive comprising the polyester copolymer described above. A pressure-sensitive adhesive prepared according to the method of the present invention.

[0096] A skin patch comprising the pressure-sensitive adhesive described above, wherein the patch is a transdermal drug delivery patch or a wound care patch. The skin patch can be manufactured by methods known in the art. For example, the skin patch can be manufactured by forming a film on a backing sheet made of materials known in the art.

[0097] 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 prepared by methods known in the art. For example, a film shaped to the form of the device can be prepared and adhered to the medical device.

[0098] A polyester copolymer comprising: random units having the following formula [-OR 4 O-]、[-OR 5 O-]、[-C(O)R 6 C(O)-]、[-OR 7O-], where R 4 It is a hydrocarbon group having 2 to 20 carbon atoms, or alternatively 2 to 5 carbon atoms, or alternatively 2 to 4 carbon atoms, R 5 It is a branched hydrocarbon group having 4 to 20 carbon atoms, a branched hydrocarbon group substituted with an alkyl group or a branched hydrocarbon group substituted with an ether, R 6 It is a hydrocarbon subgroup with 2 to 12 carbon atoms, where R 7 It is an oligomeric, copolymeric, or polymeric alkylene or alkylene glycol having a Mw of greater than 400 g / mol, or alternatively 400 to 3000 g / mol, and wherein the polyester copolymer is hydroxyl, carboxyl, or carboxylic acid ester-terminated.

[0099] R 4 It is an alkylene group having 2 to 20 carbon atoms. Examples of alkylene groups include, but are not limited to, ethylene, propyleneene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene; and branched alkylenes such as 1-methylethylene, 1-methylpropylene, 2-methylpropylene, 2-methylpropylene, 1,1-dimethylethylene, 1-methylbutylene, 1-ethylpropylene, 2-methylbutylene, 3-methylbutylene, 1,2,-dimethylpropylene, 2,2-dimethylpropylene, 1-methylhexylene, 2-methylhexylene, 1-ethylhexylene, 2 -Ethylhexene, 1-methylheptene, alkyl-substituted (i.e., branched) octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, and tetradecylene; cycloalkylene, such as cyclopentylene, cyclohexene, and methylcyclohexene; aryl, such as phenylene and naphthylene; alkylaryl, such as tolyl and xylene; arylalkylene, such as benzylene and phenylethylene; branched alkenyl, such as 1-methylalkenyl, 1-methylpropenyl, 2-methylbutenyl, 1-ethylhexenyl, and 2-ethylhexenyl.

[0100] R 5 It is a branched hydrocarbon group having 4 to 20 carbon atoms, a branched hydrocarbon group substituted with an alkyl group, or a branched hydrocarbon group substituted with an ether group. Examples of branched hydrocarbon groups are related to R. 4 The examples of alkylene groups substituted with hydroxyl groups include those for R. 5 The alkylene group substituted with one or more alkyloxy groups. Examples of alkyloxy groups include, but are not limited to, alkoxy groups such as methoxy, ethoxy, methylethoxy, ethylethoxy, methylpropoxy, ethylpropoxy, propylpropoxy, methylbutoxy, ethylbutoxy, propylbutoxy, and ethylhexyloxy. In one embodiment, R 5 It is ethylhexyloxymethyl ethylidene, [-CH2C(H)(CH2OCH(CH2CH3)((CH2)4CH3))-].

[0101] R 6 It is a hydrocarbon-like group with 4 to 12 carbon atoms. Hydroxyl group R 6 Examples include, but are not limited to, 1,3- and 1,4-phenylene, naphthylene, cyclohexylene, biphenylene, and C4-C 10 Any one of the aliphatic alkylene groups, spiroyl groups, or combinations thereof. In one embodiment, the bifunctional compound is a phenylene group.

[0102] R 7 It is an oligomeric, copolymeric, or polymeric alkylene glycol or alkylene glycol having a Mw of greater than 400 g / mol, or alternatively 400 to 3000 g / mol. Examples include, but are not limited to, polyethyleneoxy, polypropyleneoxy, and polyethylpropyleneoxy.

[0103] In one embodiment, the polyester copolymer further comprises a unit having the following structure: a polyalkylene glycol-terminated diorganosiloxane or polyether having a molecular weight of 400 to 3000 g / mol per unit. This unit is derived from the polyalkylene oxide polysiloxane described above.

[0104] In one embodiment, the polyester copolymer further comprises [-OR] 8 [O-]O-] linear polyol unit, wherein R 8 It is a trivalent hydrocarbon group having 4 to 3000 carbon atoms. Examples of trivalent hydrocarbon groups include, but are not limited to, trivalent butane, pentane, hexane, heptane, and their isomers. In one embodiment, R 7 It is 2-ethyl-2-methylenepropylene.

[0105] A particularly important application of the polyester copolymer of the present invention is in transdermal or topical drug delivery systems or in topical patches for the local application of a drug to a substrate (such as skin or mucous membrane tissue). This system comprises an active agent and the polyester copolymer of the present invention acting as a pressure-sensitive adhesive. The active agent and its relationship to the polyester copolymer in this system are described in detail below. As those skilled in the art will appreciate, the system is structural and can take many forms, including but not limited to patches, films, multilayer dressings, storage systems, and combinations thereof. The active agent in this system is used for controlled transdermal delivery to the substrate. The system may also (but is not required 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. A preferred application of the transdermal drug delivery system of the present invention is the treatment of a user or patient with the active agent. Thus, the substrate is typically the user's skin, and in this preferred application, the user applies and wears the system on their skin.

[0106] The surfactant can be any component suitable for transdermal delivery to a substrate. Suitable surfactants include, but are not limited to, those disclosed and so described in U.S. Patent No. 5,474,783 to Miranda et al., the disclosure of which is incorporated herein by reference in its entirety. These active agents include, but are not limited to, drugs acting on the heart, androgenic steroids, estrogens, hormones, fertility stimulants, drugs with effects on the central nervous system, nutritional agents, anti-inflammatory agents, antihistamines, respiratory agents, sympathomimetic agents, miotics, cholinergic agonists, antimuscarinic or muscarinic cholinergic blockers, mydriatics, psychostimulants, anti-infectives, dermatological agents, humoral agents, antispasmodics, antidepressants, antidiabetic drugs, appetite suppressants, anti-allergic drugs, sedatives, antipsychotics, decongestants, antipyretics, antimigraines, drugs for treating nausea and vomiting, antimalarial drugs, antiulcer agents, peptides, drugs for Parkinson's disease, drugs for spasticity, drugs for acute muscle spasms, anti-estrogens, anti-hormones, pain relievers, local anesthetics, drugs for dermatological treatment, therapeutic agents, and combinations thereof.

[0107] More specific examples of active agents suitable for implementation as active agents in this invention, as outlined above, include: cardiac drugs, exemplarily, organic nitrates such as nitroglycerin, isosorbide dinitrate, and isosorbide mononitrate; quinidine sulfate; procainamide; thiazides such as benzylfluorothiazide, chlorothiazide, and hydrochlorothiazide; nifedipine; nicardipine; adrenergic blockers such as timolol and propranolol; verapamil; diltiazem; captopril; clonidine and prazosin; androgenic steroids such as testosterone, methyltestosterone, and flumethyltestosterone; estrogens such as conjugated estrogens, esterified estrogens, ethinylestradiol, estrone sulfate piperazine, 17-(3-estradiol, 17-(3-)-estradiol, etc. Estradiol valerate, equilin, mestriol, estrone, estriol, 17-(3-ethinylestradiol) and diethylstilbestrol; progestins such as progesterone, 19-norprogesterone, norethindrone, norethindrone acetate, mesenterogesterone, chlormedroxyprogesterone, ethinylestradiol, medroxyprogesterone acetate, hydroxyprogesterone caproate, norethindrone diacetate, isethindrone, 17-α-hydroxyprogesterone, dydrogesterone, dimethicone, linegestrol, norethindrone, dimethicone, pymetrozine, and megestrol acetate; with effects on the central nervous system. Systemic drugs, such as sedatives, hypnotics, anti-anxiety drugs, analgesics, and anesthetics, including chloroacetaldehyde, buprenorphine, naloxone, haloperidol, fluphenazine, pentobarbital, phenobarbital, secobarbital, codeine, lidocaine, tetracaine, dacronin, decabcaine, cocaine, procaine, mepivacaine, bupivacaine, eticaine, prilocaine, benzocaine, fentanyl, and nicotine; nutritional supplements, such as vitamins (e.g., nicotinamide), essential amino acids, and essential fats; anti-inflammatory drugs. Drugs such as hydrocortisone, cortisone, dexamethasone, fluocinolone, triamcinolone, methylhydroxyzine, prednisolone, fludrocortisone, prednisolone, halcinonide, methylprednisolone, fludrocortisone, corticosteroids, peramisone, betamethasone, ibuprofen, naproxen, fenbuprofen, flurbiprofen, acetaminophen, indobuprofen, ketoprofen, sulprofen, indomethacin, piroxicam, aspirin, salicylic acid, diflunisal, methyl salicylate, phenylbutazone, sulindac, mefenamic acid, meclofenamic acid. Sodium thiazoline, naproxen, etc.; topical analgesics, such as camphor, peppermint, capsicum extract, frankincense, green tea, juniper tea, and caffeine; antihistamines, such as diphenhydramine, dimenhydrinate, perphenazine, triprolidine, pyramine, chlorcyclizine, promethazine, carbisamine, trapyridine, brompheniramine, hydroxyzine, cyclizine, meclizine, terfenadine, and chlorpheniramine.Respiratory agents, such as theophylline and β-adrenergic agonists such as salbutamol, terbutaline, orsinarine, ritodrine, capbuterol, fenoterol, quinterenol, limectin, solmefamol, soteritol, and trotoquinol; sympathomimetic drugs, such as dopamine, norepinephrine, phenylpropanolamine, and phenylephrine. Pseudoephedrine, amphetamine, hexahydrodeoxyephedrine, and adrenaline; miotics, such as pilocarpine; cholinergic agonists, such as choline, acetylcholine, methacholine, carbacholine, betaine, pilocarpine, muscarine, and arecoline; antimuscarine or muscarine-cholinergic blockers, such as atropine, scopolamine, homatropine, methylscopolamine, methylhomatropine bromide, and methylphenidate. Methanotherapeutic agents, including cyclopentolate, tropicamide, propylthiophene, sintropine, bicyclic amine, and eucatropine; mydriatics such as atropine, cyclopentolate, homatropine, scopolamine, tropicamide, eucatropine, and amphetamine; stimulants such as 3-(2-aminopropyl)indole and 3-(2-5-aminobutyl)indole; anti-infectives such as antibiotics including penicillin, tetracycline, chloramphenicol, sulfacetamide, sulfadiazine, sulfamethoxazole, and sulfisoxazole; antiviral agents including idoxuridine; antibacterial agents such as erythromycin and clarithromycin; antifungal agents such as ketoconazole; and other anti-infectives including furacilin, cyclopirox, terbinafine, and witch hazel. Hazel, etc.; dermatological agents such as retinoids; vitamins C and E; benzoyl peroxide (BPO) (commonly known as 1,5-dibenzoyl peroxide) and dapsone; humoral agents such as natural and synthetic prostaglandins, such as PGE1, PGE2-α and PGF2-α, and the PGE1 analog misoprostol; antispasmodics such as atropine, methotrexate, papaverine, cinnamedrine and scopolamine; antidepressants such as paroxetine, phenelzine, tranexamic acid, imipramine, amitriptyline, trimethoprim, doxepin, desipramine, nortriptyline, protriptyline, amoxapine, maprotiline and trazodone; antidiabetic drugs such as insulin, and anticancer drugs such as tamoxifen and methotrexate. Aminopterin; appetite suppressants such as dextroamphetamine, methamphetamine, propanolamine, fenfluramine, diethylamine acetone, masindole, and phentermine; antihistamines such as antazoline, dexamethasone, chlorpheniramine, piracetam, and fenilatin; sedatives such as reserpine and chlorpromazine; and anti-anxiety benzodiazepines such as alprazolam, clozapine, loratadine, halazepam, oxazepam, prarazepam, clonazepam, flurazepam, triazolam, lorazepam, and diazepam;Antipsychotics, such as perphenazine acetate, chlorpromazine, trifluprozine, mesoridazine, piperazine, thioridazine, acetylperphenazine, fluphenazine, perphenazine, trifluoperazine, chlorprothixone, tevothixone, haloperidol, bromopiperidine, loxapine, and morphinone; decongestants, such as phenylephrine, ephedrine, naphazoline, and tetrahydrozoline; antipyretics, such as aspirin and salicylamide; anti-migraine agents, such as dihydroergotamine and phenthiazide; drugs used to treat nausea and vomiting, such as chlorpromazine, perphenazine, and prochlorperazine. Promethazine, thiopromethazine, trifluprozine, and isoprazine; antimalarial drugs such as 4-aminoquinoline, α-aminoquinoline, chloroquine, and pyrimethamine; antiulcer agents such as misoprostol, omeprazole, and emprost; peptides such as growth-releasing factor; drugs used for Parkinson's disease, spasticity, and acute muscle spasms, such as levodopa, carbidopa, amantadine, apomorphine, bromocriptine, selegiline / deprenyl, trihexyphenidyl hydrochloride, benzalkonium chloride, propranolol hydrochloride, baclofen, diazepam, and dantrolene; and anti-estrogens or hormones such as tamoxifen or human chorionic gonadotropin.

[0108] In one embodiment, the active agent is selected from the group consisting of ketoprofen, estradiol, clonidine, and combinations thereof.

[0109] As noted above, the specific active agents are not limited to those described above. Other examples of suitable active agents for use in the system will be apparent to those skilled in the art (see, for example, pages 149-217 of Yie Chien’s monograph entitled “Novel Drug Delivery Systems,” US 8,614,278 B2, Volume 14 of Drugs and the Pharmaceutical Sciences, Marcel Dekker, Inc., New York, NY 10016 (1982)). As those skilled in the art will appreciate, the active agent can be present in the system in different forms depending on which form produces the optimal delivery characteristics, such as release rate and total amount released, as described below. For example, in the case of a drug, the drug can be in its free base or acid form, or in the form of a salt, ester, or any other pharmacologically acceptable derivative, or even as a component of a molecular complex.

[0110] Furthermore, regarding the active agent, it should be recognized that the active agent is most typically arranged within the polyester copolymer. However, it should also be understood that the active agent and the polyester copolymer can coexist in a discrete layer in the system. That is, in some embodiments, the active agent is not arranged within or directly incorporated into the polyester copolymer. Of course, transdermal drug delivery systems may also contain other known agents that accelerate the delivery of active agents through the skin or other substrates. These other agents are also referred to in the art as transdermal or penetration enhancers, accelerators, adjuvants, and absorption promoters, and are simply collectively referred to herein as "enhancers". These enhancers include those with a wide variety of mechanisms of action, including those that improve the solubility and diffusivity of the active agent within the polyester copolymer, and those that improve transdermal absorption, for example by altering the stratum corneum's ability to retain moisture, softening the skin, improving skin permeability, acting as a penetration aid or follicle opener, or altering the state of the skin (including the boundary layer). Some of these enhancers have more than one mechanism of action, but essentially they are used to enhance the delivery of the active agent to the substrate.

[0111] Some examples of enhancers are polyols such as dipropylene glycol, propylene glycol, and polyethylene glycol (which enhance the solubility of surfactants); oils such as olive oil, squalene, and lanolin; fatty ethers such as cetyl ether and oil ether; fatty acid esters such as isopropyl myristate, which enhance the diffusion of surfactants; ureas and urea derivatives such as allantoin, which affect the ability of keratin to retain moisture; polar solvents such as dimethyl decyl phosphorus oxide, methyl octyl sulfoxide, dimethyl lauramide, dodecyl pyrrolidone, isosorbide, dimethyl acetonide, dimethyl sulfoxide, decyl methyl sulfoxide, and dimethylformamide, which affect keratin permeability; salicylic acid, which softens keratin; amino acids, which are penetration aids; benzyl nicotinate, which is a hair follicle opener; and higher molecular weight aliphatic surfactants such as lauryl sulfate, which alter the surface state of the substrate (e.g., skin) and the applied surfactant. Other reagents include oleic acid and linoleic acid, ascorbic acid, panthenol, butylated hydroxytoluene, tocopherol, tocopherol acetate, tocopherol linoleate, propyl oleate, and isopropyl palmitate.

[0112] Other applications of the polyester copolymers of the present invention include skin and prosthetic adhesion for medical devices, such as prostheses, wigs, medical device assembly adhesives, adhesives for in vitro diagnostics, tape adhesives, adhesive films, adhesives for surgical dressings, conductive adhesives, adhesives for ostomy devices, adhesives for incontinence devices (such as urisheaths, bags), adhesives for securing catheters, and adhesives for dressings, border dressings, and intravenous (IV) dressings used in wound care, scar care, negative pressure wound therapy.

[0113] Other applications of the polyester copolymers of the present invention include adhesives and patches for skin beauty applications, face masks, skin moisturizing, wrinkle treatment, cosmetics, makeup, hair styling, and special effects makeup.

[0114] In some embodiments of the invention, additives (such as plasticizers or tackifiers) may be incorporated into the system, typically into the composition, to improve the adhesive characteristics of the polyester copolymer. Tackifiers are particularly useful in those embodiments in which the activator does not plasticize the polyester polymer. Suitable tackifiers are those known in the art, including: (1) aliphatic hydrocarbons; (2) mixtures of aliphatic and aromatic hydrocarbons; (3) aromatic hydrocarbons; (4) substituted aromatic hydrocarbons; (5) hydrogenated esters; (6) polyterpenes; and (7) hydrogenated rosin. The tackifiers used are typically compatible with the other components in the composition.

[0115] In some embodiments, the polyester copolymer may include fillers for mechanical reinforcement, rheological property tuning, thermal conductivity, electrical conductivity, or combinations thereof. In some embodiments, fillers may include, but are not limited to, microspheres, expandable materials (containing liquid or gas), silica, cellulose materials, polysaccharides, conductive fillers, metal fibers, graphite, conductive materials (such as carbon nanotubes and silver nanowires), and combinations thereof. Tackifiers, plasticizers, and / or filler particles are known in the art, and they are used in dosages known in the art.

[0116] The adhesive composition may be a pressure-sensitive adhesive.

[0117] The adhesive composition can be designed to be applied to any substrate. For example, the substrate can be human or animal skin. Alternatively, the substrate can be a medical device or appliance. For example, the substrate can be, but is not limited to, plastics, polymers, fabrics, nonwovens, coatings, wood, metals, and ceramics.

[0118] Examples of suitable tackifiers are silicone fluids (e.g., Q7-9120 silicone fluid, available from Dow Corning Corporation, Midland, Michigan), silicone resins (e.g., Q2-7466 INT, available from Dow Corning Corporation, Midland, Michigan), or mineral oils. Silicone fluids and silicone resins can be used in blends comprising polysiloxanes as a major component. In other embodiments where, for example, synthetic rubber is a major component, mineral oils are available as tackifiers. It is noteworthy that some active agents (such as the vasodilator nitroglycerin) act as plasticizers in the composition because they are soluble to some extent in the components of the composition. For active agents that are not readily soluble in the components, a cosolvent can be added for the active agent and other components. Cosolvents, such as lecithin, retinol derivatives, tocopherol, dipropylene glycol, triacetin, propylene glycol, saturated and unsaturated fatty acids, mineral oil, silicone fluids, alcohols, butyl benzyl phthalate, etc., may be used in the practice of this invention depending on the solubility of the active agent in the composition.

[0119] Some aspects of the present invention are as follows:

[0120] Aspect 1. A polyester copolymer comprising:

[0121] The following reaction products are: a first diol and a second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short-chain diol having 2 to 20 carbon atoms; a bifunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; and a third diol, wherein the third diol contains a branched hydrocarbon group.

[0122] Aspect 2. The polyester copolymer according to aspect 1, wherein the polyester copolymer comprises a polyol.

[0123] Aspect 3. The polyester copolymer according to aspect 2, wherein the polyol is oligomerized, polymerized, copolymerized, or copolymerized.

[0124] Aspect 4. The polyester copolymer according to any one of Aspects 2 or 3, wherein the polyol is linear.

[0125] Aspect 5. The polyester copolymer according to any one of the preceding aspects, further comprising a triol monomer.

[0126] Aspect 6. The polyester copolymer according to any one of the preceding aspects, wherein the first diol is an oligomeric polyether.

[0127] Aspect 7. The polyester copolymer according to any one of Aspects 1 to 5, wherein the first diol has polysiloxane and polyalkylene diol segments.

[0128] Aspect 8. The polyester copolymer according to aspect 7, wherein the first diol is a polysiloxane terminated with polyalkylene glycol segments.

[0129] Aspect 9. The polyester copolymer according to any one of the preceding aspects, wherein the second diol has 2 to 8 carbon atoms, alternatively 3 to 8, alternatively 2 to 6, or alternatively 3 to 6 carbon atoms.

[0130] Aspect 10. The polyester copolymer according to any one of the preceding aspects, wherein the bifunctional compound is a phthalate.

[0131] Aspect 11. The polyester copolymer according to any one of the preceding aspects, wherein the third diol is according to Formula I:

[0132] (I) ,

[0133] R1 is hydrogen, a hydrocarbon group, hydroxyl group or ether having 1 to 12 carbon atoms (C1-C12), R2 is a hydrocarbon group, hydroxyl group or ether having 1 to 12 carbon atoms (C1-C12), and R3 is a hydrocarbon subgroup having 1 to 5 carbon atoms.

[0134] Aspect 12. A method for preparing a polyester copolymer, the method comprising the steps of: combining the following to form a reaction mixture: a first diol and a second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short-chain diol having 2 to 20 carbon atoms; a bifunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; a third diol, wherein the third diol contains a branched hydrocarbon group or a hydroxyl group; and a catalyst; and exposing the reaction mixture to conditions sufficient to induce a reaction and form the polyester copolymer.

[0135] Aspect 13. A pressure-sensitive adhesive comprising a polyester copolymer composition according to any one of Aspects 1 to 11.

[0136] Aspect 14. The pressure-sensitive adhesive according to aspect 13, wherein the pressure-sensitive adhesive is prepared by the method according to claim 12.

[0137] Aspect 15. A skin patch comprising a pressure-sensitive adhesive according to any one of Aspects 13 or 14, wherein the patch is a transdermal drug delivery patch or a wound care patch.

[0138] Aspect 16. A medical device comprising a pressure-sensitive adhesive according to any one of aspects 13 or 14.

[0139] Aspect 17. A polyester copolymer comprising: random units having the following formula [-OR 4 O-]、[-OR5 O-]、[-C(O)R 6 C(O)-]、[-OR 7 O-], where R 4 It is a hydrocarbon group having 2 to 20 carbon atoms, or alternatively 2 to 5 carbon atoms, or alternatively 2 to 4 carbon atoms, R 5 It is a branched hydrocarbon group having 4 to 20 carbon atoms, a branched hydrocarbon group substituted with an alkyl group or a branched hydrocarbon group substituted with an ether, R 6 It is a hydrocarbon group having 2 to 12, or alternatively 4 to 12, carbon atoms, wherein R 7 It is an oligomeric, copolymeric, or polymeric alkylene glycol having a Mw of greater than 400 g / mol, or alternatively 400 to 6000 g / mol, or alternatively 400 to 3000 g / mol, and wherein the polyester copolymer is hydroxyl, carboxyl, or carboxylic acid ester-terminated.

[0140] Aspect 18. The polyester copolymer according to aspect 17, further comprising units having the following structure: a diorganodipolysiloxane or polyether with a molecular weight of 400 to 3000 g / mol and end-capped with a polyalkylene glycol.

[0141] Aspect 19. The polyester copolymer according to any one of Aspects 17 or 18, further comprising according to formula [-OR] 7 [O-]O-] linear polyol unit, wherein R 7 It is a trivalent hydrocarbon group having 2 to 3,000, or alternatively 4 to 3,000, carbon atoms.

[0142] Aspect 20. A polyester copolymer comprising:

[0143] A first diol and a second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short-chain diol having 2 to 20 carbon atoms; a bifunctional compound comprising a dicarboxylic acid, a dicarboxylic acid halide, an anhydride, or a diester; and a third diol comprising a branched hydrocarbon group.

[0144] The polyester copolymer of the present invention can be used in healthcare applications where pressure-sensitive adhesives are employed, exhibiting improved skin properties. The polyester copolymer can be used as a pressure-sensitive adhesive in patches and medical devices to attach patches or devices to stratum corneum and mucous membrane substrates. Example

[0145] The following examples are presented to better illustrate the method of the invention, but these examples should not be considered as limiting the invention described in the appended claims. Unless otherwise stated, all parts and percentages reported in the examples are by weight. The following table describes the abbreviations used in the examples:

[0146] All copolymerization reactions were carried out in a 2 L Büchi autoclave equipped with three belt-driven spiral impellers, a Vigreux column, a glass condenser, a vacuum line, and a separate nitrogen inlet.

[0147] By using 1 The polymer composition was determined by 1H NMR spectroscopy. The integral values ​​were normalized relative to the peaks of aromatic terephthalate protons, and the mol% of terephthalate was assumed to be 50%. Molecular weight, average molecular weight, and dispersion were determined by GPC analysis, calibrated based on UV absorption at 250 nm.

[0148] Peel adhesion, measured in Newtons (N), was determined using a tensile testing device (e.g., Instron). Samples were prepared by heating the adhesive, applying it to a suitable substrate, and pressing it to the desired thickness. The coated substrate was then cut into 2.5 cm (1 inch) strips, and a polycarbonate film was laminated onto the surface. Test parameters: 180° peel release test, test speed = 10.0 mm / s, distance = 90.0 mm. Each sample was tested three times, and the average force (N) was reported. Any observed characteristics were recorded.

[0149] Parallel plate rheology was recorded on a TA Instruments Discovery HR-1 at a sample measurement temperature of 30°C.

[0150] Table 1. Abbreviations used in this article.

[0151]

[0152] Dimethyl terephthalate (DMT), 1,4-butanediol (BDO), polypropylene glycol (PPG2000 and PPG4000), polytetramethylene ether glycol (PTMEG2000), polybutylene terephthalate (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. Ethylhexylglycerin was obtained from Ambeed. 1,2-Hexanediol; 1,2-dodecanediol; 2-methyl-2-propylpropane-1,3-diol; and PTMEG2900 were purchased from TCI USA. Commercial grade HTPB was obtained from Island Pyrochemicals. Silsurf Di-1010, Silsurf Di-2012, Silsurf A008-UP, and Silsurf Di-15I were purchased from Celtech or received from them as samples. Polyethylene terephthalate was purchased from Goodfellow. Glycerin from Procter & Gamble (P&G) was obtained through Univar. Ethylene glycol was purchased from Fisher Scientific.

[0153] For reactions initiated by DMT and BDO:

[0154] Add all reactants except the catalyst to the reactor. Evacuate the reactor and backfill with nitrogen three times. Heat the reactants to a jacket temperature of 180°C with stirring at 60 RPM. Once the reactor reaches an internal temperature of 80°C, inject the Tyzor® catalyst. Then raise the jacket temperature to 210°C for approximately 2.5 hours, simultaneously with the distillation of methanol. Once butanediol begins to azeotropically react with methanol—corresponding to a temperature drop at the bottom of the distillation column—raise the jacket temperature to 240°C and reduce the pressure in the reactor to approximately 80 Torr. After approximately 1 hour, raise the jacket temperature to 250°C. After another hour, raise the jacket temperature to 260°C and reduce the pressure to approximately 20 Torr. Increase the vacuum over the next 2–6 hours until the pressure in the reactor is approximately 0.5 Torr. Stir the reaction at this temperature and pressure until the torque plateaus at 10–110 Ncm for approximately 30 minutes. At this point, cool the reactor to room temperature and jacket it with nitrogen. The resulting polymer is manually removed from the container. For polymers using ethylene glycol (EG) instead of BDO, the same basic procedure is followed, except that 1,2-ethylene glycol is collected from the distillate instead of BDO.

[0155] For reactions initiated by PBT or PET prepolymers:

[0156] Add all reactants except the catalyst to the reactor. Evacuate the reactor and backfill with nitrogen three times. Heat the reactants to a jacket temperature of 180°C with stirring at 60 RPM. Once the reactor reaches an internal temperature of 80°C, inject the Tyzor® catalyst. Then raise the jacket temperature to 210°C until the internal temperature plateaus. At this point, raise the jacket temperature to 240°C and reduce the pressure in the reactor to approximately 80 Torr. Then, after 10 minutes, raise the jacket temperature to 250°C, and then after another 10 minutes, raise it to 260°C. Gradually increase the vacuum to 0.5 Torr over a period of 2–6 hours while keeping the distillation of 1,4-butanediol (for PBT) and 1,2-ethylene glycol (for PET) relatively constant. Then maintain the reaction at this temperature and pressure until the torque reaches its maximum value of 10–110 Ncm for approximately 30 minutes. At this point, cool the reactor to room temperature and jacket it with nitrogen. Manually remove the resulting polymer from the container.

[0157] In the following examples, Examples 1, 4, 8, 12, 14 and 15 are comparative examples.

[0158] Example 1 - This example is too hard and rubbery and has very little adhesion.

[0159] 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).

[0160] Example 2 - This sample is hard and rubbery and has very little adhesion.

[0161] DMT 100.9 g (0.519 mol); BDO ​​36.4 g (0.403 mol); PTMEG 239.1 g (0.120mol); EHG 78.0 g (0.382 mol); Ethanox 330 1.2 g (0.002 mol); Tyzor® 1.6 g (0.005mol).

[0162] Example 3 (3205) - This sample has good adhesion but is easily torn and exhibits cohesive failure, leaving some residue on the skin and polycarbonate.

[0163] 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).

[0164] Example 4 (3207) - No viscoelastic properties.

[0165] 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).

[0166] Example 5 (3210) - This sample has very strong adhesion but lacks cohesive strength.

[0167] 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).

[0168] Example 6 (3215) - This sample is too rubbery.

[0169] 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).

[0170] Example 7 (3216) - This sample is cross-linked and swells in the presence of a solvent.

[0171] 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).

[0172] Example 8 (3220) - This sample is adhesive but lacks cohesive strength.

[0173] DMT - 123.5 g (0.003 mol); PPG2000 60.0 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).

[0174] Example 9 (3221) - This sample is adhesive but lacks cohesive strength.

[0175] 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).

[0176] Example 10 (3228) - This sample is adhesive but lacks cohesive strength.

[0177] 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).

[0178] Example 11 (3230) - This sample is viscous and has good cohesive strength.

[0179] 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).

[0180] Example 12 (3234) - This sample has a viscosity of less than 11 and 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).

[0181] Example 13 (3237) - This sample shows a good balance between 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).

[0182] Example 14 (3239) - This sample has no adhesive properties.

[0183] 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).

[0184] Example 15 (3240) - This sample has no adhesive properties.

[0185] 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).

[0186] Example 16 (3244) - This sample shows a good balance between 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).

[0187] Example 17 (3253) - This is a repetition of Example 16, which is started by PBT.

[0188] PBT 90.0 g (0.002 mol); Silsurf Di-1010 156.4 g (0.087 mol); PTMEG2000293.6 g (0.147 mol); EHG 34.0 g (0.166 mol); Ethanox 1.2 g (0.002 mol); Tyzor® 0.8g (0.002 mol).

[0189] Example 18 (3257) - This sample shows a good balance between 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).

[0190] Example 19 (3261) - This sample shows a good balance between 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).

[0191] Example 20 (3266) - This sample is cross-linked and swollen in the presence of a 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 g (0.382 mol); Ethanox 330 1.2 g (0.002 mol); Tyzor® 1.6 g (0.005 mol).

[0192] Example 21

[0193] (3267) - This sample shows a good balance between adhesion and cohesive strength.

[0194] 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).

[0195] Example 22 (3274) - This sample shows a good balance between 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 11.2 g (0.017 mol), Ethanox330 1.2 g (0.002 mol), Tyzor® 1.6 g (0.005 mol).

[0196] Example 23 (3277) - This sample shows a good balance between adhesion and cohesive strength. PBT 127.6 g (0.003 mol), Silsurf Di-15I 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).

[0197] Example 24 (CO1279) - This sample shows a good balance between adhesion and cohesive strength.

[0198] PET 218 g (0.007 mol), PPG2000 216 g (0.108 mol), PTMEG2900 216 g (0.074mol), EHG 139.8 g (0.684 mol), glycerin 5.23 g (0.056 mol), Ethanox 330 2.2 g (0.003mol), Tyzor® 2.8 g (0.008 mol).

[0199] Example 25 (CS0301) - This sample exhibits good adhesion and low cohesive strength.

[0200] 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), Ethanox330 2.16 g (0.003 mol), Tyzor® 2.8 g (0.008 mol).

[0201] Example 26 (CQ3981) - This sample shows good adhesion and good cohesive strength.

[0202] PBT 127.6 g (0.0034 mol), PPG2000 120 g (0.06 mol), PTMEG2000 120 g (0.06mol), EHG 78 g (0.382 mol), TMP 2.5 g (0.019 mol), Lauryl alcohol 3.2 g (0.017 mol), Ethanox330 1.2 g (0.002 mol), Tyzor® 1.6 g (0.005 mol).

[0203] Example 27 (CS0307) - This sample shows good adhesion and good cohesive strength.

[0204] 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).

[0205] Example 28 (CO1281) - This sample exhibits good adhesion and low cohesive strength.

[0206] DMT 200.2 g (1.031 mol), ethylene glycol 50.2 g (0.81 mol), PPG2000 202.1 g (0.101 mol), PTMEG2000 202.1 g (0.104 mol), EHG 135.85 g (0.665 mol), glycerin 5.2 g (0.056 mol), Ethanox 330 2.16 g (0.003 mol), Tyzor® 2.8 g (0.008 mol).

[0207] Example 29 (CO1283) - This sample exhibits low viscosity and good cohesive strength.

[0208] 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, Dimerofolic Acid Diol 69.0 g (0.128 mol), Glycerin 5.6 g (0.061 mol), Ethanox 330 2.16 g (0.003 mol), Tyzor® 3.25 g (0.010 mol).

[0209] Table 2 describes how... 1 The characteristics of the polyester copolymers of Examples 1 to 29 were determined by ¹H NMR spectroscopy and GPC. The weight percentage of the hard segment was calculated from the combined weight percentage of terephthalic acid and the second diol. The weight percentage of the soft segment was calculated from the combined weight percentage of one or more first diols. The weight percentage of the diol refers to the weight percentage of the third diol. The weight percentage values ​​were obtained by analyzing the... 1 The values ​​of Mw, Mn, and H NMR spectral peaks are calculated by integration. It was determined by GPC.

[0210] Table 2. Characteristics of the example polyester copolymers

[0211]

[0212] The sample is cross-linked. It is either insoluble or the data obtained is unreliable due to poor solubility.

[0213] pass 1 Determined by H NMR spectroscopy in CDCl3.

[0214] Table 3 shows the wide range of desirable peel properties that can be achieved through polyester polymer formulation design compared to the comparative examples.

[0215] Table 3. Peeling characteristics

[0216]

[0217] Indicates widespread cohesion destruction

[0218] For the selected example, rheological analysis of the parallel plate at 30°C:

[0219] Table 4. Favorable adhesion properties of top-perforated samples as defined by rheological characteristics.

[0220] 。

Claims

1. A polyester copolymer comprising: The following reaction products: A first diol and a second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short-chain diol having 2 to 20 carbon atoms; A bifunctional compound, wherein the bifunctional compound comprises a dicarboxylic acid, a dicarboxylic acid halide, an acid anhydride, or a diester; Third diol, wherein the third diol comprises branched hydrocarbon groups.

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 oligomerized, polymerized, copolymerized, or copolymerized.

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 glycol is an oligomeric polyether.

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

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

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

10. The polyester copolymer according to any one of the preceding claims, wherein, The bifunctional 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) ， R1 is hydrogen, a hydrocarbon group, hydroxyl group or ether having 1 to 12 carbon atoms (C1-C12), R2 is a hydrocarbon group, hydroxyl group or ether having 1 to 12 carbon atoms (C1-C12), and R3 is a hydrocarbon subgroup having 1 to 5 carbon atoms.

12. A method for preparing a polyester copolymer, the method comprising the following steps: Combine the following to form a reaction mixture: A first diol and a second diol, wherein the first diol is an oligomer, polymer, or copolymer, and the second diol is a short-chain diol having 2 to 20 carbon atoms; A bifunctional compound, wherein the bifunctional compound comprises a dicarboxylic acid, a dicarboxylic acid halide, an acid anhydride, or a diester; A third diol, wherein the third diol comprises a branched hydrocarbon group or a hydroxyl group; and catalyst; The reaction mixture is exposed to conditions sufficient to induce a reaction and form the polyester copolymer.

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

14. The pressure-sensitive adhesive according to claim 13, wherein, The pressure-sensitive adhesive is prepared according to the method described in claim 12.

15. A skin patch comprising a pressure-sensitive adhesive according to any 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 a pressure-sensitive adhesive according to any one of claims 13 or 14.

17. A polyester copolymer comprising: Random element with the following formula [-OR 4 O-]、[-OR 5 O-]、[-C(O)R 6 C(O)-]、[-OR 7 O-], Where R 4 It is a hydrocarbon group having 2 to 20 carbon atoms, or alternatively 2 to 5 carbon atoms, or alternatively 2 to 4 carbon atoms, R 5 It is a branched hydrocarbon group having 4 to 20 carbon atoms, a branched hydrocarbon group substituted with an alkyl group or a branched hydrocarbon group substituted with an ether, R 6 It is a hydrocarbon subgroup with 4 to 12 carbon atoms, where R 7 It is an oligomeric, copolymeric, or polymeric alkylene or alkylene glycol with a molecular weight (Mw) greater than 400 g / mol.

18. The polyester copolymer of claim 17, further comprising units having the following structure: polyalkylene glycol-terminated diorganosiloxanes or polyethers having a molecular weight of 400 to 3000 g / mol per unit.

19. The polyester copolymer according to any one of claims 17 or 18, further comprising [-OR] 7 [(O-)O-] linear polyol unit, wherein R 7 It is a trivalent hydrocarbon group with 4 to 3000 carbon atoms.

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