+

WO2018140912A1 - Polyuréthannes thermoplastiques biodégradables et/ou bioabsorbables - Google Patents

Polyuréthannes thermoplastiques biodégradables et/ou bioabsorbables Download PDF

Info

Publication number
WO2018140912A1
WO2018140912A1 PCT/US2018/015842 US2018015842W WO2018140912A1 WO 2018140912 A1 WO2018140912 A1 WO 2018140912A1 US 2018015842 W US2018015842 W US 2018015842W WO 2018140912 A1 WO2018140912 A1 WO 2018140912A1
Authority
WO
WIPO (PCT)
Prior art keywords
chain extender
thermoplastic polyurethane
poly
diisocyanate
tpu
Prior art date
Application number
PCT/US2018/015842
Other languages
English (en)
Inventor
Pallavi KULKARNI
Original Assignee
Lubrizol Advanced Materials, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lubrizol Advanced Materials, Inc. filed Critical Lubrizol Advanced Materials, Inc.
Publication of WO2018140912A1 publication Critical patent/WO2018140912A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/428—Lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4283—Hydroxycarboxylic acid or ester
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic

Definitions

  • thermoplastic polyurethane (TPU) compositions having biodegradable and/or bioabsorbable hard and soft segments while still maintaining good physical properties.
  • TPUs Thermoplastic polyurethanes
  • Conventional TPUs are among biomaterials not intended to degrade, but some conventional TPUs are susceptible to hydrolytic, oxidative and enzymatic degradation in vivo. Such degradation can be utilized to design biodegradable TPUs.
  • thermoplastic polyurethanes have many mechanical properties which make them attractive for biomedical applications, degradation of the polymer presents challenges. It is known that degradation of the TPU soft segment can be achieved by appropriate selection of the soft segment chemistry. Frequently utilized biodegradable TPU soft segments include poly(e-caprolactone), poly(lactic acid), polyglycolic acid and poly(ethylene glycol) polyols. Hard segment degradation is more of a challenge owing to the urethane bonds being less susceptible to degradation. Hard segment modification has focused on varying diisocyanate structures and chain extenders. These modifications, however, often lead to inferior mechanical properties of the TPUs.
  • thermoplastic polyurethane composition that is biodegradable and/or bioabsorbable in bodily environments where both the soft segments of the TPU and the hard segments of the TPU can be biodegradable and/or bioabsorbable, breaking down at a controlled rate, without degrading to toxic byproducts, and while maintaining favorable mechanical properties in bodily environments.
  • thermoplastic polyurethane (TPU) compositions having biodegradable and/or bioabsorbable hard and biodegradable and/or bioabsorbable soft segments while still maintaining good physical properties.
  • the disclosed technology provides a biodegradable and/or bioabsorbable TPU which may be described as the reaction product of: (a) a polyisocyanate component including one or more polyisocyanates capable of breaking down into one or more non-toxic degradants; (b) a polyol component including one or more polyol s capable of breaking down into one or more non-toxic degradants; and (c) at least one chain extender component including one or more short chain diols capable of breaking down into one or more non-toxic degradants, where the short chain diol is a linear, fully saturated alkylene diol.
  • the disclosed technology further provides described TPU where the polyisocyanate component includes an aliphatic diisocyanate.
  • the polyisocyanate component is free of aromatic diisocyanate and/or aromatic polyisocyanates.
  • the overall TPU is free of aromatic diisocyanate and/or aromatic polyisocyanates, and also free of segments and/blocks derived from the same.
  • the disclosed technology further provides the described TPU where the polyisocyanate component is 1,4-butane diisocyanate (BDI), Lysine diisocyanate (LDI), 1 ,6-hexane diisocyanate (HDI), 4,4' -methylene dicyclohexyl diisocyanate (H12MDI), or any combination thereof.
  • BDI 1,4-butane diisocyanate
  • LLI Lysine diisocyanate
  • HDI 1 ,6-hexane diisocyanate
  • H12MDI 4,4' -methylene dicyclohexyl diisocyanate
  • the disclosed technology further provides the described TPU where the polyol component is poly(L-lactide) (PLA), polglycolide (PGA), polycaprolactone (PCL), polytri methylene carbonate, or any combination thereof.
  • PLA poly(L-lactide)
  • PGA polglycolide
  • PCL polycaprolactone
  • polytri methylene carbonate or any combination thereof.
  • the disclosed technology further provides the described TPU where the polyol component further includes a polyether polyol, which may be poly(propylene glycol), poly(ethylene glycol), poly(tetram ethylene ether glycol), or combinations thereof. However in other embodiments the polyol component is free of any of these additional polyether polyols.
  • the chain extender component includes at least one chain extender of the general formula HO-(CH2)n-X-(CH2) n -OH wherein n is an integer from 2 to 4 and X is oxygen (-0-) or disulfide (-S-S-).
  • the disclosed technology further provides the described TPU where the chain extender component includes dipropylene glycol, di-(2-hydroxyethyl) disulfide, diethylene glycol, or any combination thereof.
  • the disclosed technology further provides the described TPU where the chain extender component further includes one or more additional chain extenders, wherein said additional chain extenders includes at least one diol chain extender of the general formula HO-(CH2) m -OH wherein m is an integer from 2 to 6.
  • the disclosed technology further provides the described TPU where the polyol component further includes poly(propylene glycol), poly(ethylene glycol), poly(tetram ethylene ether glycol), or any combination thereof; and where the chain extender component further includes one or more additional chain extenders, wherein said additional chain extenders includes at least one diol chain extender of the general formula HO-(CH2) m -OH wherein m is an integer from 2 to 6.
  • the disclosed technology further provides the described TPU where the polyisocyanate component includes 1,4-butane diisocyanate (BDI), Lysine diisocyanate (LDI), 1,6-hexane diisocyanate (HDI), 4,4 '-methylene dicyclohexyl diisocyanate (H12MDI), or any combination thereof;
  • the polyol component is poly(L- lactide) (PLA), polglycolide (PGA), or polycaprolactone (PCL) or combinations thereof; and the chain extender component is dipropylene glycol, di-(2-hydroxyethyl) disulfide, diethylene glycol, or any combination thereof.
  • the disclosed technology further provides the described TPU where the polyisocyanate component includes 1,6-hexane diisocyanate (HDI); the polyol component includes poly(L-lactide) (PLA), polycaprolactone (PCL) or combinations thereof; and the chain extender component includes dipropylene glycol.
  • the polyisocyanate component includes 1,6-hexane diisocyanate (HDI)
  • the polyol component includes poly(L-lactide) (PLA), polycaprolactone (PCL) or combinations thereof
  • the chain extender component includes dipropylene glycol.
  • the disclosed technology further provides the described TPU where the polyisocyanate component includes 1,6-hexane diisocyanate (HDI); the polyol component includes a combination of poly(L-lactide) (PLA) and polycaprolactone (PCL); and the chain extender component includes dipropylene glycol.
  • the polyisocyanate component includes 1,6-hexane diisocyanate (HDI); the polyol component includes polycaprolactone (PCL); and the chain extender component includes dipropylene glycol.
  • the disclosed technology further provides for medical articles made from the described TPU.
  • such medical articles, which include medical devices are made from the described TPU.
  • such medical articles, which include medical devices are made from the described TPU in combination with one or more other materials, and in some embodiments one or more other polymeric materials.
  • such medical articles, which include medical devices are coated with the described TPU.
  • such medical articles, which include medical devices are coated with the described TPU where the TPU further includes a compound, such as a drug or medicine, that elutes from the TPU over time as the TPU biodegrades and/or bioabsorbs.
  • the disclosed technology further provides for a method of making a bioabsorbable TPU, where the method includes the step of (I) reacting: (a) a polyisocyanate component that includes one or more polyisocyanate capable of breaking down into one or more non-toxic degradants; with (b) a polyol component that includes one or more polyols capable of breaking down into one or more non- toxic degradants; and with (c) at least one chain extender component that includes one or more short chain diols capable of breaking down into one or more non-toxic degradants, where the short chain diol is a linear, fully saturated alkylene diol.
  • thermoplastic polyurethane (TPU) compositions having biodegradable and/or bioabsorbable hard and biodegradable and/or bioabsorbable soft segments while still maintaining good physical properties.
  • the described TPU are the reaction product of: (a) a polyisocyanate component including one or more polyisocyanates capable of breaking down into one or more non-toxic degradants; (b) a polyol component including one or more polyols capable of breaking down into one or more non-toxic degradants; and (c) at least one chain extender component including one or more short chain diols capable of breaking down into one or more non-toxic degradants, where the short chain diol is a linear, fully saturated alkylene diol.
  • the bioabsorbable thermoplastic polyurethane described herein are made using: (a) a polyisocyanate component.
  • the polyisocyanate component includes one or more polyisocyanate capable of breaking down into one or more non-toxic degradants.
  • the polyisocyanate component may include aliphatic or aromatic diisocyanates. However, in some embodiments the polyisocyanate component includes an aliphatic diisocyanate. In some embodiments, the polyisocyanate component is free of aromatic diisocyanate.
  • the polyisocyanate component includes 1,4-butane diisocyanate (BDI), Lysine diisocyanate (LDI), 1,6-hexane diisocyanate (HDI), 4,4'- methylene dicyclohexyl diisocyanate (H12MDI), or any combination thereof.
  • the polyisocyanate component includes 1,4-butane diisocyanate (BDI).
  • the polyisocyanate component includes Lysine diisocyanate (LDI).
  • the polyisocyanate component includes 1,6-hexane diisocyanate (HDI).
  • an additional polyisocyanate may be present and used in combination with the polyisocyanates described above to form the polyisocyanate component.
  • Suitable polyisocyanate which may be used in the invention include aromatic diisocyanates, aliphatic diisocyanates, or combinations thereof.
  • the polyisocyanate component includes one or more aliphatic diisocyanates.
  • the polyisocyanate component is essentially free of, or even completely free of, aromatic diisocyanates.
  • the polyisocyanate component includes one or more aliphatic diisocyanates in combination with one or more aromatic polyisocyanate.
  • the polyisocyanate component is essentially free of, or even completely free of, aromatic diisocyanates.
  • Examples of useful polyisocyanate may include aromatic diisocyanates such as 4,4'-methylenebis(phenyl isocyanate) (MDI), m-xylene diisocyanate (XDI), phenylene-l,4-diisocyanate, 3,3 '-dimethyl-4,4' -biphenylene diisocyanate (TODI), naphthalene-l,5-diisocyanate (NDI), and toluene diisocyanate (TDI); as well as aliphatic diisocyanates such as hexamethylene dissocyanate (HDI) 4,4'-Diisocyanato dicyclohexylmethane (HMD I), isophorone diisocyanate (IPDI), 1 ,4-cyclohexyl diisocyanate (CHDI), decane-l, 10-diisocyanate, lysine diisocyanate (LDI),
  • polyisocyanate is MDI and/or H12MDI. In some embodiments, the polyisocyanate includes MDI. In some embodiments, the polyisocyanate includes H12MDI.
  • the mixtures of two or more polyisocyanates may be used.
  • the thermoplastic polyurethane is prepared with a polyisocyanate component that includes HDI.
  • the thermoplastic polyurethane HDI prepared with a polyisocyanate component that consists essentially of H12MDI.
  • the thermoplastic polyurethane is prepared with a polyisocyanate component that consists of HDI.
  • the polyisocyanate used to prepare the TPU and/or TPU compositions described herein is at least 50%, on a weight basis, a cycloaliphatic diisocyanate.
  • the polyisocyanate includes an a, co-alkylene diisocyanate having from 5 to 20 carbon atoms.
  • the polyisocyanate used to prepare the TPU and/or TPU compositions described herein includes hexamethylene-l,6-diisocyanate, 1, 12-dodecane diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4,4-trimethyl- hexamethylene diisocyanate, 2-methyl-l,5-pentamethylene diisocyanate, or combinations thereof.
  • the described TPU is prepared with a polyisocyanate component that includes HDI, H12MDI, LDI, IPDI, or combinations thereof.
  • the TPU is prepared with a polyisocyanate component consists of, or even consists essentially of HDI.
  • the polyisocyanate component is essentially free of (or even completely free of) any non-linear aliphatic diisocyanates, any aromatic diisocyanates, or both. In still other embodiments, the polyisocyanate component is essentially free of (or even completely free of) any polyisocyanate other than the linear aliphatic diisocyanates described above.
  • the polyol component is the polyol component
  • thermoplastic polyurethane compositions described herein are made using (b) a polyol component that includes one or more polyol s capable of breaking down into one or more non-toxic degradants.
  • the polyol component includes poly(L-lactide) (PLA). In some embodiments, the polyol component includes polyol polglycolide (PGA). In some embodiments, the polyol component includes a polycaprolactone (PCL).
  • PLA poly(L-lactide)
  • PGA polyol polglycolide
  • PCL polycaprolactone
  • the polyol component includes an additional polyol.
  • the additional polyol includes a polyether polyol.
  • the additional polyol is poly(propylene glycol), poly(ethylene glycol), poly(tetramethylene ether glycol), or any combination thereof.
  • an additional polyol may be present and used in combination with the polyols described above to form the polyol component.
  • Polyols suitable for use in the invention may include polyether polyols, polyester polyols, polycarbonate polyols, polysiloxane polyols, polyhydrocarbon polyols and combinations thereof.
  • Suitable polyols which may also be described as hydroxyl terminated intermediates, when present, may include one or more hydroxyl terminated polyesters, one or more hydroxyl terminated polyethers, one or more hydroxyl terminated polycarbonates, one or more hydroxyl terminated polysiloxanes, or mixtures thereof.
  • Suitable hydroxyl terminated polyester intermediates include linear polyesters having a number average molecular weight (Mn) of from about 500 to about 10,000, from about 700 to about 5,000, or from about 700 to about 4,000, and generally have an acid number less than 1.3 or less than 0.5.
  • Mn number average molecular weight
  • the molecular weight is determined by assay of the terminal functional groups and is related to the number average molecular weight.
  • the polyester intermediates may be produced by (1) an esterification reaction of one or more glycols with one or more dicarboxylic acids or anhydrides or (2) by transesterification reaction, i.e., the reaction of one or more glycols with esters of dicarboxylic acids.
  • Suitable polyester intermediates also include various lactones such as polycaprolactone typically made from ⁇ - caprolactone and a Afunctional initiator such as di ethylene glycol.
  • the dicarboxylic acids of the desired polyester can be aliphatic, cycloaliphatic, aromatic, or combinations thereof.
  • Suitable dicarboxylic acids which may be used alone or in mixtures generally have a total of from 4 to 15 carbon atoms and include: succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic, isophthalic, terephthalic, cyclohexane dicarboxylic, and the like.
  • Anhydrides of the above dicarboxylic acids such as phthalic anhydride, tetrahydrophthalic anhydride, or the like, can also be used.
  • Adipic acid is a preferred acid.
  • the glycols which are reacted to form a desirable polyester intermediate can be aliphatic, aromatic, or combinations thereof, including any of the glycols described above in the chain extender section, and have a total of from 2 to 20 or from 2 to 12 carbon atoms.
  • Suitable examples include ethylene glycol, 1,2-propanediol, 1,3 -propanediol, 1,3-butanediol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, 2, 2-dimethyl- 1,3 -propanediol, 1 ,4- cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and mixtures thereof.
  • the polyol component may also include one or more polycaprolactone polyester polyols.
  • the polycaprolactone polyester polyols useful in the technology described herein include polyester diols derived from caprolactone monomers.
  • the polycaprolactone polyester polyols are terminated by primary hydroxyl groups.
  • Suitable polycaprolactone polyester polyols may be made from ⁇ -caprolactone and a bifunctional initiator such as di ethylene glycol, 1,4-butanediol, or any of the other glycols and/or diols listed herein.
  • the polycaprolactone polyester polyols are linear polyester diols derived from caprolactone monomers.
  • Useful examples include CAPATM 2202A, a 2,000 number average molecular weight (Mn) linear polyester diol, and CAPATM 2302A, a 3,000 Mn linear polyester diol, both of which are commercially available from Perstorp Polyols Inc. These materials may also be described as polymers of 2-oxepanone and 1,4- butanediol.
  • the polycaprolactone polyester polyols may be prepared from 2- oxepanone and a diol, where the diol may be 1,4-butanediol, di ethylene glycol, monoethylene glycol, 1 ,6-hexanediol, 2, 2-dimethyl- 1,3 -propanediol, or any combination thereof.
  • the diol used to prepare the polycaprolactone polyester polyol is linear.
  • the polycaprolactone polyester polyol has a number average molecular weight from 500 to 10,000, or from 500 to 3,000, or 600 to 1,000, or 1,000 to 3,000 or from 500, or 600, or from 1,000 or even 2,000 to 4,000 or even 3,000, or even about 2,000.
  • Suitable hydroxyl terminated polyether intermediates include polyether polyols derived from a diol or polyol having a total of from 2 to 15 carbon atoms, in some embodiments an alkyl diol or glycol which is reacted with an ether comprising an alkylene oxide having from 2 to 6 carbon atoms, typically ethylene oxide or propylene oxide or mixtures thereof.
  • hydroxyl functional polyether can be produced by first reacting propylene glycol with propylene oxide followed by subsequent reaction with ethylene oxide. Primary hydroxyl groups resulting from ethylene oxide are more reactive than secondary hydroxyl groups and thus are preferred.
  • Useful commercial polyether polyols include poly(ethylene glycol) comprising ethylene oxide reacted with ethylene glycol, poly(propylene glycol) comprising propylene oxide reacted with propylene glycol, poly(tetramethylene ether glycol) comprising water reacted with tetrahydrofuran which can also be described as polymerized tetrahydrofuran, and which is commonly referred to as PTMEG.
  • the polyether intermediate includes PTMEG.
  • Suitable polyether polyols also include polyamide adducts of an alkylene oxide and can include, for example, ethylenediamine adduct comprising the reaction product of ethylenediamine and propylene oxide, diethylenetriamine adduct comprising the reaction product of diethylenetriamine with propylene oxide, and similar polyamide type polyether polyols.
  • Copolyethers can also be utilized in the described compositions. Typical copolyethers include the reaction product of THF and ethylene oxide or THF and propylene oxide. These are available from BASF as PolyTHF® B, a block copolymer, and PolyTHF® R, a random copolymer.
  • the various polyether intermediates generally have a number average molecular weight (Mn) as determined by assay of the terminal functional groups which is an average molecular weight greater than about 700, such as from about 700 to about 10,000, from about 1,000 to about 5,000, or from about 1 ,000 to about 2,500.
  • the polyether intermediate includes a blend of two or more different molecular weight polyethers, such as a blend of 2,000 Mn and 1,000 Mn PTMEG.
  • Suitable hydroxyl terminated polycarbonates include those prepared by reacting a glycol with a carbonate.
  • U. S. Patent No. 4, 131,73 1 is hereby incorporated by reference for its disclosure of hydroxyl terminated polycarbonates and their preparation.
  • Such polycarbonates are linear and have terminal hydroxyl groups with essential exclusion of other terminal groups.
  • the essential reactants are glycols and carbonates.
  • Suitable glycols are selected from cycloaliphatic and aliphatic diols containing 4 to 40, and or even 4 to 12 carbon atoms, and from polyoxyalkylene glycols containing 2 to 20 alkoxy groups per molecule with each alkoxy group containing 2 to 4 carbon atoms.
  • Suitable diols include aliphatic diols containing 4 to 12 carbon atoms such as 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6- hexanediol, 2,2,4-trimethyl- l,6-hexanediol, 1, 10-decanediol, hydrogenated dilinoleylglycol, hydrogenated dioleylglycol, 3 -methyl -1,5-pentanediol; and cycloaliphatic diols such as 1,3-cyclohexanediol, 1 ,4-dimethylolcyclohexane, 1,4- cyclohexanediol-, 1,3-dimethylolcyclohexane-, l,4-endomethylene-2-hydroxy-5- hydroxymethyl cyclohexane, and polyalkylene glycols.
  • the diols used in the reaction may be a single diol or a mixture of diols depending on the properties desired in the finished product.
  • Polycarbonate intermediates which are hydroxyl terminated are generally those known to the art and in the literature.
  • Suitable carbonates are selected from alkylene carbonates composed of a 5 to 7 member ring. Suitable carbonates for use herein include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-ethylene carbonate, 1,3-pentylene carbonate, 1 ,4-pentylene carbonate, 2,3- pentylene carbonate, and 2,4-pentylene carbonate.
  • dialkylcarbonates can contain 2 to 5 carbon atoms in each alkyl group and specific examples thereof are diethylcarbonate and dipropylcarbonate.
  • Cycloaliphatic carbonates, especially dicycloaliphatic carbonates can contain 4 to 7 carbon atoms in each cyclic structure, and there can be one or two of such structures.
  • the other can be either alkyl or aryl.
  • the other can be alkyl or cycloaliphatic.
  • suitable diarylcarbonates which can contain 6 to 20 carbon atoms in each aryl group, are diphenylcarbonate, ditolylcarbonate, and dinaphthylcarbonate.
  • Suitable polysiloxane polyols include ⁇ - ⁇ -hydroxyl or amine or carboxylic acid or thiol or epoxy terminated polysiloxanes. Examples include poly(dimethysiloxane) terminated with a hydroxyl or amine or carboxylic acid or thiol or epoxy group. In some embodiments, the polysiloxane polyols are hydroxyl terminated polysiloxanes. In some embodiments, the polysiloxane polyols have a number-average molecular weight in the range from 300 to 5,000, or from 400 to 3,000.
  • Polysiloxane polyols may be obtained by the dehydrogenation reaction between a polysiloxane hydride and an aliphatic polyhydric alcohol or polyoxyalkylene alcohol to introduce the alcoholic hydroxy groups onto the polysiloxane backbone.
  • the polysiloxanes may be represented by one or more compounds having the following formula:
  • each Rl and R2 are independently a 1 to 4 carbon atom alkyl group, a benzyl, or a phenyl group; each E is OH or NHR 3 where R 3 is hydrogen, a 1 to 6 carbon atoms alkyl group, or a 5 to 8 carbon atoms cyclo-alkyl group; a and b are each independently an integer from 2 to 8; c is an integer from 3 to 50.
  • R 3 is hydrogen, a 1 to 6 carbon atoms alkyl group, or a 5 to 8 carbon atoms cyclo-alkyl group
  • a and b are each independently an integer from 2 to 8
  • c is an integer from 3 to 50.
  • amino- containing polysiloxanes at least one of the E groups is NHR 3 .
  • the hydroxyl- containing polysiloxanes at least one of the E groups is OH.
  • both R 1 and R 2 are methyl groups.
  • Suitable examples include ⁇ , ⁇ -hydroxypropyl terminated poly(dimethysiloxane) and ⁇ , ⁇ -amino propyl terminated poly(dimethysiloxane), both of which are commercially available materials. Further examples include copolymers of the poly(dimethysiloxane) materials with a poly(alkylene oxide).
  • the polyol component when present, may include poly(ethylene glycol), poly(tetramethylene ether glycol), poly(trimethylene oxide), ethylene oxide capped poly(propylene glycol), poly(butylene adipate), poly(ethylene adipate), poly(hexamethylene adipate), poly(tetramethylene-co-hexamethylene adipate), poly(3-methyl-l,5-pentamethylene adipate), polycaprolactone diol, poly(hexamethylene carbonate) glycol, poly(pentamethylene carbonate) glycol, poly(trimethylene carbonate) glycol, dimer fatty acid based polyester polyols, vegetable oil based polyols, or any combination thereof.
  • dimer fatty acids that may be used to prepare suitable polyester polyols include PriplastTM polyester glycols/polyols commercially available from Croda and Radia® polyester glycols commercially available from Oleon.
  • the polyol component includes a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, or any combination thereof.
  • the polyol component includes a polyether polyol.
  • the polyol component is essentially free of or even completely free of polyester polyols. In some embodiments, the polyol component used to prepare the TPU is substantially free of, or even completely free of polysiloxanes.
  • the polyol component includes ethylene oxide, propylene oxide, butylene oxide, styrene oxide, poly(tetram ethylene ether glycol), poly(propylene glycol), poly(ethylene glycol), copolymers of poly(ethylene glycol) and poly(propylene glycol), epichlorohydrin, and the like, or combinations thereof.
  • the polyol component includes poly(tetramethylene ether glycol).
  • the polyol component is essentially free of (or even completely free of) any polyester polyols, polycarbonate polyols, polysiloxane polyols, or all of the above.
  • Suitable polyamide oligomers including telechelic polyamide polyols, are not overly limited and include low molecular weight polyamide oligomers and telechelic polyamides (including copolymers) that include N-alkylated amide groups in the backbone structure. Telechelic polymers are macromolecules that contain two reactive end groups. Amine terminated polyamide oligomers can be useful as polyols in the disclosed technology.
  • the term polyamide oligomer refers to an oligomer with two or more amide linkages, or sometimes the amount of amide linkages will be specified. A subset of polyamide oligomers are telechelic polyamides.
  • Telechelic polyamides are polyamide oligomers with high percentages, or specified percentages, of two functional groups of a single chemical type, e.g. two terminal amine groups (meaning either primary, secondary, or mixtures), two terminal carboxyl groups, two terminal hydroxyl groups (again meaning primary, secondary, or mixtures), or two terminal isocyanate groups (meaning aliphatic, aromatic, or mixtures). Ranges for the percent difunctional that can meet the definition of telechelic include at least 70, 80, 90 or 95 mole% of the oligomers being difunctional as opposed to higher or lower functionality.
  • Reactive amine terminated telechelic polyamides are telechelic polyamide oligomers where the terminal groups are both amine types, either primary or secondary and mixtures thereof, i.e. excluding tertiary amine groups.
  • the thermoplastic polyurethane is prepared with a polyol component that consists essentially of a polyester polyol.
  • the polyester polyol is polycaprolactone.
  • the TPU compositions described herein are made using: (c) at least one chain extender component including one or more short chain diols capable of breaking down into one or more non-toxic degradants, where the short chain diol is a linear, fully saturated alkylene diol.
  • the disclosed technology further provides the described TPU where the chain extender component includes at least one chain extender of the general formula HO-(CH2)n-X-(CH2)n-OH wherein n is an integer from 2 to 4 and X is oxygen (-0-) or disulfide (-S-S-).
  • the chain extender component includes at least one chain extender of the general formula HO-(CH2)n-X-(CH2)n-OH wherein n is an integer from 2 to 4 and X is oxygen (-0-) or disulfide (-S-S-).
  • the disclosed technology further provides the described TPU where the chain extender component includes dipropylene glycol, di-(2-hydroxyethyl) disulfide, diethylene glycol, or any combination thereof.
  • the disclosed technology further provides the described TPU where the chain extender component further includes one or more additional chain extenders, where these additional chain extenders includes at least one diol chain extender of the general formula HO-(CH2) m -OH wherein m is an integer from 2 to 6.
  • the chain extender component includes dipropylene glycol, di-(2-hydroxyethyl) disulfide, diethylene glycol, or any combination thereof.
  • an additional chain extender may be present and used in combination with the chain extenders described above to form the chain extender component.
  • the TPU compositions are co-extended and are made using an additional chain extender component that includes at least one diol chain extender of the general formula HO-(CH2) x -OH wherein x is an integer from 2 to 6 or even from 4 to 6. In other embodiments, x is the integer 4.
  • Useful additional coextenders include diol chain extenders include relatively small polyhydroxy compounds, for example lower aliphatic or short chain glycols having from 2 to 20, or 2 to 12, or 2 to 10 carbon atoms. Suitable examples include ethylene glycol, di ethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol (BDO), 1,6-hexanediol (HDO), 1,3-butanediol, 1,5-pentanediol, neopentylglycol, 1,4- cyclohexanedimethanol (CHDM), 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane (HEPP), heptanediol, nonanediol, dodecanediol, ethylenediamine, butanediamine, hexamethylenediamine, and hydroxyethyl resorcinol (HER), and the like, as
  • the chain extender includes BDO, HDO, or a combination thereof. In some embodiments, the chain extender includes BDO.
  • Other glycols, such as aromatic glycols could be used, but in some embodiments the TPUs described herein are essentially free of or even completely free of such materials, or a combination thereof.
  • the additional chain extender includes a cyclic chain extender. Suitable examples include CHDM, HEPP, HER, and combinations thereof. In some embodiments, the additional chain extender may include an aromatic cyclic chain extender, for example HEPP, HER, or a combination thereof. In some embodiments, the additional chain extender may include an aliphatic cyclic chain extender, for example CHDM. In some embodiments, the additional chain extender is substantially free of, or even completely free of aromatic chain extenders, for example aromatic cyclic chain extenders. In some embodiments, the additional chain extender is substantially free of, or even completely free of polysiloxanes.
  • compositions described herein are TPU compositions. These TPU are prepared by reacting: a) the polyisocyanate component described above; b) the polyol component described above; and c) the chain extender component described above.
  • the TPU compositions of the invention have a hard segment content of 10 to 50 percent by weight, where the hard segment content is the portion of the TPU derived from the polyisocyanate component and the chain extender component (the hard segment content of the TPU may be calculated by adding the weight percent content of chain extender and polyisocyanate in the TPU and dividing that total by the sum of the weight percent contents of the chain extender, polyisocyanate, and polyol in the TPU).
  • the hard segment content is at least 10, or at least 15, or from 10 to 60, or from 15 to 45 percent by weight.
  • the described compositions include the TPU materials described above and also TPU compositions that include such TPU materials and one or more additional components. These additional components include other polymeric materials that may be blended with the TPU described herein. These additional components also include one or more additives that may be added to the TPU, or blends containing the TPU, to impact the properties of the composition.
  • the TPU described herein may also be blended with one or more other polymers.
  • the polymers with which the TPU described herein may be blended are not overly limited.
  • the described compositions include a two or more of the described TPU materials.
  • the compositions include at least one of the described TPU materials and at least one other polymer, which is not one of the described TPU materials.
  • the described blends will have the same combination of properties described above for the TPU composition.
  • the TPU composition will of course have the described combination of properties, while the blend of the TPU composition with one or more of the other polymeric materials described above may or may not.
  • TPU materials described herein also include more conventional TPU materials such as non- caprolactone polyester-based TPU, polyether-based TPU, or TPU containing both non-caprolactone polyester and polyether groups.
  • suitable materials that may be blended with the TPU materials described herein include polycarbonates, polyolefins, styrenic polymers, acrylic polymers, polyoxymethylene polymers, polyamides, polyphenylene oxides, polyphenylene sulfides, polyvinylchlorides, chlorinated polyvinylchlorides, polylactic acids, or combinations thereof.
  • Polymers for use in the blends described herein include homopolymers and copolymers. Suitable examples include: (i) a polyolefin (PO), such as polyethylene (PE), polypropylene (PP), polybutene, ethylene propylene rubber (EPR), polyoxyethylene (POE), cyclic olefin copolymer (COC), or combinations thereof; (ii) a styrenic, such as polystyrene (PS), acrylonitrile butadiene styrene (ABS), styrene acrylonitrile (SAN), styrene butadiene rubber (SBR or HIPS), polyalphamethylstyrene, styrene maleic anhydride (SMA), styrene-butadiene copolymer (SBC) (such as styrene-butadiene-styrene copolymer (SBS) and styrene-
  • PO
  • these blends include one or more additional polymeric materials selected from groups (i), (iii), (vii), (viii), or some combination thereof. In some embodiments, these blends include one or more additional polymeric materials selected from group (i). In some embodiments, these blends include one or more additional polymeric materials selected from group (iii). In some embodiments, these blends include one or more additional polymeric materials selected from group (vii). In some embodiments, these blends include one or more additional polymeric materials selected from group (viii).
  • Suitable additives include pigments, UV stabilizers, UV absorbers, antioxidants, lubricity agents, heat stabilizers, hydrolysis stabilizers, cross-linking activators, flame retardants, layered silicates, radio opacifiers, such as barium sulfate, tungsten metal, non-oxide bismuth salts, fillers, colorants, reinforcing agents, adhesion mediators, impact strength modifiers, antimicrobials, and any combination thereof.
  • the TPU compositions described herein may also include additional additives, which may be referred to as a stabilizer.
  • the stabilizers may include antioxidants such as phenolics, phosphites, thioesters, and amines, light stabilizers such as hindered amine light stabilizers and benzothiazole UV absorbers, and other process stabilizers and combinations thereof.
  • the preferred stabilizer is Irganox®-1010 from BASF and Naugard®-445 from Chemtura.
  • the stabilizer is used in the amount from about 0.1 weight percent to about 5 weight percent, in another embodiment from about 0.1 weight percent to about 3 weight percent, and in another embodiment from about 0.5 weight percent to about 1.5 weight percent of the TPU composition.
  • additives may be used in the TPU compositions described herein.
  • the additives include colorants, antioxidants (including phenolics, phosphites, thioesters, and/or amines), antiozonants, stabilizers, inert fillers, lubricants, inhibitors, hydrolysis stabilizers, light stabilizers, hindered amines light stabilizers, benzotriazole UV absorber, heat stabilizers, stabilizers to prevent discoloration, dyes, pigments, inorganic and organic fillers, reinforcing agents and combinations thereof.
  • All of the additives described above may be used in an effective amount customary for these substances. These additional additives can be incorporated into th e components of, or into the reaction mixture for, the preparation of the TPU resin, or after making the TPU resin. In another process, all the materials can be mixed with the TPU resin and then melted or they can be incorporated directly into the melt of the TPU resin.
  • thermoplastic polyurethanes of the invention can be prepared by processes which are conventional in the art for the synthesis of polyurethane elastomers such as but not limited to a two-step, batch process or a one-shot technique.
  • a prepolymer intermediate is reacted with an excess amount of diisocyanate, followed by chain extending the same.
  • the components i.e., the diisocyanate(s), the polyol(s), and the chain extenders (s), as well as the catalyst(s) and any other additive(s), if desired, are introduced into a container, mixed, dispensed into trays and allowed to cure.
  • the cured TPU can then be granulated and pelletized.
  • the one-shot procedure is performed in an extruder, e.g., single screw, twin screw, wherein the formative components, introduced individually or as a mixture into the extruder, and reacted at a temperature generally in one embodiment from about 100°C to about 300°C, and in another embodiment from about 150°C to about 250°C, and even from about 150°C to about 240°C.
  • One or more polymerization catalysts may be present during the polymerization reaction.
  • any conventional catalyst can be utilized to react the diisocyanate with the polyol intermediates or the chain extender.
  • suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates and the hydroxy groups of the polyols and chain extenders are the conventional tertiary amines known from the prior art, e.g.
  • organometallic compounds such as titanic esters, iron compounds, e.g. ferric acetyl acetonate, tin compounds, e.g. stannous diacetate, stannous dioctoate, stannous dilaurate, or the dialkyltin salts of aliphatic carboxylic acids, e.g.
  • the amounts usually used of the catalysts are from 0.0001 to 0.1 part by weight per 100 parts by weight of polyhydroxy compound (b).
  • the TPU materials used in the compositions of the disclosed technology are made using l ,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) as catalyst.
  • the catalyst is used at a concentration of 5 mol % of macrodiol.
  • the TPU materials used in the compositions of the disclosed technology are made using stannous octoate as a catalyst.
  • the catalyst is used at a concentration of 8 mol % of macrodiol.
  • the TPU materials described above may be prepared by a process that includes the step of (I) reacting: a) the polyisocyanate component described above, that includes at least one aliphatic diisocyanate; b) the polyol component described above, that includes at least one polyester polyol; and c) the chain extender component described above that includes a substituted 2,5-diketopiperazine, as described above.
  • the process may further include the step of: (II) mixing the TPU composition of step (I) with one or more blend components, including one or more additional TPU materials and/or polymers, including any of those described above.
  • the process may further include the step of: (II) mixing the TPU composition of step (I) with one or more additional additives selected from the group consisting of pigments, UV stabilizers, UV absorbers, antioxidants, lubricity agents, heat stabilizers, hydrolysis stabilizers, cross-linking activators, flame retardants, layered silicates, fillers, colorants, reinforcing agents, adhesion mediators, impact strength modifiers, and antimicrobials.
  • additional additives selected from the group consisting of pigments, UV stabilizers, UV absorbers, antioxidants, lubricity agents, heat stabilizers, hydrolysis stabilizers, cross-linking activators, flame retardants, layered silicates, fillers, colorants, reinforcing agents, adhesion mediators, impact strength modifiers, and antimicrobials.
  • the process may further include the step of: (II) mixing the TPU composition of step (I) with one or more blend components, including one or more additional TPU materials and/or polymers, including any of those described above, and/or the step of: (III) mixing the TPU composition of step (I) with one or more additional additives selected from the group consisting of pigments, UV stabilizers, UV absorbers, antioxidants, lubricity agents, heat stabilizers, hydrolysis stabilizers, cross-linking activators, flame retardants, layered silicates, fillers, colorants, reinforcing agents, adhesion mediators, impact strength modifiers, and antimicrobials.
  • additional additives selected from the group consisting of pigments, UV stabilizers, UV absorbers, antioxidants, lubricity agents, heat stabilizers, hydrolysis stabilizers, cross-linking activators, flame retardants, layered silicates, fillers, colorants, reinforcing agents, adhesion mediators, impact strength modifiers, and antimicrobials.
  • the process may further include in step I of including a co-extender component that includes at least one diol chain extender of the general formula HO- (CH2)x-OH wherein x is an integer from 2 to 6.
  • a co-extender component that includes at least one diol chain extender of the general formula HO- (CH2)x-OH wherein x is an integer from 2 to 6.
  • the invention further provides an article made with the TPU materials and/or compositions described herein.
  • examples include but are not limited to medical applications, as well as used in, personal care applications, pharmaceutical applications, health care product applications, or any other number of applications.
  • these articles are prepared by extruding, injection molding, or any combination thereof.
  • the TPU materials and/or compositions described herein may be used as medical devices, such as implants or coatings on implants, where the TPU delivers one or more therapeutic agents at the site of implantation.
  • therapeutic agents and “drugs” are used herein interchangeably to mean any material that has a therapeutic effect at an implantation site.
  • the device of the present invention is said to "deliver” or “elute” therapeutic agent— these terms are used synonymously and generally to refer to any mechanism by which the therapeutic agent comes into contact with tissue.
  • the therapeutic agent(s) may be delivered in a number of ways.
  • the therapeutic agent(s) are embedded within a coating that is made using the TPU materials and/or compositions described herein that adheres to one or more surfaces of an implant or other medical article or medical device.
  • the coating is made from one or more of the TPU materials and/or compositions described herein admixed with the therapeutic agent(s) such that the agent is eluted from the polymer over time, or is released from the coating as it degrades in-vivo.
  • one or more therapeutic agents are applied in discrete areas on one or more individual section or surfaces of the implant or other medical article or medical device.
  • TPU materials and/or compositions described herein are meant to biodegrade and/or bioabsorb slowly enough that the materials may have physical properties suitable for and sufficiently long lasting enough to be used in the construction of medical devices. Further, they are meant to biodegrade and/or bioabsorb quickly enough that the materials are suitable for use in the construction of medical devices meant to break down in the body. Still further, they are meant to break down in such a way that there are no toxic byproducts caused by their biodegrading and/or bioabsorbing.
  • the compositions described herein have been found to meet this unique set of conditions.
  • the TPU materials and/or compositions described herein retain at least 30% of their initial ultimate tensile strength after 1 week of exposure to the degradation protocol described herein. In other embodiments, the compositions retain at least 50% of their initial ultimate tensile strength after 1 week. In some of these embodiments the materials also lose 100% of their initial ultimate tensile strength after 5 weeks, or even 4 weeks, of exposure to the degradation protocol described herein. In other embodiments, the materials also lose at least 80% of their initial ultimate tensile strength after 3 weeks of exposure to the degradation protocol described herein. This combination of tensile strength retention for so long and then so much tensile strength loss by such a point in time, which are indicators of the controlled degradation rate of the material, can be important for medical device application where these materials may be used.
  • each chemical component described is presented exclusive of any solvent which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated.
  • each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
  • the reaction is catalyzed by using stannous octoate (8 mol % of macrodiol) as catalyst.
  • stannous octoate 8 mol % of macrodiol
  • the reaction exotherms and levels off at 80°C to 90°C.
  • the reaction mixture is then allowed to cool to ⁇ 60°C and the chain extender is added.
  • the reaction is again allowed to exotherm to ⁇ 80°C and then the contents are poured in a pan. The pan is then put in curing oven to cure and complete the reaction at 125°C for 5 hours.
  • the 1-pot reaction is conducted by adding calculated equivalent amounts of the macrodiol, chain extender and the isocyanate in the reaction vessel at 60°C while mixing using overhead stirrer and then adding catalyst. Once the exotherm is complete, the contents of the vessel are transferred in to a pan and cured similar to the 2-step procedure.
  • the hard segment of the polyurethanes is calculated according to the following formula:
  • Inventive Example 1 and Inventive Example 2 contain hydrolysable soft segments and oxidizable hard segments. Comparative Example 3 contains neither oxidizable nor hydrolysable moieties.
  • Each sample in Table 1 is tested to verify its mechanical properties (strength, modulus and elongation as measured by ASTM D412) and degradation rates where degradation was measured using the following protocol: (1) each example is extruded into a tape and small (ASTM D1708) dogbones are punched out; three dogbones per sample were tested at each time point. (2) A degradation solution is prepared by making a solution of 20% H2O2 (hydrogen peroxide) and 0.1M Cobalt Chloride (oxidative solution) meant to simulate an in-vivo environment. (3) The dogbones of each sample are immersed in the degradation solution and held at 50 °C.
  • dogbones are removed once a week for up to ten weeks and tested for mechanical properties (strength, modulus and elongation as measured by ASTM D412).
  • the degradation solution is changed two times every week to maintain the concentration of the free radicals in the solution.
  • UTS is ultimate tensile strength and is tested by ASTM Dl 708 and reported in MP a.
  • ELG is elongation and is tested by ASTM D 1708 and reported as a percent.
  • Mw is weight average molecular weight as is measured by GPC using polystyrene calibration standards.
  • %Loss ELG is the percent the elongation has dropped compared to the original result at time zero.
  • the Inventive Example 1 and Inventive Example 2 have hydrolysable soft segment and so the polymer breaks down faster in presence of water which is further enhanced by the presence of oxidizable hard segments which break down in the presence of peroxides. So, there is a dual degradation mechanism responsible for the degradation of the TPUs of the invention.
  • BDI is 1, 4-butane diisocyanate
  • LDI Lysine diisocyanate
  • HDI 1, 6-hexane diisocyanate
  • PLA poly(L-lactide)
  • PGA polglycolide
  • PCL polycaprolactone
  • DPG dirpopylene glycol
  • DHS di-(2-hydroxyethyl) disulfide
  • DEG diethylene glycol.
  • BDI is 1, 4-butane diisocyanate
  • LDI Lysine diisocyanate
  • HDI 1, 6-hexane diisocyanate
  • PLA poly(L-lactide)
  • PGA polglycolide
  • PCL polycaprolactone
  • DPG dirpopylene glycol
  • DHS di-(2-hydroxyethyl) disulfide
  • DEG diethylene glycol.
  • BDI 1,4-butane diisocyanate
  • LDI Lysine diisocyanate
  • HDI 1,6-hexane diisocyanate
  • PLA poly(L-lactide)
  • PGA polglycolide
  • PCL polycaprolactone
  • DPG dirpopylene glycol
  • DHS di-(2-hydroxyethyl) disulfide
  • DEG diethylene glycol.
  • BDI 1,4-butane diisocyanate
  • LDI Lysine diisocyanate
  • HDI 1,6-hexane diisocyanate
  • PLA poly(L-lactide)
  • PGA polglycolide
  • PCL polycaprolactone
  • dirpopylene glycol DHS is di-(2-hydroxyethyl) disulfide
  • DEG diethylene
  • BDI is 1, 4-butane diisocyanate
  • LDI Lysine diisocyanate
  • HDI 1, 6-hexane diisocyanate
  • PLA poly(L-lactide)
  • PGA polglycolide
  • PCL polycaprolactone
  • DPG dirpopylene glycol
  • DHS di-(2-hydroxyethyl) disulfide
  • DEG diethylene glycol
  • weight average and number weight average molecular weights of the materials described are obtained by integrating the area under the peak corresponding to the material of interest, excluding peaks associated with diluents, impurities, uncoupled star polymer chains and other additives.
  • the transitional term "comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
  • the term also encompass, as alternative embodiments, the phrases “consisting essentially of and “consisting of,” where “consisting of excludes any element or step not specified and “consisting essentially of permits the inclusion of additional un-recited elements or steps that do not materially affect the basic and novel characteristics of the composition or method under consideration. That is “consisting essentially of permits the inclusion of substances that do not materially affect the basic and novel characteristics of the composition under consideration.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des compositions de polyuréthane thermoplastique (PUT) qui comportent des segments durs et mous biodégradables et/ou bioabsorbables. Le segment dur en PUT est formé à partir d'un ou de plusieurs polyisocyanates capables de décomposer en un ou plusieurs produits de dégradation non toxiques et un ou plusieurs diols à chaîne courte capables de se décomposer en un ou plusieurs produits de dégradation non toxiques. Le segment mou en PUT est formé à partir d'un ou de plusieurs polyols capables de se décomposer en un ou plusieurs produits de dégradation non toxiques. Le PUT obtenu présente une vitesse de dégradation contrôlable et peut être formulé pour avoir de bonnes propriétés physiques, ce qui le rend idéal pour une utilisation dans des articles et des dispositifs médicaux.
PCT/US2018/015842 2017-01-30 2018-01-30 Polyuréthannes thermoplastiques biodégradables et/ou bioabsorbables WO2018140912A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762451910P 2017-01-30 2017-01-30
US62/451,910 2017-01-30

Publications (1)

Publication Number Publication Date
WO2018140912A1 true WO2018140912A1 (fr) 2018-08-02

Family

ID=61193133

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2018/015842 WO2018140912A1 (fr) 2017-01-30 2018-01-30 Polyuréthannes thermoplastiques biodégradables et/ou bioabsorbables

Country Status (1)

Country Link
WO (1) WO2018140912A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109929088A (zh) * 2019-03-20 2019-06-25 嘉兴学院 一种双硫键聚氨酯及其制备方法和应用
CN115260433A (zh) * 2022-06-24 2022-11-01 中国科学院宁波材料技术与工程研究所 生物基高阻尼热塑性聚氨酯弹性体材料及其制法和应用
CN115572366A (zh) * 2022-09-06 2023-01-06 中国科学院宁波材料技术与工程研究所 耐压温敏型热塑性聚乳酸基聚氨酯弹性体及其制法与应用
CN116554430A (zh) * 2023-05-11 2023-08-08 青岛格林沃德新材料科技有限公司 一种含动态二硫键的高性能聚氨酯阻尼材料及其制备方法
WO2024261718A1 (fr) * 2023-06-22 2024-12-26 G.P.S. Tech S.R.L. Utilisation de polyols de polyester spécifiques en tant que phase molle pour la préparation d'adhésifs polyuréthane amovibles et utilisation desdits adhésifs

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3875118A (en) * 1972-10-03 1975-04-01 Bayer Ag Thermoplastic polyurethanes and a two-stage process for their preparation
US4131731A (en) 1976-11-08 1978-12-26 Beatrice Foods Company Process for preparing polycarbonates
WO2005089778A1 (fr) * 2004-03-24 2005-09-29 Commonwealth Scientific And Industrial Research Organisation Polyurethanne et urees de polyurethanne biodegradables
WO2017116798A1 (fr) * 2015-12-31 2017-07-06 Lubrizol Advanced Materials, Inc. Composition de polyuréthane thermoplastique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3875118A (en) * 1972-10-03 1975-04-01 Bayer Ag Thermoplastic polyurethanes and a two-stage process for their preparation
US4131731A (en) 1976-11-08 1978-12-26 Beatrice Foods Company Process for preparing polycarbonates
WO2005089778A1 (fr) * 2004-03-24 2005-09-29 Commonwealth Scientific And Industrial Research Organisation Polyurethanne et urees de polyurethanne biodegradables
WO2017116798A1 (fr) * 2015-12-31 2017-07-06 Lubrizol Advanced Materials, Inc. Composition de polyuréthane thermoplastique

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Macromolecules, an Introduction to star polymer Science", 1979, ACADEMIC PRESS, pages: 296 - 312
P.J. FLORY: "Principles of star polymer Chemistry", CORNELL UNIVERSITY PRESS, pages: 266 - 315
TATAI ET AL: "Thermoplastic biodegradable polyurethanes: The effect of chain extender structure on properties and in-vitro degradation", BIOMATERIALS, ELSEVIER SCIENCE PUBLISHERS BV., BARKING, GB, vol. 28, no. 36, 22 October 2007 (2007-10-22), pages 5407 - 5417, XP022308839, ISSN: 0142-9612, DOI: 10.1016/J.BIOMATERIALS.2007.08.035 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109929088A (zh) * 2019-03-20 2019-06-25 嘉兴学院 一种双硫键聚氨酯及其制备方法和应用
CN109929088B (zh) * 2019-03-20 2021-07-23 嘉兴学院 一种双硫键聚氨酯及其制备方法和应用
CN115260433A (zh) * 2022-06-24 2022-11-01 中国科学院宁波材料技术与工程研究所 生物基高阻尼热塑性聚氨酯弹性体材料及其制法和应用
CN115572366A (zh) * 2022-09-06 2023-01-06 中国科学院宁波材料技术与工程研究所 耐压温敏型热塑性聚乳酸基聚氨酯弹性体及其制法与应用
CN115572366B (zh) * 2022-09-06 2024-03-29 中国科学院宁波材料技术与工程研究所 耐压温敏型热塑性聚乳酸基聚氨酯弹性体及其制法与应用
CN116554430A (zh) * 2023-05-11 2023-08-08 青岛格林沃德新材料科技有限公司 一种含动态二硫键的高性能聚氨酯阻尼材料及其制备方法
CN116554430B (zh) * 2023-05-11 2024-04-19 青岛格林沃德新材料科技有限公司 一种含动态二硫键的高性能聚氨酯阻尼材料及其制备方法
WO2024261718A1 (fr) * 2023-06-22 2024-12-26 G.P.S. Tech S.R.L. Utilisation de polyols de polyester spécifiques en tant que phase molle pour la préparation d'adhésifs polyuréthane amovibles et utilisation desdits adhésifs

Similar Documents

Publication Publication Date Title
EP3201249B1 (fr) Polyuréthanes thermoplastiques résilients non ramollissants
US11525028B2 (en) Biodegradable and/or bioabsorbable thermoplastic polyurethanes
WO2018140912A1 (fr) Polyuréthannes thermoplastiques biodégradables et/ou bioabsorbables
AU2018212997B2 (en) Antimicrobial thermoplastic polyurethanes
US11685806B2 (en) Melt processable thermoplastic polyurethane-urea elastomers
EP2914641B1 (fr) Mélanges de polymères bioabsorbables

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18704758

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18704758

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载