Patent Grant
10835638
The present disclosure relates to block copolymers. More specifically, the disclosure relates to cross-linked polyisobutylene-based polyurethanes, methods for making cross-linked polyisobutylene-based polyurethanes, and medical devices containing cross-linked polyisobutylene-based polyurethanes.
Polymeric materials are widely used in the field of implantable medical devices. For example, polymeric materials such as silicone rubber, polyurethane, and fluoropolymers are used as coating and/or insulating materials for medical leads, stents, and other devices. Polymeric materials may also be used for leaflets in replacement heart valves.
Block copolymers are polymeric materials made of alternating sections of polymerized monomers. Polyisobutylene-polyurethane block copolymers are polymeric materials that can have many desirable physical and mechanical properties, including thermal stability, chemical resistance, biocompatibility, and gas impermeability, among others.
Example 1 is a block copolymer including a plurality of polymeric chains and a plurality of cross-linking compound residues linking together the plurality of polymeric chains. The plurality of polymeric chains forms a plurality of hard domains and a plurality of soft domains. Each polymeric chain includes a plurality of soft segments and a plurality of hard segments. The plurality of soft segments includes a polyisobutylene diol or diamine residue. The plurality of soft segments forms the plurality of soft domains. The plurality of hard segments including a diisocyanate residue. The plurality of hard segments forms the plurality of hard domains. The cross-linking compound residues link together the hard segments of the plurality of polymeric chains.
Example 2 is the block copolymer of Example 1, wherein the cross-linking compound residues are residues of a polyfunctional benzophenone.
Example 3 is the block copolymer of Example 2, wherein the polyfunctional benzophenone has a benzophenone functionality greater than 2 and less than 7.
Example 4 is the block copolymer of any of Examples 1-3, wherein the copolymer includes of a first portion and a second portion, the plurality of cross-linking compound residues disposed in the hard domains of the first portion, the second portion free of the plurality of cross-linking compound residues.
Example 5 is the block copolymer of Example 4, wherein the copolymer further includes a cross-linking compound, wherein the cross-linking compound is a precursor of the plurality of cross-linking compound residues, the cross-linking compound disposed in the hard domains of the second portion.
Example 6 is the block copolymer of any of Examples 1-5, wherein the diisocyanate residue includes 4,4′-methylene diphenyl diisocyanate residue.
Example 7 is the block copolymer of any of Examples 1-6, wherein the hard segments further include a chain extender residue.
Example 8 is the block copolymer of Example 7, wherein the chain extender residue is 1,4-butanediol residue.
Example 9 is the block copolymer of any of Examples 1-8, wherein the polyisobutylene diol or diamine residue is 5-tert-butyl-1,3-bis(1-methoxy-1-methylethyl)benzene.
Example 10 is the block copolymer of any of Examples 1-9, wherein the plurality of cross-linking compound residues link together at least a portion of the hard segments of the plurality of polymeric chains by covalent bonds.
Example 11 is a medical device including the block copolymer of any of Examples 1-10.
Example 12 is the medical device of Example 11, wherein the medical device is a heart valve.
Example 13 is a method of making a block copolymer. The method includes heating a mixture including soft segment components and hard segment components to an elevated temperature. The soft segment components include at least one polyisobutylene diol or diamine. The hard segment components include at least one diisocyanate. The method further includes maintaining the heated mixture for a time sufficient for the soft segment components and the hard segment components to form of a plurality of polymeric chains including soft segments and hard segments. The polymeric chains form a polymer matrix of soft domains including soft segments of the polymeric chains, and hard domains including hard segments of the polymeric chains. The method further includes adding a cross-linking compound to the polymer matrix, the cross-linking compound concentrating in the hard domains. The method further includes exposing at least a portion of the polymer matrix to radiation to activate the cross-linking compound. The activated cross-linking compound bonds to the polymeric chains in the exposed portion. The bonding is concentrated in the hard domains to form the block copolymer.
Example 14 is the method of Example 13, wherein the cross-linking compound is a polyfunctional benzophenone.
Example 15 is the method of either of Examples 13 or 14, wherein the entire polymer matrix is exposed to the radiation.
Example 16 is a block copolymer including a plurality of polymeric chains and a plurality of cross-linking compound residues linking together the plurality of polymeric chains. The plurality of polymeric chains forms a plurality of hard domains and a plurality of soft domains. Each polymeric chain includes a plurality of soft segments and a plurality of hard segments. The plurality of soft segments includes a polyisobutylene diol or diamine residue. The plurality of soft segments forms the plurality of soft domains. The plurality of hard segments including a diisocyanate residue. The plurality of hard segments forms the plurality of hard domains. The cross-linking compound residues link together the hard segments of the plurality of polymeric chains by covalent bonds.
Example 17 is the block copolymer of Example 16, wherein the cross-linking compound residues are residues of a polyfunctional benzophenone.
Example 18 is the block copolymer of Example 17, wherein the polyfunctional benzophenone has a benzophenone functionality greater than 2 and less than 7.
Example 19 is the block copolymer of any of Examples 16-18, wherein the copolymer includes of a first portion and a second portion, the plurality of cross-linking compound residues disposed in the hard domains of the first portion, the second portion free of the plurality of cross-linking compound residues.
Example 20 is the block copolymer of Example 19, wherein the copolymer further includes a cross-linking compound, wherein the cross-linking compound is a precursor of the plurality of cross-linking compound residues, the cross-linking compound disposed in the hard domains of the second portion.
Example 21 is the block copolymer of any of Examples 16-20, wherein the diisocyanate residue includes 4,4′-methylene diphenyl diisocyanate residue.
Example 22 is the block copolymer of Example 16, wherein the hard segments further include a chain extender residue.
Example 23 is the block copolymer of Example 22, wherein the chain extender residue is 1,4-butanediol residue.
Example 24 is a medical device including a block copolymer. The block copolymer includes a plurality of polymeric chains and a plurality of cross-linking compound residues linking together the plurality of polymeric chains. The plurality of polymeric chains forms a plurality of hard domains and a plurality of soft domains. Each polymeric chain includes a plurality of soft segments and a plurality of hard segments. The plurality of soft segments includes a polyisobutylene diol or diamine residue. The plurality of soft segments forms the plurality of soft domains. The plurality of hard segments including a diisocyanate residue. The plurality of hard segments forms the plurality of hard domains. The cross-linking compound residues link together the hard segments of the plurality of polymeric chains by covalent bonds.
Example 25 is the medical device of Example 24, wherein the cross-linking compound residues are residues of a polyfunctional benzophenone.
Example 26 is the medical device of Example 25, wherein the polyfunctional benzophenone has a benzophenone functionality greater than 2 and less than 7.
Example 27 is the medical device of any of Examples 24-26, wherein the copolymer includes of a first portion and a second portion, the plurality of cross-linking compound residues disposed in the hard domains of the first portion, the second portion free of the plurality of cross-linking compound residues.
Example 28 is the medical device of Example 27, wherein the copolymer further includes a cross-linking compound, wherein the cross-linking compound is a precursor of the plurality of cross-linking compound residues, the cross-linking compound disposed in the hard domains of the second portion.
Example 29 is the medical device of any of Examples 24-28, wherein the diisocyanate residue includes 4,4′-methylene diphenyl diisocyanate residue.
Example 30 is the medical device of any of Examples 24-29, wherein the hard segments further include a chain extender residue.
Example 31 is the medical device of Example 30, wherein the chain extender residue is 1,4-butanediol residue.
Example 32 is the medical device of any of Examples 24-31, wherein the medical device is a heart valve.
Example 33 is a method of making a block copolymer. The method includes heating a mixture including soft segment components and hard segment components to an elevated temperature. The soft segment components include at least one polyisobutylene diol or diamine. The hard segment components include at least one diisocyanate. The method further includes maintaining the heated mixture for a time sufficient for the soft segment components and the hard segment components to form of a plurality of polymeric chains including soft segments and hard segments. The polymeric chains form a polymer matrix of soft domains including soft segments of the polymeric chains, and hard domains including hard segments of the polymeric chains. The method further includes adding a cross-linking compound to the polymer matrix, the cross-linking compound concentrating in the hard domains. The method further includes exposing at least a portion of the polymer matrix to radiation to activate the cross-linking compound. The activated cross-linking compound covalently bonds to the polymeric chains in the exposed portion. The bonding is concentrated in the hard domains to form the block copolymer.
Example 34 is the method of Example 33, wherein the cross-linking compound is a polyfunctional benzophenone.
Example 35 is the method of either of Examples 33 or 34, wherein the entire polymer matrix is exposed to the radiation.
While multiple examples are disclosed, still other examples in accordance with this disclosure will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive.
While this disclosure is amenable to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and are described in detail below. The intention, however, is not to limit the disclosure to the particular embodiments described. On the contrary, this disclosure is intended to cover all modifications, equivalents, and alternatives falling within the scope of the disclosure as defined by the appended claims.
Medical devices can include synthetic polymers which substitute for natural tissues. For example, in some replacement heart valves, a synthetic polymer can substitute for the natural tissue forming the valve leaflets. The natural tissue includes collagen and elastin. Without wishing to be bound by any theory, it is believed that the combination of collagen and elastin permits the valve leaflets to move easily under low stress and then stiffen significantly when higher stresses are reached. This non-linear “strain stiffening” provides for a natural heart valve that is soft, efficient, and able to move with little stress at low stress levels, but stiffens at higher stress levels to reduce creep induced damage.
Polyisobutylene polyurethane (PIB-PUR) block copolymers are durable, biocompatible polymers suitable for a wide variety of medical applications. The PIB-PUR block copolymers are made of polymeric chains including hard segments and soft segments. The components making up the hard segments are more polar than the components making up the soft segments. As the PIB-PUR block copolymers are formed, there is a natural phase separation between the hard segment components and the soft segment components driven by associated hydrogen bonding and intermolecular forces arising from the polarity of the hard segment components. This self-organizing behavior can provide physical crosslinking of the bulk material, which may provide some of the advantageous properties of the PIB-PUR block copolymer.
In thermoplastic PIB-PUR block copolymers, hydrogen bonding and intermolecular forces act to organize the polymeric chains into a polymer matrix such that the hard segment components of adjacent polymeric chains are bonded together to form hard domains, leaving the soft segment components to form soft domains. The strength of the hydrogen bonding and intermolecular forces bonding the polymeric chains together in the hard domains is relatively weak, permitting the polymeric chains to separate from each other with the application of heat or stress, and then reconnect when the heat or stress is removed. Valve leaflets formed of thermoplastic PIB-PUR block copolymers can be soft and can efficiently move under stress due to the weak bonding. However, because of the weak bonding, thermoplastic PIB-PUR block copolymers can creep under stress as the polymer matrix is distorted by the breaking and reforming of the weak bonds, resulting in creep-induced damage to the leaflets. In some cases, the creep-induced damage can deform the leaflets enough to cause the valves to leak.
In thermoset PIB-PUR block copolymers, the polymeric chains are cross-linked to each other by covalent bonds. The covalent bonds can form all along the polymeric chains in the soft domains as well as the hard domains, resulting in a stiff polymer matrix. The strength of the covalent bonds is about three orders of magnitude greater than the strength of the bonds formed by hydrogen bonding and intermolecular forces. As a result, valve leaflets formed of thermoset PIB-PUR block copolymers my not creep under stress. However, thermoset PIB-PUR block copolymers are stiff and may not move easily under stress, so valve leaflets made formed of thermoset PIB-PUR block copolymers may be less efficient by requiring more energy to function. Thus, neither thermoplastic PIB-PUR block copolymers nor thermoset PIB-PUR block copolymers exhibit the desired non-linear strain stiffening found in some natural tissues, such as heart valve leaflets.
Embodiments of the present disclosure include PIB-PUR block copolymers that are soft and easily moved under low stresses, and stiffen significantly when higher stresses are reached. Such PIB-PUR block copolymers can exhibit the non-linear strain stiffening found in some natural tissues and can be used, for example, in leaflets in replacement heart valves to provide a more efficient and durable heart valve compared to other synthetic polymers.
In use, the heart valve 10 can have a closed position, as shown in
Although the embodiment describe above includes the PIB-PUR block copolymer according to embodiments described below incorporated into the heart valve 10, it is understood that the PIB-PUR block copolymer according to embodiments described below can be incorporated into any of a variety of medical devices which can be implanted or inserted into the body of a patient and which undergo significant amounts of dynamic stress. Example medical devices may include, without limitation: electrical leads and cables for rhythm management devices, artificial pericardium, aortic cuffs, and catheters, such as, for example, biliary drainage catheters.
The soft segments 28 can be formed from a polyisobutylene diol or diamine, and thus include a residue of the polyisobutylene diol or diamine. For example, the polyisobutylene diol may be a telechelic polyisobutylene diol formed from by carbocationic polymerization beginning with a difunctional initiator compound, such as 5-tert-butyl-1,3-bis(1-methoxy-1-methylethyl)benzene (hindered dicumyl ether). The resulting compound may be a polyisobutylene diol according to Formula I:
Optionally, in some embodiments, the soft segments may additionally be formed from one or more polyether diols, and thus include a residue of the one or more polyether diols. Suitable optional polyether diols may include polytetramethylene oxide diol (PTMO diol), polyhexametheylene oxide diol (PHMO diol), polyoctamethylene oxide diol, and polydecamethylene oxide diol.
The hard segments 30 can be formed from polyfunctional isocyanates, such as diisocyanates, including both aliphatic and aromatic diisocyanates, and thus include a diisocyanate residue. Diisocyanates for use in forming the PIB-PUR block copolymer matrix 20 can include aromatic and non-aromatic (e.g., aliphatic) diisocyanates. Aromatic diisocyanates may be selected from suitable members of the following, among others: 4,4′-methylenediphenyl diisocyanate (MDI), 2,4′-methylenediphenyl diisocyanate (2,4-MDI), 2,4- and/or 2,6-toluene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), para-phenylene diisocyanate, 3,3′-tolidene-4,4′-diisocyanate and 3,3′-dimethyl-diphenylmethane-4,4′-diisocyanate. Non-aromatic diisocyanates may be selected from suitable members of the following, among others: 1,6-hexamethylene diisocyanate (HDI), 4,4′-dicyclohexylmethane diisocyanate (H12-MDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate or IPDI), cyclohexyl diisocyanate, and 2,2,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI).
In some embodiments, the hard segments 30 may further include one or more optional chain extender residues. The chain extenders can increase the hard segment length, which can in turn results in a copolymer with a higher tensile modulus, lower elongation at break and/or increased strength. Chain extenders can be formed from aliphatic or aromatic diols, in which case a urethane bond is formed upon reaction with an isocyanate group. Chain extenders may be selected from suitable members of the following, among others: 1,4 cyclohexanedimethanol, alpha,omega-alkane diols such as ethylene glycol (1,2-ethane diol), 1,4-butanediol (BDO), and 1,6-hexanediol.
A PIB-PUR block copolymer having the PIB-PUR block copolymer matrix 36 shown in
The plurality of hard domains 24 may include amorphous portions and crystalline portions. Until activated, the cross-linking compound 34 can act as a plasticizer in the hard domains 24 by interfering with the formation of the crystalline portions. However, due to its polarity, the cross-linking compound 34 may not drive the hard segments 30 apart. Once activated, the cross-linking compound 34 replaces the impermanent hydrogen bonds in the plurality of hard domains 24 with permanent covalent bonds. Thus, in some embodiments, the cross-linking compound 34 can act as a cross-linkable plasticizer.
In the embodiments described above in reference to
In some embodiments, the cross-linking compound 34 is a polyfunctional benzophenone. The polyfunctional benzophenones are aromatic rich and quite polar due to the benzophonones and the coordinating core of molecules. In some embodiments, the polyfunctional benzophenone can be a dibenzophenone with a functionality of 2, for example, 4,4″-oxy-di-benzophenone (CAS: 6966-89-8). In some other embodiments, the polyfunctional benzophenone can have a functionality greater than 2 and less than 7 to provide for greater cross-linking.
Prior art initiator systems can have separate cross-linking initiators that generate free radicals which then must propagate to the cross-linking agents for successful cross-linking. Such systems can require maintaining an inert atmosphere to prevent oxygen from reacting with the free radicals before they get to the cross-linking agent. In embodiments in which the cross-linking compound 34 is a polyfunctional benzophenone, the cross-linking compound 34 acts as both cross-linking initiator and cross-linking agent. For such embodiments, there is no need to maintain an inert atmosphere because there is no need for a free radical produced by the initiator to propagate because the activated cross-linking compound 34 bonds directly to the polymeric chain 22.
The PIB-PUR block copolymer matrix 20 can be made by heating a mixture including soft segment components and hard segment components to an elevated temperature. An elevated temperature is any temperature above room temperature, such as 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., or 100° C., or any temperature between any of the preceding temperatures. The soft segment components can include at least one polyisobutylene diol or diamine, such as the polyisobutylene diol according to Formula I above. The hard segment components can include at least one diisocyanate, such as 4,4′-methylene diphenyl diisocyanate. In some embodiments, the hard segment components can further include a chain extender, for example, 1,4-butanediol. The heated mixture is maintained for a time sufficient for the soft segment components and the hard segment components to form of the plurality of polymeric chains 22 including the soft segments 28 and the hard segments 30, the polymeric chains self-organizing to form the PIB-PUR block copolymer matrix 20 of the soft domains 26 including primarily the soft segments 28 of the polymeric chains 22 and the hard domains 24 including primarily hard segments 30 of the polymeric chains 22, as shown in
In some embodiments, a catalyst can be added to the mixture to increase the reaction rate and significantly reduce the time for substantial completion of the reaction. Tin(II) 2-ethylhexanoate and 2,6-dimethylpyridine are examples of such a catalyst.
Once the PIB-PUR block copolymer matrix 20 has formed, the cross-linking compound 34 can be added to the PIB-PUR block copolymer matrix 20. The cross-linking compound 34 can be, for example, any of the polyfunctional benzophenones described above. The cross-linking compound 34 has an affinity for the hard segments 30 due to its polarity and will diffuse through the polymeric chains 22 and concentrate in the hard domains 24 to form the PIB-PUR block copolymer matrix 32 as shown in
In some embodiments, at least the first portion 42 can be exposed to radiation to activate the cross-linking compound 34, the cross-linking compound 34 bonding to the polymeric chains 22 in the first portion 42 to form the PIB-PUR block copolymer matrix 40 as shown in
In some embodiments, exposing the PIB-PUR block copolymer matrix 32, or the first portion 42 of the PIB-PUR block copolymer matrix 40, to radiation to activate the cross-linking compound 34 can include exposure to actinic photons, electron beams, or infrared sources. In some embodiments, actinic photons can be from an ultraviolet light source, which may, for example, be partially masked if only the first portion 42 is to be exposed. In some other embodiments, the infrared source can be from an infrared laser.
Various modifications and additions can be made to the embodiments discussed without departing from the scope of this disclosure. For example, while the embodiments described above refer to particular features, the scope of this disclosure also includes embodiments having different combinations of features and embodiments that do not include all of the described features. Accordingly, the scope of this disclosure is intended to embrace all such alternatives, modifications, and variations as fall within the scope of the claims, together with all equivalents thereof.
In this Example, the manufacture of a photocrosslinked polyisobutylene-polyether-polyurethane block copolymer is demonstrated. 3 g of a polyisobutylene-polyether-polyurethane block copolymer was dissolved in 27 g of tetrahydrofuran (THF). The polyisobutylene-polyether-polyurethane block copolymer consisted of 55 wt. % polyisobutylene diol residue, 10 wt. % polytetramethylene oxide diol residue, and 35 wt. % of a stoichiometric ratio of 4,4′-methylenediphenyl diisocyanate and 1,4-butanediol. A 10 g aliquot of the 10 wt. % solution of polyisobutylene-polyether-polyurethane block copolymer was treated with a 1 g aliquot of an isopropanol solution of 0.1 wt. % 1,3,5-tris[3-(4-benzoylphenoxy)-2-hydroxypropyk]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and 0.9 wt. % 1-hydroxycyclohexyl phenyl ketone. The resulting solution was cast as a film in two aluminum pans, and placed in an oven under nitrogen gas flow at 50° C. until dry. One of the films was then treated using a Dymax UV curing chamber for 4 minutes, allowed to stand for 1 hour, flipped over, and treated on the other side in a similar fashion for 1 hour to cure, or crosslink the polyisobutylene-polyether-polyurethane block copolymer. The other film received no UV treatment.
The untreated film was submerged in THF and dissolved. The UV treated film was also submerged in THF, but showed no sign of dissolution, thus indicating that the film had been successfully covalently crosslinked and confirming that that the UV initiated crosslinking had worked as intended.
This application claims priority to Provisional Application No. 62/547,059, filed Aug. 17, 2017, which is herein incorporated by reference in its entirety.
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| Number | Date | Country | |
|---|---|---|---|
| 20190054204 A1 | Feb 2019 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62547059 | Aug 2017 | US |
