Polymer systems suitable for blood-contacting surfaces of a biomedical device, and methods for forming

Claim 2

A modified, solid polymer formed of a base polymer and a solid thermoplastic segmented block copolymer additive blended with said base polymer, said additive comprising an essentially linear segmented copolymer chain; said additive characterized by a γ c less than said base polymer and said segmented copolymer chain characterized by the presence of at least one polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and a nonpolar soft block having a glass transition temperature below 37° C. said additive further comprising a second essentially linear polymer chain chemically bonded to said segmented copolymer chain, said second polymer chain being selected from a polar homopolymer or a second segmented copolymer, said second segmented copolymer or polar homopolymer characterized by the presence of at least one second polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., said polar hard segments independently selected from the group consisting of a polyurethane and a polyurethaneurea, and said second segmented copolymer further characterized by the presence of a polar soft block having a glass transition temperature or crystalline melting temperature below 37° C. with the proviso that said base polymer is not a polycarbonate of 4,4'-diphenyldimethylmethane.

Claim 3

A polymer according to claim 1 wherein said nonpolar soft block is characterized by a γ c less than 30 dyne/cm and a tendency to exude, and said polar hard segments lower said tendency to exude.

Claim 4

A polymer according to claim 1 wherein said nonpolar soft block is characterized by a γ c less than 40 dyne/cm and a tendency to exude, and said polar hard segments lower said tendency to exude.

Claim 5

A modified solid polymer blend formed of a base polymer and a solid thermoplastic segmented block copolymer additive blended with said base polymer, said additive comprising a first essentially linear segmented copolymer chain and a second essentially linear polymer chain chemically bonded to said first segmented copolymer chain, said second polymer chain being selected from a polar homopolymer or a second segmented copolymer said additive characterized by a γ c less than said base polymer and said first segmented copolymer chain characterized by the presence of at least one polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and a nonpolar soft block having a glass transition temperature or crystalline melting temperature below 37° C.; said second segmented copolymer or polar homopolymer characterized by the presence of at least one second polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and said second segmented copolymer further characterized by the presence of a polar soft block having a glass transition temperature or crystalline melting temperature below 37° C., said polar hard segments independently selected from the group consisting of a polyurethane and a polyurethaneurea, with the proviso that said base polymer is not a polycarbonate of 4,4'-diphenylmethylmethane, wherein said nonpolar and polar soft blocks control the surface properties of said modified solid polymer blend.

Claim 6

A modified solid polymer blend formed of a base polymer and a solid thermoplastic segmented block copolymer additive blended with said base polymer, said additive comprising a first essentially linear segmented copolymer chain and a second essentially linear polymer chain chemically bonded to said first segmented copolymer chain, said second polymer chain being selected from a polar homopolymer or a second segmented copolymer said additive characterized by a γ c less than said base polymer and said first segmented copolymer chain characterized by the presence of at least one polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and a nonpolar soft block having a glass transition temperature or crystalline melting temperature below 37° C.; said second segmented copolymer or polar homopolymer characterized by the presence of at least one second polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and said second segmented copolymer further characterized by the presence of a polar soft block having a glass transition temperature or crystalline melting temperature below 37° C., said polar hard segments independently selected from the group consisting of a polyurethane and a polyurethaneurea, with the proviso that said base polymer is not a polycarbonate of 4,4'-diphenylmethylmethane, wherein said nonpolar and polar soft blocks control the surface properties of said modified solid polymer blend.

Claim 7

A polymer according to claim 1 wherein said second polymer chain is said second segmented copolymer.

Claim 8

A polymer according to claim 3 wherein said second polymer chain is said second segmented copolymer.

Claim 9

A polymer according to claim 4 wherein said second polymer chain is said second segmented copolymer.

Claim 10

A polymer according to claim 5 wherein said polar soft block segment comprises polydimethylsiloxane oligomers having polyethylene oxide terminal groups.

Claim 11

A polymer according to claim 6 wherein said polar soft block segment comprises polydimethylsiloxane oligomers having polyethylene oxide terminal groups.

Claim 12

A polymer according to claim 7 wherein said polar soft block segment comprises polydimethylsiloxane oligomers having polyethylene oxide terminal groups.

Claim 13

The modified solid polymer of claim 4 in which the base polymer is selected from the group consisting of a polyurethane, polyester, polyester-polyether, polyamide, polyether-polyamide, styrene-isoprene, styrene-butadiene, thermoplastic polyolefin, styrene-saturated olefin, polyester-polyester, ethylene-vinyl acetate, ethylene ethylacrylate, ionomers, and thermoplastic polydiene.

Claim 14

The modified solid polymer of claim 1 in which the base polymer is selected from the group consisting of a polyurethane, polyester, polyester-polyether, polyamide, polyether-polyamide, styrene-isoprene, styrene-butadiene, thermoplastic polyolefin, styrene-saturated olefin, polyester-polyester, ethylene-vinyl acetate, ethylene-ethylacrylate, ionomers, or thermoplastic polydiene.

Claim 15

A modified solid polymer according to claim 5 wherein said polar soft blocks are independently selected from the group consisting of polyalkylene oxide-copolyalkylene oxides, polyvinylalkanoates and polyalkylene oxides, and said nonpolar soft blocks are independently selected from the group consisting of polydialkylsiloxanes, polyfluoroalkyl alkylsiloxanes, polyolefins, polydienes and polyfluorocarbons.

Claim 16

A modified solid polymer according to claim 6 wherein said polar soft blocks are independently selected from the group consisting of polyalkylene oxide-copolyalkylene oxides, polyvinylalkanoates and polyalkylene oxides, and said nonpolar soft blocks are independently selected from the group consisting of polydialkylsiloxanes, polyfluoroalkyl alkylsiloxanes, polyolefins, polydienes and polyfluorocarbons.

Claim 17

A modified solid polymer according to claim 7 wherein said polar soft blocks are independently selected from the group consisting of polyalkylene oxide-copolyalkylene oxides, polyvinylalkanoates and polyalkylene oxides, and said nonpolar soft blocks are independently selected from the group consisting of polydialkylsiloxanes, polyfluoroalkyl alkylsiloxanes, polyolefins, polydienes and polyfluorocarbons.

Claim 18

A modified solid polymer according to claim 11 wherein said base polymer comprises a thermoplastic polyolefin polymer admixed with plasticizers.

Claim 19

A modified solid polymer according to claim 12 wherein said base polymer comprises a thermoplastic polyolefin polymer admixed with plasticizers.

Claim 20

A modified solid polymer according to claim 4 wherein said base polymer is polyvinyl chloride.

Claim 21

A modified solid polymer according to claim 1 wherein said base polymer is polyvinyl chloride.

Claim 22

A polymer blend for controllably varying the balance of polar to nonpolar groups on the surface of said blend comprising an admixture of a minor portion of a solid thermoplastic polymer additive distributed throughout a major portion of a base polymer, said additive comprising an essentially linear first segmented copolymer chain and a second essentially linear polymer chain chemically bonded to said first segmented copolymer chain, said second polymer chain being selected from a polar homopolymer or a second segmented polymer, said first chain characterized by a γ c less than said base polymer and said first chain segmented copolymer characterized by the presence of at least one polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., a nonpolar soft block having a glass transition temperature or crystalline melting temperature below 37° C.; said second segmented copolymer or polar homopolymer characterized by the presence of at least one polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and said second segmented copolymer further characterized by the presence of a polar soft block having a glass transition temperature of crystalline melting temperature below 37° C., said polar hard segments independently selected from the group consisting of a polyurethane and a polyurethaneurea; with the proviso that said base polymer is not a polycarbonate of 4,4'-diphenyldimethylmethane.

Claim 23

A polymer blend for controllably varying the balance of polar to nonpolar groups on the surface of said blend comprising an admixture of a minor portion of a solid thermoplastic polymer additive distributed throughout a major portion of a base polymer, said additive comprising an essentially linear first segmented copolymer chain and a second essentially linear polymer chain chemically bonded to said first segmented copolymer chain, said second polymer chain being selected from a polar homopolymer or a second segmented polymer, said first chain characterized by a γ c less than said base polymer and said first chain segmented copolymer characterized by the presence of at least one polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., a nonpolar soft block having a glass transition temperature or crystalline melting temperature below 37° C.; said second segmented copolymer or polar homopolymer characterized by the presence of at least one polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and said second segmented copolymer further characterized by the presence of a polar soft block having a glass transition temperature of crystalline melting temperature below 37° C., said polar hard segments independently selected from the group consisting of a polyurethane and a polyurethaneurea; with the proviso that said base polymer is not a polycarbonate of 4,4'-diphenyldimethylmethane.

Claim 24

A modified solid polymer of claim 4 or 20 containing no greater than 5 volume % of said polar and nonpolar soft blocks.

Claim 25

A modified solid polymer of claim 1 containing no greater than 5 volume % of said polar and nonpolar soft blocks.

Claim 26

The modified solid polymer of claim 4 or 20 containing in excess of 5 volume % of said polar and nonpolar soft blocks.

Claim 27

The modified solid polymer of claim 1 containing in excess of 5 volume % of said polar and nonpolar soft blocks.

Claim 28

The modified solid polymer of claim 4 or 20 characterized by a hardness as measured by the Shore A or Shore D scale of at least 5 shore hardness units less than that of the base polymer without the additive.

Claim 29

The modified solid polymer of claim 1 characterized by a hardness as measured by the Shore A or Shore D scale of at least 5 shore hardness units less than that of the base polymer without the additive.

Claim 30

The modified solid polymer of claim 1 in which the soft block of the additive has a molecular weight of at least 5 repeat units.

Claim 31

The polymer of claim 1 in which said segmented copolymer chain comprises a nonplar soft block of a polydialkylsiloxane, and a polar hard segment of a polyurethane.

Claim 32

The polymer of claim 4 or 20 in which said segmented copolymer chain comprises a nonpolar soft block of a polydialkylsiloxane, and a polar hard segment of a polyurethane.

Claim 33

The polymer of claim 1 in which said polymer additive comprises at least about 20 volume % of said homopolymer.

Claim 34

The polymer blend of claim 4 or 20 in which said polymer additive comprises at least about 20 volume % of said homopolymer.

Claim 35

The polymer of claim 1 in which said polymer additive comprises about 20 to 80 volume % of said polar and nonpolar soft blocks.

Claim 36

The polymer of claim 4 or 20 in which said polymer additive comprises about 20 to 80 volume % of said polar and nonpolar soft blocks.

Claim 37

The polymer of claim 4 in which said polymer additive comprises about 80 to 20 volume % of said polar hard segments.

Claim 38

The polymer of claim 1 in which said polymer additive comprises about 80 to 20 volume % of said polar hard segments.

Claim 43

In a method of forming a polymer admixture of low surface free energy from a base polymer and solid copolymer additive wherein said base polymer includes end groups capable of hydrogen bonding ore reacting with protein, the steps of (a) fractionating a base polymer to remove a lower molecular weight fraction to reduce the γ c of the remaining base polymer, (b) thoroughly dispersing no greater than about 5 volume % of a solid copolymer additive throughout at least 95 volume % of a base polymer, while said copolymer additive and base polymer are in fluid form, to form a polymer admixture, said copolymer additive comprising an essentially linear segmented copolymer chain; said additive characterized by a γ c less than the said base polymer and said segmented copolymer chain characterized by the presence of at least one polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and a nonpolar soft block having a glass transition temperature or crystalline melting temperature below 37° C., said additive further comprises a seciond essentially linear polymer chain chemically bonded to said segmented copolymer chain, and second polymer chain being a polar homopolymer or a second segmented copolymer, said second segmented copolymer or polar homopolymer characterized by the presence of at least one polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and second segmented copolymer further characterized by the presence of a polar soft block having a glass transition temperature of crystalline melting temperature below 37° C., said polar hard segment independently selected from the group consisting of a polyurethane and a polyurethaneurea with the proviso that said base polymer is not a polycarbonate of 4,4'-diphenyldimethylmethane, said polymer additive being characterized by a γ c less than said base polymer and said polymer admixture being characterized by a γ c between about 10 and 35 dyne/cm., and (c) solidifying said polymer admixture.

Claim 44

In a method of forming a polymer admixture of low surface free energy from a base polymer and solid copolymer additive wherein said base polymer includes end groups capable of hydrogen bonding ore reacting with protein, the steps of (a) fractionating a base polymer to remove a lower molecular weight fraction to reduce the γ c of the remaining base polymer, (b) thoroughly dispersing no greater than about 5 volume % of a solid copolymer additive throughout at least 95 volume % of a base polymer, while said copolymer additive and base polymer are in fluid form, to form a polymer admixture, said copolymer additive comprising an essentially linear segmented copolymer chain; said additive characterized by a γ c less than the said base polymer and said segmented copolymer chain characterized by the presence of at least one polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and a nonpolar soft block having a glass transition temperature or crystalline melting temperature below 37° C., said additive further comprises a seciond essentially linear polymer chain chemically bonded to said segmented copolymer chain, and second polymer chain being a polar homopolymer or a second segmented copolymer, said second segmented copolymer or polar homopolymer characterized by the presence of at least one polar hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and second segmented copolymer further characterized by the presence of a polar soft block having a glass transition temperature of crystalline melting temperature below 37° C., said polar hard segment independently selected from the group consisting of a polyurethane and a polyurethaneurea with the proviso that said base polymer is not a polycarbonate of 4,4'-diphenyldimethylmethane, said polymer additive being characterized by a γ c less than said base polymer and said polymer admixture being characterized by a γ c between about 10 and 35 dyne/cm., and (c) solidifying said polymer admixture.

Claim 45

A polymer solid at a 37° C. comprising a block polymer including an essentially linear sequence of block segments represented by the formula (A) (B) (C) (D), in which A is a hard polymer segment with a crystalline melting point above 37° C. or a glass transition temperature above 37° C., B is a poly(dialkylsiloxane), C is a hard polymer segment with a crystalline melting point above 37° C. or a glass transition temperature above 37° C., and D is a soft polymer block having a crystalline melting point below 37° C. or a glass transition temperature below 37° C., or C and D together form a homopolymer having a repeating unit comprising at least one hard segment having a crystalline melting point above 37° C. or glass transition temperature above 37° C. chemically bonded to at least one polymer selected from the group consisting of polyethylene oxide, polyethylene oxide copolypropylene oxide, polyvinyl acetate, polyvinylpyrolidone, and poly(hydroxyethyl methacrylate), said hard polymer segments independently selected from the group consisting of a polyurethane and a polyurethaneurea.

Claim 46

A polymer solid at a 37° C. comprising a block polymer including an essentially linear sequence of block segments represented by the formula (A) (B) (C) (D), in which A is a hard polymer segment with a crystalline melting point above 37° C. or a glass transition temperature above 37° C., B is a poly(dialkylsiloxane), C is a hard polymer segment with a crystalline melting point above 37° C. or a glass transition temperature above 37° C., and D is a soft polymer block having a crystalline melting point below 37° C. or a glass transition temperature below 37° C., or C and D together form a homopolymer having a repeating unit comprising at least one hard segment having a crystalline melting point above 37° C. or glass transition temperature above 37° C. chemically bonded to at least one polymer selected from the group consisting of polyethylene oxide, polyethylene oxide copolypropylene oxide, polyvinyl acetate, polyvinylpyrolidone, and poly(hydroxyethyl methacrylate), said hard polymer segments independently selected from the group consisting of a polyurethane and a polyurethaneurea.

Claim 47

A polymer solid at 37° C. comprising a block polymer including an essentially linear sequence of block segments represented by the formula (A) (B) (D)) p , in which A is a hard polymer segment having a crystalline melting point above 37° C. or a glass transition temperature above 37° C., said hard polymer segment selected from the group consisting of a polyurethane and a polyurethaneurea, B is a poly(dialkylsiloxane), D is a soft polymer block having a crystalline melting point below 37° C. or a glass transition temperature below 37° C. and p is a positive integer.

Claim 48

A polymer solid at 37° C. comprising a block polymer including an essentially linear sequence of block segments represented by the formula (A) (B) (D)) p , in which A is a hard polymer segment having a crystalline melting point above 37° C. or a glass transition temperature above 37° C., said hard polymer segment selected from the group consisting of a polyurethane and a polyurethaneurea, B is a poly(dialkylsiloxane), D is a soft polymer block having a crystalline melting point below 37° C. or a glass transition temperature below 37° C. and p is a positive integer.

Claim 49

The polymer according to claim 39 or 40 blended with a blood incompatible base polymer in the ratio of at least 95 volume % base polymer and no greater than 5 volume % polymer additive to form a blood-compatible admixture.

Claim 50

A blood-compatible polymer solid at 37° C. comprising a block polymer including an essentially linear sequence of block segments represented by the formula (A) (B) (C), in which A is a polyalkylsiloxane, B is a hard segment with a crystalline melting point above 37° C. or a glass transition temperature above 37° C., said hard segment selected from the group consisting of a polyurethane and a polyurethaneurea, and C is a hydrophilic polymer selected from the group consisting of polyethylene oxide and polyethylene oxide-copolypropylene oxide.

Claim 51

A blood-compatible polymer solid at 37° C. comprising a block polymer including an essentially linear sequence of block segments represented by the formula (A) (B) (C), in which A is a polyalkylsiloxane, B is a hard segment with a crystalline melting point above 37° C. or a glass transition temperature above 37° C., said hard segment selected from the group consisting of a polyurethane and a polyurethaneurea, and C is a hydrophilic polymer selected from the group consisting of polyethylene oxide and polyethylene oxide-copolypropylene oxide.

Claim 52

In a method of forming the exposed blood-contacting surface of a biomedical device, or components thereof, the steps of (a) thoroughly dispersing no greater than about 5 volume % of a polymer additive throughout at least 95 volume % of a base polymer, while said polymer additive and base polymer are in fluid form, to form a polymer admixture, said polymer additive comprising a thermoplastic segmented block copolymer characterized by the presence of at least one polar hard segment of from 1 to 10 repeating monomer units, said segment selected from the group consisting of a polyurethane and a polyurethaneurea and having a glass transition temperature or crystalline melting temperature above 37° C. and a nonpolar soft block having a glass transition temperature or a crystalline melting temperature below 37° C., said polymer additive beingf characterized by a γ c less than said base polymer and said polymer admixture being characterized by a γ c between about 10 and 35 dyne/cm; and (b) solidifying said polymer mixture and forming it into the blood-contacting surface of a biomedical device or component thereof.

Claim 53

In a method of forming the exposed blood-contacting surface of a biomedical device, or components thereof, the steps of (a) thoroughly dispersing no greater than about 5 volume % of a polymer additive throughout at least 95 volume % of a base polymer, while said polymer additive and base polymer are in fluid form, to form a polymer admixture, said polymer additive comprising a thermoplastic segmented block copolymer characterized by the presence of at least one polar hard segment of from 1 to 10 repeating monomer units, said segment selected from the group consisting of a polyurethane and a polyurethaneurea and having a glass transition temperature or crystalline melting temperature above 37° C. and a nonpolar soft block having a glass transition temperature or a crystalline melting temperature below 37° C., said polymer additive beingf characterized by a γ c less than said base polymer and said polymer admixture being characterized by a γ c between about 10 and 35 dyne/cm; and (b) solidifying said polymer mixture and forming it into the blood-contacting surface of a biomedical device or component thereof.

Claim 54

The method of claim 43 in which said first component is characterized by a γ c less than 30 dyne/cm. and a tendency to exude, and said second component lowers said tendency to exude.

Claim 55

The method of claim 43 in which said first component is a homopolymer selected from the group consisting of polydialkylsiloxanes, polyfluoroalkyl alkylsiloxanes, polyalkylene oxides, polyolefins, polydienes and polyfluorocarbons.

Claim 56

The method of claim 45 in which said first component is poly(dimethylsiloxane).

Claim 57

The method of claim 43 in which said first component is polydialkylsiloxane, and said second component is a polyurethane.

Claim 58

The method of claim 43 in which said second component and said base polymer are formed of the same type of homopolymer.

Claim 59

The method of claim 43 in which said base polymer includes end groups capable of hydrogen bonding or reacting with protein, together with the step of fractionating said base polymer to remove a lower molecular weight fraction to reduce the hydrogen bonding capacity of the remaining base polymer prior to said dispersion step.

Claim 60

The method of claim 43 together with the step of annealing said polymer admixture.

Claim 61

The method of claim 43 in which about 0.00002 to 2 volume % polymer additive is added to said base polymer based on the total polymer admixture.

Claim 62

The method of claim 43 in which said polymer additive comprises at least about 20 volume % of said first component.

Claim 63

The method of claim 43 in which said polymer additive comprises at about 20 to 80 volume % of said first component and about 20 to 80 volume % of said second component.

Claim 64

A blood-compatible polymer admixture comprising at least 95 volume % of a base polymer and no greater than 5 volume % of a solid polymer additive comprising a poly(dialkysiloxane) block chemically bonded to a polyurethane segment of from 1 to 10 repeating monomer units said polymer additive being dispersed throughout said base polymer and being characterized by a γ c les than said base polymer, said polymer admixture being characterized by a γ c between about 10 to 35 dyne/cm.

Claim 65

A blood-compatible polymer admixture comprising at least 95 volume % of a base polymer and no greater than 5 volume % of a solid polymer additive comprising a poly(dialkysiloxane) block chemically bonded to a polyurethane segment of from 1 to 10 repeating monomer units said polymer additive being dispersed throughout said base polymer and being characterized by a γ c les than said base polymer, said polymer admixture being characterized by a γ c between about 10 to 35 dyne/cm.

Claim 66

The polymer admixture of claim 54 in which said polymer additive is a graft copolymer.

Claim 67

The polymer admixture of claim 54 in which said polymer additive is a block copolymer.

Claim 68

The polymer admixture of claim 54 in which said base polymer is a polyurethane.

Claim 69

In a method of forming a blood-compatible polymer admixture, the steps of (a) thoroughly dispersing no greater than about 5 volume % of an essentially linear segmented block copolymer additive throughout at least 95 volume % of a base polymer, while said copolymer additive and base polymer are in fluid form, to form a polymer admixture, said copolymer additive comprising a poly(dialkylsiloxane) block component chemically bonded to a polyurethane segment of from 1 to 10 repeating monomer units, said cpolymer additive being characterized by a γ c less than said base polymer and said polymer admixture being characterized by a γ c between about 10 and 35 dyne/cm.; and (b) solidifying said polymer admixture.

Claim 70

In a method of forming a blood-compatible polymer admixture, the steps of (a) thoroughly dispersing no greater than about 5 volume % of an essentially linear segmented block copolymer additive throughout at least 95 volume % of a base polymer, while said copolymer additive and base polymer are in fluid form, to form a polymer admixture, said copolymer additive comprising a poly(dialkylsiloxane) block component chemically bonded to a polyurethane segment of from 1 to 10 repeating monomer units, said cpolymer additive being characterized by a γ c less than said base polymer and said polymer admixture being characterized by a γ c between about 10 and 35 dyne/cm.; and (b) solidifying said polymer admixture.

Claim 71

The polymer of claim 42 blended with the blood-incompatible base polymer in the ratio of at least 95 volume % base polymer and no greater than 5 volume % polymer additive.

Claim 72

A solid, thermoplastic, essentially linear, segmented block copolymer characterized by the presence of at least one polar polyurethane or polyurethaneurea hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and a nonpolar polysiloxane soft block having a glass transition temperature or crystalline melting temperature below 37° C.

Claim 73

A solid, thermoplastic, essentially linear, segmented block copolymer characterized by the presence of at least one polar polyurethane or polyurethaneurea hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and a nonpolar polysiloxane soft block having a glass transition temperature or crystalline melting temperature below 37° C.

Claim 74

A copolymer according to claim 60 further comprising polyalkylene oxide soft blocks.

Claim 75

A copolymer according to claim 60 wherein said polysiloxane is a polydialkylsiloxane.

Claim 76

A copolymer according to claim 62 wherein said hard segment is a polyurethane.

Claim 77

A copolymer according to claim 63 wherein said polydialkylsiloxane comprises polydimethylsiloxane and said polyurethane is formed from diphenylmethane diisocyanate and 1,4-butanediol.

Claim 78

A copolymer according to claim 60 further comprising a chain extending diamine.

Claim 79

A modified solid polymer formed of a base polymer and a solid thermoplastic segmented block copolymer additive blended with said based polymer, said additive comprising an essentially linear, segmented block copolymer characterized by the presence of at least one polar polyurethane or polyurethaneurea hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and a nonpolar polysiloxane soft block having a glass transition temperature or crystalline melting temperature below 37° C.

Claim 80

A modified solid polymer formed of a base polymer and a solid thermoplastic segmented block copolymer additive blended with said based polymer, said additive comprising an essentially linear, segmented block copolymer characterized by the presence of at least one polar polyurethane or polyurethaneurea hard segment having a glass transition temperature or crystalline melting temperature above 37° C., and a nonpolar polysiloxane soft block having a glass transition temperature or crystalline melting temperature below 37° C.

Claim 81

A modified polymer according to claim 66 wherein said polysiloxane is a polydialkylsiloxane and said hard segment is a polyurethane.

Claim 82

A modified polymer according to claim 67 wherein said polydiaalkylsiloxane comprises polydimethylsiloxane and said polyurethane is formed from diphenylmethane diisocyanate and 1,4-butanediol.

Claim 83

In a method of forming a polymer admixture of low surface free energy from a base polymer and polymer additive wherein said base polymer includes end groups capable of hydrogen bonding or reacting with protein, the steps of (a) fractionating a base polymer to remove a lower molecular weight fraction to reduce the γ c of the remaining base polymer, (b) thoroughly dispersing no greater than about 5 volume % of a polymer additive throughout at least 5 volume % of a base polymer, while said polymer additive and base polymer are in fluid form, to form a polymer admixture, said polymer additive comprising a thermoplastic segmented block copolymer characterized by the presence of at least one polar hard segment of from 1 to 10 repeating monomer units, said segment selected from the group consisting of a polyurethane and a polyurethaneurea and having a glass transition temperature or crystalline melting temperature above 37° C. and a nonpolar soft block having a glass transition temperature or crystalline melting temperature below 37° C., said polymer additive being characterized by a γ c less than said base polymer and said polymer admixture being characterized by a γ c between about 10 and 35 dyne/cm; and (c) solidifying said polymer admixture.

Claim 84

In a method of forming a polymer admixture of low surface free energy from a base polymer and polymer additive wherein said base polymer includes end groups capable of hydrogen bonding or reacting with protein, the steps of (a) fractionating a base polymer to remove a lower molecular weight fraction to reduce the γ c of the remaining base polymer, (b) thoroughly dispersing no greater than about 5 volume % of a polymer additive throughout at least 5 volume % of a base polymer, while said polymer additive and base polymer are in fluid form, to form a polymer admixture, said polymer additive comprising a thermoplastic segmented block copolymer characterized by the presence of at least one polar hard segment of from 1 to 10 repeating monomer units, said segment selected from the group consisting of a polyurethane and a polyurethaneurea and having a glass transition temperature or crystalline melting temperature above 37° C. and a nonpolar soft block having a glass transition temperature or crystalline melting temperature below 37° C., said polymer additive being characterized by a γ c less than said base polymer and said polymer admixture being characterized by a γ c between about 10 and 35 dyne/cm; and (c) solidifying said polymer admixture.

Claim 85

A modified solid polymer blend formed of a base polymer and a solid thermoplastic segmented block copolymer additive blended with said base polymer, said additive comprising an essentially linear segmented copolymer chain; said additive characterized by a γ c less than said base polymer and said segmented copolymer chain characterized by the presence of at least one polar hard segment of from 1 to 10 repeating monomer units, said segment selected from the group consisting of a polyurethane and a polyurethaneurea and having a glass transition temperature or crystalline melting temperature above 37° C.; and a nonpolar soft block having a glass transition temperature or crystalline melting temperature below 37° C. with the proviso that said base polymer is not a polycarbonate of 4,4'-diphenyldimethylmethane.

Claim 86

A modified solid polymer blend formed of a base polymer and a solid thermoplastic segmented block copolymer additive blended with said base polymer, said additive comprising an essentially linear segmented copolymer chain; said additive characterized by a γ c less than said base polymer and said segmented copolymer chain characterized by the presence of at least one polar hard segment of from 1 to 10 repeating monomer units, said segment selected from the group consisting of a polyurethane and a polyurethaneurea and having a glass transition temperature or crystalline melting temperature above 37° C.; and a nonpolar soft block having a glass transition temperature or crystalline melting temperature below 37° C. with the proviso that said base polymer is not a polycarbonate of 4,4'-diphenyldimethylmethane.

Claim 87

A modified solid polymer according to claim 70 wherein said nonpolar soft block is 5 to 350 repeating monomer units in length.

Claim 88

A modified solid polymer according to claim 70 wherein said polar hard segment is 1 to 2 repeating monomer units in length.

Claim 89

A modified solid polymer according to claim 71 wherein said nonpolar soft block is 20-50 repeating monomer units in length.