Polymer systems suitable for blood-contacting surfaces of a biomedical device, and methods for forming
First Claim
1. 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.
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Abstract
A polymer admixture is formed from a base polymer and thermoplastic copolymer additive including polar hard segments and polar and nonpolar soft blocks in graft or block copolymer form. The polymer admixture is characterized by increased contact angle hysteresis and is formed into blood and tissue-contacting surfaces of a biomedical device or into textiles. A preferred additive comprises a segmented block copolymer having polydialkylsiloxanes as nonpolar soft blocks, and a polyurethane as hard segments and a polyalkylene oxide as a polar soft block.
325 Citations
73 Claims
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1. 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. - View Dependent Claims (2, 3, 5, 6, 8, 9, 12, 13, 14, 17, 19, 22, 24, 26, 27, 28, 30, 32, 35)
- said additive characterized by a γ
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4. 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. - View Dependent Claims (7, 10, 11, 15, 16, 18, 34)
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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°
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20. 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. - View Dependent Claims (21, 23, 25, 29, 31, 33)
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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°
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36. A method for controllably varying the balance of polar to nonpolar groups on the surface of a polymer blend comprising the steps of thoroughly blending a minor portion of a solid thermoplastic polymer additive throughout a major portion of a base polymer while said polymer additive and base polymer are in fluid form, to form said polymer blend, said additive comprising an essentially linear first segmented copolymer chain and a second essentially linear polymer chain chemically bonded to said first segmented polymer chain being 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., 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 polar hard segment having a glass transition 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.
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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°
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37. A method of forming a polymer of low surface free energy and increased contact angle hysteresis comprising the steps of
(a) reacting up to about 2 volume % of a reactive polysiloxane oligomer with at least 98 volume % of a base polymer, while said oligomer and base polymer are in fluid form to form a fluid polymer admixture of at least 95 volume % pure base polymer and no greater than 5 volume % of a copolymer of said base polymer and said oligomer, and (b) solidifying said polymer ad mixture, said copolymer comprising an essentially linear segmented copolymer chain; - said copolymer 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 polyurethane or polyurethane urea 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. with the proviso that said base polymer is not a polycarbonate of 4,4'"'"'-diphenyldimethylmethane and said polymer admixture being characterized by a γ
c between about 10 and 35 dyne/cm.
- said copolymer characterized by a γ
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38. 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.
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c of the remaining base polymer,
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39. 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. - View Dependent Claims (41)
- 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°
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40. 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.
- 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°
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42. 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. - View Dependent Claims (59)
- 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°
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43. 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. - View Dependent Claims (44, 45, 46, 47, 48, 49, 50, 51, 52, 53)
- C. and a nonpolar soft block having a glass transition temperature or a crystalline melting temperature below 37°
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54. 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. - View Dependent Claims (55, 56, 57)
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c les than said base polymer, said polymer admixture being characterized by a γ
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58. 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.
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c less than said base polymer and said polymer admixture being characterized by a γ
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60. 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. - View Dependent Claims (61, 62, 63, 64, 65)
- C., and a nonpolar polysiloxane soft block having a glass transition temperature or crystalline melting temperature below 37°
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66. 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. - View Dependent Claims (67, 68)
- C., and a nonpolar polysiloxane soft block having a glass transition temperature or crystalline melting temperature below 37°
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69. 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.
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c of the remaining base polymer,
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70. 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. - View Dependent Claims (71, 72, 73)
- said additive characterized by a γ
Specification