Bone cement having chemically joined reinforcing fillers

• US 5,336,699 A
• Filed: 12/28/1992
• Issued: 08/09/1994
• Est. Priority Date: 02/20/1992
• Status: Expired due to Fees

• Current Assignee: Orthopaedic Research Institute
• Original Assignee: Orthopaedic Research Institute
• Inventors: Yasuda, Hirotsuga K., Marrero, Thomas R., Cooke, Francis W.
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): DEWITT, LAVONDA R
• Application Number:
  US07/998,881
• Time in Patent Office: 589 Days
• Field of Search: 523/115, 523/209, 523/212, 523/213, 523/222, 523/116, 606/76, 606/92
• US Class Current: 523/115
• CPC Class Codes: A61B 17/8802 Equipment for handling bone cement or other fluid fillers
• CPC Class Codes: A61B 90/39 Markers, e.g. radio-opaque or breast lesions markers
• CPC Class Codes: A61F 2/30767 Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
• CPC Class Codes: A61F 2/30965 Reinforcing the prosthesis by embedding particles or fibres during moulding or dipping
• CPC Class Codes: A61F 2002/3008 radio-opaque, e.g. radio-opaque markers
• CPC Class Codes: A61F 2002/4631 the prosthesis being specially adapted for being cemented
• CPC Class Codes: A61F 2250/0098 radio-opaque, e.g. radio-opaque markers
• CPC Class Codes: A61L 24/0094 containing macromolecular fillers
• CPC Class Codes: A61L 24/06 obtained by reactions only involving carbon-to-carbon unsaturated bonds A61L24/043, A61L24/046 take precedence
• CPC Class Codes: A61L 2430/02 for reconstruction of bones; weight-bearing implants
• CPC Class Codes: C08L 33/12 Homopolymers or copolymers of methyl methacrylate

Abstract

Improved polymeric orthopaedic compositions are disclosed wherein sized, functional fibers are incorporated into a physiologically acceptable matrix. The compositions of the invention can be fabricated in the form of particulate powders adapted for reinforcment of bone cements, continuous media for such cements, and orthopaedic implant coatings. A complete implant attachment system is also provided, made up of a fiber reinforced implant coating, and a compatible fiber-reinforced cement. In preferred forms, the fibers have a layer of sizing thereover which is chemically joined both to the surface of the fibers and to the surrounding matrix, and the fibers are present at a level of at least about 6 volume percent. If desired, sized radiopaque particles may be incorporated into the compositions of the invention. The fibers are advantageously polymeric in nature and of intermediate stiffness, whereas the matrix fraction is preferably polymethylmethacrylate.

Claims

1. An orthopaedic composition, comprising:

an amount of a physiologically acceptable polymeric matrix material; and

a quantity of fibers disbursed in said matrix for enhancing functional qualities of the composition, said fibers having a layer of a sizing material thereover which is chemically joined to the surface of the fibers, said sizing material on the fibers also being chemically joined with the matrix material,

said fibers being present in said composition in an effective amount for reinforcing said matrix and having an average length of from about 1 μ

m to about 2 cm,

said fibers having a stiffness defined as the product of the tensile elastic modulus of the fibers and the area moment of inertia of the fibers, said stiffness being from about 1.0×

10^-13 to 150×

10^-13 Nm².

2. An orthopaedic composition as set forth in claim 1, wherein said sizing material is directly chemically joined to said fibers.

3. An orthopaedic composition as set forth in claim 1, wherein said sizing material is a coupling agent different from said matrix.

4. An orthopaedic composition as set forth in claim 1, wherein said fibers comprise polymeric reinforcing fibers formed of a relatively high strength polymer of intermediate stiffness.

5. An orthopaedic composition as set forth in claim 1, said composition being in the form of a particulate powder adapted for placement in a continuous medium to form a bone cement.

6. An orthopaedic composition as set forth in claim 5, the particles of said powder having an average size of from about 5 to 100 μ

m.

7. An orthopaedic composition as set forth in claim 5, said fibers being in the form of polymeric fibers.

8. An orthopaedic composition as set forth in claim 7, said fibers being selected from the group consisting of polyaramids, polyesters, polyalkenes and polyamides.

9. An orthopaedic composition as set forth in claim 7, said fibers having a diameter of from about 1 μ

m to 100 μ

m.

10. An orthopaedic composition as set forth in claim 9, wherein at least certain of said fibers have a diameter of from about 2-15 μ

m.

11. An orthopaedic composition as set forth in claim 7, said fibers having a length of up to about the diameter of said particle.

13. An orthopaedic composition as set forth in claim 7, wherein said fibers have a room temperature fatigue strength of at least about 7 MPa at 10⁶ cycles.

14. An orthopaedic composition as set forth in claim 13, said fatigue strength being at least 30 MPa at 10⁶ cycles.

15. An orthopaedic composition as set forth in claim 7, said fibers being present in said powder at a level of from about 6 to 70 volume percent.

16. An orthopaedic composition as set forth in claim 15, said level being about 50 volume percent.

17. An orthopaedic composition as set forth in claim 5, wherein said matrix is a substituted or unsubstituted acrylate.

18. An orthopaedic composition as set forth in claim 17, said matrix being polymethylmethacrylate.

19. An orthopaedic composition as set forth in claim 18, said polymethylmethacrylate having a viscosity average molecular weight of not less than about 1×

10⁵ g./mole.

20. An orthopaedic composition as set forth in claim 5, wherein said sizing material is selected from the group consisting of ethyl silane, methylmethacrylate, ethylmethacrylate, ethylene, propylene and methane.

21. An orthopaedic composition as set forth in claim 20, wherein said sizing material is an acrylate.

22. An orthopaedic composition as set forth in claim 20, wherein said sizing material is methylmethacrylate.

23. An orthopaedic composition as set forth in claim 5, including a radiopaque agent, said agent having said sizing material thereover.

24. An orthopaedic composition as set forth in claim 5, wherein said sizing material has been chemically joined to the fibers by a technique selected from the group consisting of glow discharge induced reaction, ultraviolet induced reaction, free-radical induced reaction and catalytic reaction.

25. An orthopaedic composition as set forth in claim 24, wherein glow discharge reaction of the sizing material while in contact with said fibers is carried out at a frequency of up to about 100 MHz at a power level of at least about 20 W.

26. An orthopaedic composition as set forth in claim 25, wherein glow discharge reaction of the sizing material while in contact with said fibers is carried out at a frequency between about 5-15 MHz

27. An orthopaedic composition as set forth in claim 24, wherein glow discharge reaction of the sizing material while in contact with said fibers is carried out for a time period equivalent to 30 minutes exposure for each 0.05 kg of fibers having a density of about 1 g/cm³ and an average diameter of about 10 μ

m.

28. An orthopaedic composition as set forth in claim 1, said composition being in the form of a continuous medium adapted for mixing with reinforced particles to form a bone cement.

29. An orthopaedic composition as set forth in claim 28, said fibers being in the form of polymeric fibers.

30. An orthopaedic composition as set forth in claim 29, said fibers being selected from the group consisting of polyaramids, polyesters, polyalkenes and polyamides.

31. An orthopaedic composition as set forth in claim 29, said fibers having a diameter of from about 1 μ

m to 100 μ

m.

32. An orthopaedic composition as set forth in claim 31, wherein at least certain of said fibers have a diameter of from about 2-15 μ

m.

33. An orthopaedic composition as set forth in claim 28, said fibers having a length of up to about 5 min.

34. An orthopaedic composition as set forth in claim 29, wherein said stiffness is from about 10×

10^-3 to 75×

10^-13 Nm².

35. An orthopaedic composition as set forth in claim 28, wherein said fibers have a room temperature fatigue strength of at least about 7 MPa at 10⁶ cycles.

36. An orthopaedic composition as set forth in claim 35, said fatigue strength being at least 30 MPa at 10⁶ cycles.

37. An orthopaedic composition as set forth in claim 28, said fibers being present in said medium at a level of from about 6-20 volume percent.

41. An orthopaedic composition as set forth in claim 28, wherein said sizing material is selected from the group consisting of ethyl silane, methylmethacrylate, ethylmethacrylate, ethylene, propylene and methane.

42. An orthopaedic composition as set forth in claim 41, wherein said sizing material is an acrylate.

43. An orthopaedic composition as set forth in claim 41, wherein said sizing material is polymethylmethacrylate.

44. An orthopaedic composition as set forth claim 28, including a radiopaque agent, said agent having said sizing material thereover.

45. An orthopaedic composition as set forth in claim 28, wherein said sizing material has been chemically joined to the fibers by a technique selected from the group consisting of glow discharge induced reaction, ultraviolet induced reaction, free-radical induced reaction and catalytic reaction.

46. An orthopaedic composition as set forth in claim 45, wherein glow discharge reaction of the sizing material while in contact with said fibers is carried out at a frequency of up to about 100 MHz at a power level of at least about 20 W.

47. An orthopaedic composition as set forth in claim 46, wherein glow discharge reaction of the sizing material while in contact with said fibers is carried out at a frequency between about 5-15 MHz.

48. An orthopaedic composition as set forth in claim 45, wherein glow discharge reaction of the sizing material while in contact with said fibers is carried out for a time period equivalent to 30 minutes exposure for each 0.05 kg of fibers having a density of about 1 g/cm³ and an average diameter of about 10 μ

m.

49. An orthopaedic composition as set forth in claim 1, said composition being in the form of a coating for application to an orthopaedic appliance.

50. An orthopaedic composition as set forth in claim 49, said fibers being in the form of polymeric fibers.

51. An orthopaedic composition as set forth in claim 50, said fibers being selected from the group consisting of polyaramids, polyesters, polyalkenes and polyamides.

52. An orthopaedic composition as set forth in claim 50, said fibers having a diameter of from about 1μ

m to 100μ

m.

53. An orthopaedic composition as set forth in claim 52, wherein at least certain of said fibers have a diameter of from about 2-15 μ

m.

54. An orthopaedic composition as set forth in claim 49, wherein said stiffness is from about 10×

10^-13 to 75×

10^-13 Nm².

55. An orthopaedic composition as set forth in claim 49, wherein said fibers have a room temperature fatigue strength of at least about 7 MPa at 10⁶ cycles.

56. An orthopaedic composition as set forth in claim 55, said fatigue strength being at least 30 MPa at 10⁶ cycles.

57. An orthopaedic composition as set forth in claim 49, said fibers being present at a level of from about 6 to 70 volume percent.

58. An orthopaedic composition as set forth in claim 57, said level being about 50 volume percent.

59. An orthopaedic composition as set forth in claim 49, wherein said matrix is a substituted or unsubstituted acrylate.

60. An orthopaedic composition as set forth in claim 59, said matrix being polymethylmethacrylate.

61. An orthopaedic composition as set forth in claim 60, said polymethylmethacrylate having a viscosity average molecular weight of not less than about 1×

10⁵ g./mole.

62. An orthopaedic composition as set forth in claim 49, wherein said sizing material is selected from the group consisting of ethyl silane, methylmethacrylate, ethylmethacrylate, ethylene, propylene and methane.

63. An orthopaedic composition as set forth in claim 62, wherein said sizing material is an acrylate.

64. An orthopaedic composition as set forth in claim 63, wherein said sizing material is polymethylmethacrylate.

65. An orthopaedic composition as set forth in claim 49, including a radiopaque agent, said agent having said sizing material thereover.

66. An orthopaedic composition as set forth in claim 49, wherein said sizing material has been chemically joined to the fibers by a technique selected from the group consisting of glow discharge induced reaction, ultraviolet induced reaction, free-radical induced reaction and catalytic reaction.

67. An orthopaedic composition as set forth in claim 66, wherein glow discharge reaction of the sizing material while in contact with said fibers is carried out at a frequency of up to about 100 MHz at a power level of at least about 20 W.

68. An orthopaedic composition as set forth in claim 67, wherein glow discharge reaction of the sizing material while in contact with said fibers is carried out at a frequency between about 5-15 MHz.

69. An orthopaedic composition as set forth in claim 67, wherein glow discharge reaction of the sizing material while in contact with said fibers is carried out for a time period equivalent to 30 minutes exposure for each 0.05 kg of fibers having a density of about 1 g/cm³ and an average diameter of about 10 μ

m.

12. An orthopaedic composition as set forth in claim 12, wherein said stiffness is from about 10×

10^-13 to 75×

10^-13 Nm².

38. An orthopaedic composition as set forth in claim 38, wherein said matrix is a substituted or unsubstituted acrylate.

39. An orthopaedic composition as set forth in claim 38, said matrix being polymethylmethacrylate.

40. An orthopaedic composition as set forth in claim 39, said polymethylmethacrylate having a viscosity average molecular weight of not less than about 1×

10⁵ g./mole.

70. A bone cement comprising:

a continuous medium comprising a physiologically acceptable polymeric material; and

a particulate powder dispersed in said continuous medium, the particles making up said powder including a physiologically acceptable polymeric matrix and reinforcing fibers extending through and at least partially out of the particles,

said polymeric material of the continuous medium being chemically joined with said fibers.

71. The bone cement of claim 70, said powder comprising from about 55-80% by weight of the bone cement.

72. The bone cement of claim 70, said continuous medium comprising a substituted or unsubstituted acrylate.

73. The bone cement of claim 72, said continuous medium comprising polymethylmethacrylate.

74. The bone cement of claim 70, said continuous medium including therein fibers distinct from the fibers present in said particles.

75. The bone cement of claim 70, said continuous medium including therein an amount of sized radiopaque agent.

76. The bone cement of claim 70, said fibers being selected from the group consisting of polyaramids, polyesters, polyalkenes and polyamides.

77. The bone cement of claim 77, said fibers having a layer of sizing material thereover chemically joined to the surface thereof, said sizing material on the fibers also being chemically joined with said matrix material.

78. The bone cement of claim 77, said continuous medium also being chemically joined to the sizing material on said fibers.

79. A method of preparing an orthopaedic composition comprising the steps of:

chemically bonding a layer of a sizing material onto the outer surfaces of a quantity of fibers; and

polymerizing a monomeric material in the presence of said sized fibers for chemically joining the sized fibers to the resultant polymerized material in order to enhance the properties of the orthopaedic composition.

80. A method of preparing an orthopaedic composition as set forth in claim 79, wherein said step of chemically bonding a sizing material to the fibers comprises using a technique selected from the group consisting of glow discharge induced reaction, ultraviolet induced reaction, free-radical induced reaction, and catalytic reaction.

81. A method of preparing an orthopaedic composition as set forth in claim 80, wherein glow discharge polymerization is employed to couple a sizing layer onto the surface of the fibers, said glow discharge polymerization being effected by exposing the surfaces of the fibers and the sizing material to an electromagnetic field at a frequency of 1 to 100 MHz at a power of at least 20 W per square centimeter of fiber surface area.

82. A method of preparing an orthopaedic composition as set forth in claim 81, wherein said composition is in the form of a bulk solid, and further including the steps of comminuting said bulk solid to form a particulate powder.

83. An orthopaedic composition, consisting essentially of:

an amount of a physiologically acceptable polymeric matrix material, said material selected from the group consisting of substituted acrylates and unsubstituted acrylates; and

a quantity of fibers disbursed in said matrix for enhancing functional qualities of the composition, said fibers having a layer of a sizing material thereover which is chemically joined to the surface of the fibers, said sizing material of the fibers also being chemically joined with the matrix material,

said fibers being present in said composition in an effective amount for reinforcing said matrix and having an average length of from about 1 μ

m to about 2 cm,

said fibers having a stiffness defined as the product of the tensile elastic modulus of the fibers and the area moment of inertia of the fibers, said stiffness being from about 1.0×

10^-13 to 150×

10^-13 Nm².