Hydrocarbon block copolymer with dispersed polysiloxane

• US 4,511,354 A
• Filed: 02/10/1983
• Issued: 04/16/1985
• Est. Priority Date: 05/07/1980
• Status: Expired due to Term

• Current Assignee: Klingel Family Corp. (Compagnie de Saint-Gobain SA)
• Original Assignee: Optical Research Associates (Synopsys Incorporated)
• Inventors: Sterling, Robert E.
• Primary Examiner(s): Yasko, John D.
• Assistant Examiner(s): Samaras, Harrie
• Application Number:
  US06/465,586
• Time in Patent Office: 796 Days
• Field of Search: 128/207.15, 604/96-103, 524/1, 524/314, 524/269, 524/574, 524/575
• US Class Current: 604/98.01
• CPC Class Codes: A61L 29/049 Mixtures of macromolecular compounds
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 53/025 modified
• CPC Class Codes: C08L 83/04 Polysiloxanes

Abstract

A composition of matter composed of a thermoplastic elastomeric hydrocarbon block copolymer having 0.1 to 8 percent polysiloxane, or silicone oil, uniformly distributed throughout. The composition exhibits improved surface, elasticity, and tensile strength characteristics as well as superior processibility. The block copolymer may take the form of styrene-ethylene-butylene-styrene in which the styrene blocks have a molecular weight of 5,000 to 40,000 and the ethylene-butylene block has a molecular weight of 20,000 to 500,000. Uniformly dispersed mineral oil may constitute 10 to 60 percent of the composition'"'"'s total weight which may also include less than 45 percent polypropylene. Combining the copolymer with the silicone oil occurs under the influence of a pressure of 1,500 to 2,500 p.s.i. such as provided by extrusion blending. The resulting elastomeric composition may extrude in sheets as thin as 0.015, 0.010, or even 0.005 inch, which a puller may thin even further. The resulting composition has a surface smoothness microscopically characteristic of silicone rubber. As one of its many varied uses, the elastomer may find use as an inflatable cuff or balloon on such medical devices as endotracheal tubes. The high elasticity of the composition permits it to act, when in the trachea, as a high residual volume type endotracheal tube, except that it avoids the folds which permit aspiration fluids to channel to the patient'"'"'s lungs. The pressure it exerts against the tracheal wall falls even below the high volume device. When not inflated, the material returns to a sufficiently small volume that it acts as a low volume device for ease of insertion and withdrawal.

Claims

1. An inflatable cuff in the form of a web surrounding a medical tubing, the ends of the web being sealed to said medical tubing to define an inflatable space, said cuff being formed of a composition comprising

an elastomeric, thermoplastic hydrocarbon block copolymer, said copolymer having a total molecular weight of about 50,000 to 600,000;

polysiloxane dispersed substantially uniformly throughout said copolymer, having a viscosity of about 20 to 13,000 centistokes, and comprising about 0.1 to 8 percent of the total weight of said composition; and

mineral oil dispersed substantially uniformly throughout said copolymer and comprising less than about 60 percent of the total weight of said composition.

2. The cuff of claim 1 wherein the composition further includes polypropylene dispersed substantially uniformly throughout said copolymer and comprising less than about 45 percent of the total weight of said composition.

3. The cuff of claim 2 wherein said block copolymer has an A--B--A configuration wherein A is a monovinylarene polymer block and B is a hydrogenated or nonhydrogenated conjugated diene polymer block.

4. The cuff of claim 3 wherein said block copolymer is a styrene-ethylene-butylene-styrene block copolymer;

said polysiloxane comprises about 1 to 7 percent of the total weight of said composition;

said mineral oil comprises about 25 to 50 percent of the total weight of said composition; and

said polypropylene comprises about 5 to 10 percent of the total weight of said composition.

5. The cuff of claim 4 wherein the styrene blocks of said copolymer have a molecular weight of about 8,000 to 20,000 and comprises about 20 to 35 percent of the total weight of said copolymer and the ethylene-butylene block has a molecular weight of about 20,000 to 500,000 and comprises about 65 to 80 percent of the total weight of said copolymer.

6. In a medical device having:

(A) an elongated hollow tube through which fluid can pass;

(B) an inflatable, fluid tight cuff sealed to and surrounding said tube and near the distal end of said tube; and

(C) pressure means for introducing an inflating fluid pressure into said cuff the improvement wherein at least a portion of said cuff is formed from an elastomeric composition comprising an elastomeric, thermoplastic, hydrocarbon block copolymer and polysiloxane substantially uniformly distributed throughout said copolymer.

7. The device of claim 6 wherein said copolymer is a styrene-ethylene-butylene-styrene block copolymer.

8. The device of claim 7 wherein:

(A) the styrene blocks of said copolymer have a molecular weight of about 5,000 to 40,000 and the ethylene-butylene block of said copolymer has a molecular weight of about 20,000 to 500,000; and

(B) said polysiloxane has a viscosity of about 20 to 13,000 centistokes.

9. The device of claim 8 further including mineral oil dispersed substantially uniformly throughout said copolymer and comprising about 25 to 60 percent of the total weight of said composition.

10. The device of claim 9 further including polypropylene distributed substantially uniformly throughout said copolymer and comprising about 2 to 20 percent of the total weight of said composition.

11. The device of claim 10 wherein said polysiloxane constitutes about 1 to 7 percent of the total weight of said composition.

12. The device of claim 11 wherein said device is an endotracheal tube.

13. The device of claim 12 wherein said cuff is formed at least in part from a web in the form of an extruded cylinder of material.

14. The device of claim 13 wherein said hollow tube is a plastic and is substantially rigid.

15. The device of claim 14 wherein (a) said plastic of said tube and said hydrocarbon polymer will wet each other and (b) a portion of said web is permanently sealed to said plastic by heat.

16. The device of claim 14 further including two sleeves of plastic material each sleeve surrounding one end of said cuff and wherein said sleeves each exerts a compressive force on said web against said tube on a continuous line surrounding said tube to hold said web onto said tube.

17. The device of claim 14 wherein said cuff is formed in part from said web and in part from said plastic with said web and said plastic held together over a portion of said web in a fluid-tight fashion to form a chamber.

18. The device of claim 17 wherein at least part of said web has a thickness no greater than 0.10 inch.

19. The device of claim 14 wherein said polypropylene comprises about 5 to 10 percent of the total weight of said composition.

20. The device of claim 19 wherein:

(A) said block copolymer has a total molecular weight in the range of about 50,000 to 600,000; and

(B) said polysiloxane has a viscosity of about 200 to 500 centistokes.

21. The device of claim 20 wherein said polysiloxane has the formula:

##STR6## wherein R₁, R₂ =H, CH₃ or ##STR7##

22. The device of claim 21 wherein the surface of said copolymer has a greater concentration of polysiloxane than the interior thereof.

23. The device of claim 22 wherein said elastomer has a surface characterized microscopically by a smoothness comparable to the surface of silicone rubber.

24. The device of claim 23 wherein said elastomer is substantially gas impermeable.

25. The device of claim 24 wherein said composition is elongatable in at least one direction to a stretched size of at least 500 percent of the unstretched size of said composition in said direction when no elongating force is applied to said composition, said composition remaining elastic when elongated to said stretched size.

26. The device of claim 7 wherein:

(A) the styrene blocks of said copolymer have a molecular weight of about 8,000 to 20,000 and the ethylene-butylene block of said copolymer has a molecular weight of about 20,000 to 200,000; and

(B) said polysiloxane has a viscosity of about 20 to 13,000 centistokes.

27. The device of claim 26 further including mineral oil dispersed substantially uniformly throughout said elastomer and comprising about 25 to 50 percent of the total weight of said elastomer.

28. The device of claim 27 further including polypropylene distributed substantially uniformly throughout said composition and comprising about 2 to 20 percent of the total weight of said composition.

29. The device of claim 28 wherein said device is an endotracheal tube.

30. The device of claim 29 wherein said composition is elongatable in at least one direction to a stretched size of at least 500 percent of the unstretched size of said composition in said direction when no elongating force is applied to said composition, said composition remaining elastic when elongated in said direction to said stretched size.

31. The method of fabricating a medical device comprising:

(A) placing a fluid-tight web forming from a thermoplastic composition comprising an elastomeric thermoplastic hydrocarbon block copolymer and polysiloxane substantially uniformly distributed throughout said copolymer (1) around an elongated hollow tube through which fluid can pas, said tube having fluid passage means for channeling the flow of fluid under pressure from one end of said tube to an area exterior of said tube and nearer the other end of said tube and (2) over said area of said tube; and

(B) sealing said web to said tube to provide a fluidtight chamber around and on the exterior of said tube, said chamber being (1) formed in part from said web and (2) in fluid communication with said fluid passage means.

32. The method of claim 31 wherein said copolymer is a styrene-ethylene-butylene-styrene block copolymer.

33. The method of claim 32 wherein:

(A) the styrene blocks of said copolymer have a molecular weight of about 5,0000 to 40,000 and the ethylene-butylene block of said copolymer has a molecular weight of about 20,000 to 500,000;

(B) said block copolymer has a total molecular weight in the range of about 50,000 to 600,000.

(C) said polysiloxane has a viscosity within the range of about 20 to 13,000 centistokes;

(D) said polysiloxane comprises 1 to 7 percent of the total weight of said compoition; and

(E) said composition further includes mineral oil and polypropylene dispersed substantially uniformly throughout said mineral oil comprising about 25 to 60 percent of the total weight of said composition and said polypropylene comprising about 2 to 20 percent of the total weight of said composition.

34. The method of claim 33 wherein said tube is a plastic and is substantially rigid.

35. The method of claim 34 wherein said web takes the form of an extruded cylinder of material.

36. The method of claim 35 further including, when said web and said plastic will wet each other, the step of applying sufficient heat to said web to melt a portion of said web and said plastic.

37. The method of claim 35 further including the step of placing at least two sleeves formed of heat shrinkable plastic around at least a portion of said web and said tube and applying sufficient heat to said sleeves to shrink said sleeves to a size where said sleeves exert a compressive force entirely around said web against said tube, one of said sleeves being placed on one side of said area and the other of said sleeves being placed on the other side of said area.

38. The method of claim 37 wherein at least part of each of said sleeves contact said tube and including the further step of, after the heat has been applied to said sleeves placing an adhesive at the junction of each of said sleeves and said tube.

39. The method of claim 35 wherein said metal tube is an endotracheal tube.

40. The method of claim 39 wherein said web has a thickness of no greater than 0.010 inch.

41. The method of claim 40 wherein:

(A) said polypropylene constitutes about 5 to 10 percent of the total weight of said composition; and

(B) the styrene blocks of said copolymer have a molecular weight in the range of about 8,000 to 20,000 and the ethylene-butylene block of said copolymer has a molecular weight of about 20,000 to 200,000.

42. The method of claim 41 wherein said polysiloxane has:

(A) a viscosity of about 200 to 500 centistokes

(B) been devolitilized;

(C) the formula;

##STR8## wherein R₁, R₂ =H CH₃ or ##STR9##

43. The method of claim 42 wherein said composition is substantially gas impermeable.

44. The method of claim 43 wherein said composition is elongatable in at least one direction to a stretched size of at least 500 percent of the unstretched size of said composition in said direction when no elongating force is applied to said composition, said composition remaining elastic when elongated in said direction to said stretched size.