Polysilocarb materials and methods

• US 9,815,943 B2
• Filed: 05/02/2014
• Issued: 11/14/2017
• Est. Priority Date: 03/15/2013
• Status: Active Grant

• Current Assignee: Melior Innovations, Inc.
• Original Assignee: Melior Innovations, Inc.
• Inventors: Sherwood, Walter, Land, Mark, Benac, Brian, Mueller, Michael, Keith, George, Wilding, Jr., Oliver, Dukes, Douglas
• Primary Examiner(s): MOORE, MARGARET G
• Application Number:
  US14/268,150
• Publication Number:
  US 20140274658A1
• Time in Patent Office: 1,292 Days
• CPC Class Codes: C04B 2235/3418 Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint glass constituents C04B2235/36
• CPC Class Codes: C04B 2235/3826 Silicon carbides
• CPC Class Codes: C04B 2235/44 Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
• CPC Class Codes: C04B 2235/48 Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
• CPC Class Codes: C04B 2235/483 Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
• CPC Class Codes: C04B 2235/528 Spheres
• CPC Class Codes: C04B 2235/5427 millimeter or submillimeter sized, i.e. larger than 0,1 mm
• CPC Class Codes: C04B 2235/5436 micrometer sized, i.e. from 1 to 100 micron
• CPC Class Codes: C04B 2235/6581 Total pressure below 1 atmosphere, e.g. vacuum
• CPC Class Codes: C04B 2235/77 Density
• CPC Class Codes: C04B 2235/96 Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
• CPC Class Codes: C04B 35/515 based on non-oxide ceramics
• CPC Class Codes: C04B 35/56 based on carbides or oxycarbides containing free metal binder C22C29/00
• CPC Class Codes: C04B 35/5603 with a well-defined oxygen content, e.g. oxycarbides
• CPC Class Codes: C04B 35/571 obtained from Si-containing polymer precursors or organosilicon monomers
• CPC Class Codes: C04B 35/64 Burning or sintering processes C04B33/32 takes precedence ; powder metallurgy B22F
• CPC Class Codes: C04B 35/80 Fibres, filaments, whiskers, platelets, or the like
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/50 by carbon linkages C08G77/485 takes precedence
• CPC Class Codes: C08L 83/00 : Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 : Polysiloxanes
• CPC Class Codes: C09K 8/80 : Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open

Abstract

Silicon (Si) based materials and methods of making those materials. More specifically, methods and materials having silicon, oxygen and carbon that form filled and unfilled plastic materials and filled and unfilled ceramics.

Claims

1. A solvent free method for making a ceramic material, the method comprising:

a. mixing a first liquid polysilocarb precursor with a second liquid precursor in the absence of a solvent to form a solvent free liquid polysilocarb precursor formulation;

wherein the first liquid polysilocarb precursor is a linear polymer having a backbone of —

[Si—

O]—

repeating units, a molecular weight of about 400 to about 1,000, and a viscosity of about 20 to 40 cps at 25°

C.;

whereby the first liquid polysilocarb precursor is not chemically reacted with the second liquid precursor;

b. curing the polysilocarb precursor formulation into a hard cured neat solid material having no reinforcements, whereby the first liquid polysilocarb precursor and the second liquid precursor chemically react to form the hard cured solid material, whereby none of the polysilocarb precursor formulation remains as a liquid;

c. pyrolyzing the hard cured solid material in an inert atmosphere to form a ceramic material consisting essentially of silicon, oxygen and carbon; and

,

d. wherein the process of steps a. through c. is performed in absence of a solvent.

2. The method of claim 1, wherein the first liquid precursor is methyl hydrogen fluid.

3. The method of claim 1, wherein the first liquid precursor is a methyl terminated hydride substituted polysiloxane.

4. The method of claim 1, wherein the first liquid precursor is selected from the group consisting of a methyl terminated vinyl polysiloxane, a vinyl terminated vinyl polysiloxane, a hydride terminated vinyl polysiloxane, and an allyl terminated dimethyl polysiloxane.

5. The method of claim 1, wherein the first liquid precursor is selected from the group consisting of a vinyl terminated dimethyl polysiloxane, a hydroxy terminated dimethyl polysiloxane, a hydride terminated dimethyl polysiloxane, and a hydroxy terminated vinyl polysiloxane.

6. The method of claim 1, wherein the first liquid precursor is selected from the group consisting of a phenyl terminated dimethyl polysiloxane, a phenyl and methyl terminated dimethyl polysiloxane, a methyl terminated dimethyl diphenyl polysiloxane, a vinyl terminated dimethyl diphenyl polysiloxane, a hydroxy terminated dimethyl diphenyl polysiloxane, and a hydride terminated dimethyl diphenyl polysiloxane.

7. The method of claim 1, wherein the second liquid precursor is selected from the group consisting of a methyl terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane, and a divinyl cyclosiloxane.

8. The method of claim 1, wherein the second liquid precursor is selected from the group consisting of a trivinyl hydride cyclosiloxane, a divinyl dihydride cyclosiloxane, and a dihydride cyclosiloxane.

9. The method of claim 1, wherein the second liquid precursor is a silane.

10. The method of claim 1, wherein the second liquid precursor is selected from the group consisting of a methyl terminated dimethyl ethyl methyl phenyl silyl silane, an ethyl methyl phenyl silyl-cyclosiloxane, a cyclosiloxane and an orthosilicate.

11. The method of claim 1, wherein the first liquid precursor is methyl hydrogen fluid;

and wherein the second liquid precursor is selected from the group consisting of a methyl terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane, and a divinyl cyclosiloxane.

12. The method of claim 1, wherein the first liquid precursor is a methyl terminated hydride substituted polysiloxane;

and wherein the second liquid precursor is selected from the group consisting of a methyl terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane, and a divinyl cyclosiloxane.

13. The method of claim 1, wherein the first liquid precursor is selected from the group consisting of a methyl terminated vinyl polysiloxane, a vinyl terminated vinyl polysiloxane, a hydride terminated vinyl polysiloxane, and an allyl terminated dimethyl polysiloxane;

and, wherein the second liquid precursor is selected from the group consisting of a methyl terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane, a divinyl cyclosiloxane, a trivinyl hydride cyclosiloxane, a divinyl dihydride cyclosiloxane, a dihydride cyclosiloxane, a silane, a methyl terminated dimethyl ethyl methyl phenyl silyl silane, an ethyl methyl phenyl silyl-cyclosiloxane, a cyclosiloxane and an orthosilicate.

14. The method of claim 1, wherein the first liquid precursor is selected from the group consisting of a vinyl terminated dimethyl polysiloxane, a hydroxy terminated dimethyl polysiloxane, a hydride terminated dimethyl polysiloxane, and a hydroxy terminated vinyl polysiloxane and, wherein the second liquid precursor is selected from the group consisting of a methyl terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane, a divinyl dihydride cyclosiloxane, a dihydride cyclosiloxane, a silane, a methyl terminated dimethyl ethyl methyl phenyl silyl silane, an ethyl methyl phenyl silyl-cyclosiloxane, a cyclosiloxane and an orthosilicate.

15. The method of claim 1, wherein the first liquid precursor is selected from the group consisting of a phenyl terminated dimethyl polysiloxane, a phenyl and methyl terminated dimethyl polysiloxane, a methyl terminated dimethyl diphenyl polysiloxane, a vinyl terminated dimethyl diphenyl polysiloxane, a hydroxy terminated dimethyl diphenyl polysiloxane, and a hydride terminated dimethyl diphenyl polysiloxane and, wherein the second liquid precursor is selected from the group consisting of a methyl terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane, a divinyl cyclosiloxane, a trivinyl hydride cyclosiloxane, a divinyl dihydride cyclosiloxane, a dihydride cyclosiloxane, a silane, a cyclosiloxane and an orthosilicate.

67. The method of claim 1, wherein the first precursor is selected from the group consisting of methyl hydrogen, siloxane backbone additive, vinyl substituted and vinyl terminated polydimethyl siloxane, vinyl substituted and hydrogen terminated polydimethyl siloxane, allyl terminated polydimethyl siloxane, silanol terminated polydimethyl siloxane, hydrogen terminated polydimethyl siloxane, vinyl terminated diphenyl dimethyl polysiloxane, hydroxyl terminated diphenyl dimethyl polysiloxane, hydride terminated diphenyl dimethyl polysiloxane, and styrene vinyl benzene dimethyl polysiloxane.

16. A solvent free method for making a neat ceramic material, the method comprising:

a. preparing a mixture, the mixture consisting of liquid reactive precursors, the reactive precursors comprising a first liquid polysilocarb precursor and a second liquid precursor in the absence of a solvent to form a solvent free liquid polysilocarb precursor formulation;

wherein the first liquid polysilocarb precursor is a linear polymer, whereby the first liquid polysilocarb precursor is not chemically reacted with the second liquid precursor;

b. curing the mixture into a neat solid material having no reinforcements, whereby the first liquid polysilocarb precursor and the second liquid precursor chemically react to form the neat solid material, whereby none of the mixture remains as a liquid; and

,

c. pyrolyzing the neat solid material in an inert atmosphere to form a neat ceramic material comprising silicon, oxygen and carbon.

17. The method of claim 16, wherein the pyrolysis is conducted under a reduced pressure atmosphere.

18. The method of claim 17, wherein the reduced pressure atmosphere is a vacuum.

19. The method of claim 16, wherein the first liquid precursor is methyl hydrogen fluid.

20. The method of claim 16, wherein the first liquid precursor is a methyl terminated hydride substituted polysiloxane.

21. The method of claim 18, wherein the first liquid precursor is selected from the group consisting of a methyl terminated vinyl polysiloxane, a vinyl terminated vinyl polysiloxane, a hydride terminated vinyl polysiloxane, and an allyl terminated dimethyl polysiloxane.

22. The method of claim 16, wherein the first liquid precursor is selected from the group consisting of a vinyl terminated dimethyl polysiloxane, a hydroxy terminated dimethyl polysiloxane, a hydride terminated dimethyl polysiloxane, and a hydroxy terminated vinyl polysiloxane.

23. The method of claim 18, wherein the first liquid precursor is selected from the group consisting of a phenyl terminated dimethyl polysiloxane, a phenyl and methyl terminated dimethyl polysiloxane, a methyl terminated dimethyl diphenyl polysiloxane, a vinyl terminated dimethyl diphenyl polysiloxane, a hydroxy terminated dimethyl diphenyl polysiloxane, and a hydride terminated dimethyl diphenyl polysiloxane.

24. The method of claim 16, wherein the second liquid precursor is selected from the group consisting of a methyl terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane, and a divinyl cyclosiloxane.

25. The method of claim 16, wherein the second liquid precursor is selected from the group consisting of a trivinyl hydride cyclosiloxane, a divinyl dihydride cyclosiloxane, and a dihydride cyclosiloxane.

26. The method of claim 16, wherein the second liquid precursor is a silane.

27. The method of claim 18, wherein the second liquid precursor is selected from the group consisting of a methyl terminated dimethyl ethyl methyl phenyl silyl silane, an ethyl methyl phenyl silyl-cyclosiloxane, a cyclosiloxane and an orthosilicate.

28. The method of claim 16, wherein the first liquid precursor is methyl hydrogen fluid;

and wherein the second liquid precursor is selected from the group consisting of a methyl terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane, and a divinyl cyclosiloxane.

29. The method of claim 16, wherein the first liquid precursor is a methyl terminated hydride substituted polysiloxane;

and wherein the second liquid precursor is selected from the group consisting of a methyl terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane, and a divinyl cyclosiloxane.

30. The method of claim 16, wherein the first liquid precursor is selected from the group consisting of a methyl terminated vinyl polysiloxane, a vinyl terminated vinyl polysiloxane, a hydride terminated vinyl polysiloxane, and an allyl terminated dimethyl polysiloxane;

and, wherein the second liquid precursor is selected from the group consisting of a methyl terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane, a divinyl cyclosiloxane, a trivinyl hydride cyclosiloxane, a divinyl dihydride cyclosiloxane, a dihydride cyclosiloxane, a silane, a methyl terminated dimethyl ethyl methyl phenyl silyl silane, an ethyl methyl phenyl silyl-cyclosiloxane, a cyclosiloxane and an orthosilicate.

31. The method of claim 16, wherein the first liquid precursor is selected from the group consisting of a vinyl terminated dimethyl polysiloxane, a hydroxy terminated dimethyl polysiloxane, a hydride terminated dimethyl polysiloxane, and a hydroxy terminated vinyl polysiloxane and, wherein the second liquid precursor is selected from the group consisting of a methyl terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane, a divinyl dihydride cyclosiloxane, a dihydride cyclosiloxane, a silane, a methyl terminated dimethyl ethyl methyl phenyl silyl silane, an ethyl methyl phenyl silyl-cyclosiloxane, a cyclosiloxane and an orthosilicate.

32. The method of claim 16, wherein the first liquid precursor is selected from the group consisting of a phenyl terminated dimethyl polysiloxane, a phenyl and methyl terminated dimethyl polysiloxane, a methyl terminated dimethyl diphenyl polysiloxane, a vinyl terminated dimethyl diphenyl polysiloxane, a hydroxy terminated dimethyl diphenyl polysiloxane, and a hydride terminated dimethyl diphenyl polysiloxane and, wherein the second liquid precursor is selected from the group consisting of a methyl terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane, a divinyl cyclosiloxane, a trivinyl hydride cyclosiloxane, a divinyl dihydride cyclosiloxane, a dihydride cyclosiloxane, a silane, a cyclosiloxane and an orthosilicate.

33. The methods of claim 16, wherein the neat ceramic material is a spherical bead shaped.

34. The methods of claim 17, wherein the neat ceramic material is sheet shaped.

35. The method of claim 18, wherein the neat ceramic material is a spherical bead shaped.

36. The method of claim 16, wherein the solvent free liquid polysilocarb precursor formulation contains hydride groups.

37. The method of claim 18, wherein the solvent free liquid polysilocarb precursor formulation contains hydride groups.

38. The method of claim 19, wherein the solvent free liquid polysilocarb precursor formulation contains hydride groups.

39. The method of claim 20, wherein the solvent free liquid polysilocarb precursor formulation contains hydride groups.

40. The method of claim 27, wherein the solvent free liquid polysilocarb precursor formulation contains hydride groups.

41. The method of claim 16, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups.

42. The method of claim 17, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups.

43. The method of claim 19, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups.

44. The method of claim 20, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups.

45. The method of claim 21, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups.

46. The method of claim 22, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups.

47. The method of claim 27, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups.

48. The method of claim 16, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups and hydride groups.

49. The method of claim 17, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups and hydride groups.

50. The method of claim 18, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups and hydride groups.

51. The method of claim 19, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups and hydride groups.

52. The method of claim 20, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups and hydride groups.

53. The method of claim 21, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups and hydride groups.

54. The method of claim 22, wherein the solvent free liquid polysilocarb precursor formulation contains vinyl groups and hydride groups.

55. The method of claim 48, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 1.50 to 1.

56. The method of claim 48, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 3.93 to 1.

57. The method of claim 48, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 5.93 to 1.

58. The method of claim 48, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 0.08 to 1 to about 24.00 to 1.

59. The method of claim 48, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 2.03 to 1 to about 24.00 to 1.

60. The method of claim 48, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 3.93 to 1 to about 24.00 to 1.

61. The method of claim 48, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 0.08 to 1 to about 1.82 to 1.

62. The method of claim 48, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 1.12 to 1 to about 2.36 to 1.

63. The method of claim 48, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 1.75 to 1 to about 23.02 to 1.

64. The method of claim 48, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 1.50 to 1 to about 3.93 to 1.

65. The method of claim 48, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 1.26 to 1 to about 4.97 to 1.

66. The method of claim 48, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 0.08 to 1 to about 1.50 to 1.

68. The method of claim 16, wherein the first precursor is selected from the group consisting of methyl hydrogen, siloxane backbone additive, vinyl substituted and vinyl terminated polydimethyl siloxane, vinyl substituted and hydrogen terminated polydimethyl siloxane, allyl terminated polydimethyl siloxane, silanol terminated polydimethyl siloxane, hydrogen terminated polydimethyl siloxane, vinyl terminated diphenyl dimethyl polysiloxane, hydroxyl terminated diphenyl dimethyl polysiloxane, hydride terminated diphenyl dimethyl polysiloxane, and styrene vinyl benzene dimethyl polysiloxane.

69. A neat ceramic material made by the process of claim 16.

70. A method for making a neat ceramic material, the method comprising:

a. mixing a first liquid polysilocarb precursor with a second liquid precursor in the absence of a solvent to form a solvent free liquid polysilocarb precursor formulation;

wherein the first liquid polysilocarb precursor is a linear polymer, whereby the first liquid polysilocarb precursor is not chemically reacted with the second liquid precursor, wherein the liquid polysilocarb precursor formulation consists essentially of the first and second liquid precursors;

b. wherein the first liquid comprises a vinyl terminated polysiloxane and the second liquid comprises a reaction cross-linkable group, wherein the cross-linkable group is selected form the group consisting of hydride groups and vinyl groups;

c. curing the polysilocarb precursor formulation at temperature of 650°

C. or less, for at least about 2 hours, into a neat hard cure solid material having no reinforcements, whereby the first liquid polysilocarb precursor and the second liquid precursor chemically react to form the neat solid material, whereby none of the precursor formulation remains as a liquid;

d. pyrolyzing the solid material, in a reduced pressure inert atmosphere, at temperatures of from about 650°

C. to about 1,200°

C. to form a neat ceramic material consisting essentially of carbon, silicon and oxygen; and

,

e. wherein the process steps of a through d are performed in absence of a solvent.

71. The method of claim 70, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 3.93 to 1.

72. The method of claim 70, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 5.93 to 1.

73. The method of claim 70, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 0.08 to 1 to about 24.00 to 1.

74. The method of claim 70, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 2.03 to 1 to about 24.00 to 1.

75. The method of claim 70, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 3.93 to 1 to about 24.00 to 1.

76. The method of claim 70, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 0.08 to 1 to about 1.82 to 1.

77. The method of claim 70, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 1.12 to 1 to about 2.36 to 1.

78. A method for making a ceramic material, the method comprising:

a. mixing a first liquid polysilocarb precursor with a second liquid precursor in the absence of a solvent to form a solvent free liquid polysilocarb precursor formulation;

wherein the first liquid polysilocarb precursor is a linear polymer, having a backbone of —

[Si—

O]—

repeating units, whereby the liquid polysilocarb precursor formulation remains stable and will not chemically react at room temperature for more than a week;

b. wherein the first liquid comprises a vinyl terminated polysiloxane and the second liquid comprises a reaction cross-linkable group;

c. curing the polysilocarb precursor formulation at temperature of 650°

C. or less, for at least about 2 hours, into a hard cure solid neat material having no reinforcements whereby the first liquid polysilocarb precursor and the second liquid precursor chemically react to form the solid material, and whereby none of the precursor formulation remains as a liquid; and

,

d. pyrolyzing the solid material, in a reduced pressure inert atmosphere, at temperatures of from about 650°

C. to about 1,200°

C. to form a ceramic material consisting essentially of carbon, silicon and oxygen.

79. The method of claim 78, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 3.93 to 1.

80. The method of claim 78, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 5.93 to 1.

81. The method of claim 78, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 0.08 to 1 to about 24.00 to 1.

82. The method of claim 78, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 2.03 to 1 to about 24.00 to 1.

83. The method of claim 78, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 3.93 to 1 to about 24.00 to 1.

84. The method of claim 78, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 0.08 to 1 to about 1.82 to 1.

85. The method of claim 78, wherein the molar ratio of hydride groups to vinyl groups in the formulation is about 1.12 to 1 to about 2.36 to 1.