Polymer and inorganic-organic hybrid composites and methods for making same

• US 5,977,241 A
• Filed: 04/04/1997
• Issued: 11/02/1999
• Est. Priority Date: 02/26/1997
• Status: Expired due to Term

• Current Assignee: Integument Technologies, Inc.
• Original Assignee: Integument Technologies, Inc.
• Inventors: Koloski, Timothy S., Vargo, Terrence G.
• Primary Examiner(s): MERRIAM, ANDREW EDWIN
• Application Number:
  US08/833,290
• Time in Patent Office: 942 Days
• Field of Search: 524/403, 524/430, 524/433, 524/439, 524/520, 524/544, 524/546, 524/431, 524/515, 524/502, 428/319.1, 428/319.3, 525/903, 528/490, 528/502 R
• US Class Current: 524/502
• CPC Class Codes: C08F 283/00 Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
• CPC Class Codes: C09D 5/1612 Non-macromolecular compounds
• CPC Class Codes: H01M 4/667 in the form of layers, e.g. coatings
• CPC Class Codes: H01M 50/409 Separators, membranes or diaphragms characterised by the material
• CPC Class Codes: H01M 8/1004 characterised by membrane-electrode assemblies [MEA] H01M8/12 takes precedence
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y10S 525/903 Interpenetrating network
• CPC Class Codes: Y10T 428/24999 Inorganic
• CPC Class Codes: Y10T 428/249991 Synthetic resin or natural rubbers

Abstract

Composites which include a polymer matrix having natural free volume therein and an inorganic or organic material disposed in the natural free volume of the polymer matrix are disclosed. In addition, methods for making a composite are described. A polymer matrix having free volume therein is provided. The free volume is evacuated, and inorganic or organic molecules are infused into the evacuated free volume of the polymer matrix. The inorganic or organic molecules can then be polymerized under conditions effective to cause the polymerized inorganic or organic molecules to assemble into macromolecular networks. Alternatively, where the polymer matrix contains a functionality, the inorganic or organic molecules can be treated underconditions effective to cause the inorganic or organic molecules to interact with the polymer matrix'"'"'s functionality. Use of the disclosed composites as photoradiation shields and filters, electromagnetic radiation shields and filters, antistatic layers, heterogeneous catalytic substrates, conducting electrodes, materials having flame and heat retardant properties, and components in the construction of electrolytic cells, fuel cells, and optoelectronic devices is also described.

Claims

1. A composite comprising:

a polymer matrix having natural free volume therein; and

an inorganic or organic material disposed in the natural free volume of said polymer matrix, wherein said polymer matrix is at least partially amorphous and wherein said polymer matrix comprises a halopolymer.

2. A composite according to claim 1, wherein said natural free volume contains substantially no carrier liquid.

3. A composite according to claim 1, wherein the natural free volume is defined by free volume surfaces and wherein said inorganic or organic material is present as a layer on or along the free volume surfaces.

4. A composite according to claim 1, wherein said polymer matrix comprises a functionality selected from the group consisting of a halogen atom, an amine group, an alkene group, an alkyne group, a carbonyl group, an alcohol group, a thiol group, and combinations thereof.

5. A composite according to claim 4, wherein the functionality is a halogen atom.

6. A composite according to claim 4, wherein the functionality is a fluorine atom.

7. A composite according to claim 4, wherein said inorganic or organic material is an inorganic or organic macromolecular network.

8. A composite according to claim 7, wherein the inorganic or organic macromolecular network is an inorganic macromolecular network.

9. A composite according to claim 7, wherein the inorganic macromolecular network has the formula (X(O)_n --O_y --X(O)_n)_m, wherein m is an integer from about 1 to about 10,000;

X represents a metal ion having a charge of +s;

s is an integer from 1 to the metal'"'"'s highest attainable oxidation state;

y is an integer from 0 to s; and

n is between zero and s/2.

10. A composite according to claim 1, wherein said inorganic or organic material is a metal network containing a Group IIIa, IVa, Va, VIa, or VIIa metal or a metal selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt.

11. A composite according to claim 7, wherein the inorganic or organic macromolecular network is an organic macromolecular network.

12. A composite according to claim 11, wherein the organic macromolecular network has the formula .paren open-st.R--R.paren close-st._n, wherein n is an integer from about 1 to about 10,000 and R is a monomer radical.

13. A composite according to claim 11, wherein the organic macromolecular network comprises polyacetylene, polypyrrole, polyaniline, polythiophene, or combinations thereof.

14. A composite according to claim 1, wherein said polymer matrix comprises a fluoropolymer.

15. A composite according to claim 1, wherein said polymer matrix has a crystallinity of less than about 99%.

16. A composite according to claim 1 having a volume of V_c, wherein the natural free volume is greater than about 1×

10^-6 V_c.

17. A composite according to claim 1, wherein said inorganic or organic material is an inorganic material comprising a metal selected from the group consisting of V, W, Fe, Ti, Si, Al, P, Sb, As, Ba, B, Cd, Ca, Ce, Cs, Cr, Co, Cu, Ga, Ge, In, Pb, Mg, Hg, Mo, Ni, Nb, Re, Ta, Tl, Sn, Ir, Rh, Th, Ru, Os, Pd, Pt, Zn, Au, Ag, and combinations thereof.

38. A method for making a composite according to claim 1, said method comprising:

providing a polymer matrix having natural free volume therein, wherein the polymer matrix is at least partially amorphous and wherein the polymer matrix comprise a halopolymer;

evacuating the natural free volume of the polymer matrix; and

infusing inorganic or organic molecules into the evacuated natural free volume of the polymer matrix.

39. A method according to claim 38 further comprising:

polymerizing the inorganic or organic molecules under conditions effective to assemble the inorganic or organic molecules into macromolecular networks.

40. A method according to claim 39, wherein said polymerizing is carried out photochemically, chemically, or electrochemically.

41. A method according to claim 39, wherein said polymerizing is carried out by oxidizing, hydrolyzing, or hydrogenating the inorganic or organic molecules.

42. A method according to claim 41 wherein the oxidizing, hydrolyzing, or hydrogenating comprises:

exposing the inorganic or organic molecules to a gas comprising water, oxygen, hydrogen, or combination thereof.

43. A method according to claim 42, wherein said polymerizing is carried out by oxidizing or hydrolyzing the inorganic or organic molecules and wherein the gas ia ambient air.

44. A method according to claim 39, wherein the inorganic or organic molecules are inorganic molecules comprising metal atoms and ligands bonded thereto which can be cleaved from the metal atoms by exposure to actinic radiation and wherein said polymerizing comprises:

exposing the inorganic molecules to actinic radiation under conditions effective to cleave the ligands from the metal atoms and

exposing the metal atoms having ligands cleaved therefrom to an oxygen-containing or water-containing gas under conditions effective to cause the metal atoms to assemble into macromolecular networks.

45. A method according to claim 38, wherein the inorganic or organic molecules are pi-allyl compounds of a Group IIIa, IVa, Va, or VIIa metals or a metal selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, or Pt and wherein said polymerizing comprises:

contacting the pi-allyl compounds with hydrogen gas under conditions effective to cause the formation of a conductive metal network.

46. A method according to claim 38, wherein the polymer matrix comprises a functionality selected from the group consisting of a halogen atom, an amine group, an alkene group, an alkyne group, a carbonyl group, an alcohol group, a thiol group, and combinations thereof and wherein said method further comprises:

treating the inorganic or organic molecules under conditions effective to cause the inorganic or organic molecules to interact with the polymer matrix'"'"'s functionality.

47. A method according to claim 46, wherein the functionality is a halogen atom.

48. A method according to claim 46, wherein the functionality is a fluorine atom.

49. A method according to claim 46, wherein said treating is carried out photochemically, chemically, or electrochemically.

50. A method according to claim 46, wherein said treating comprises oxidizing, hydrolyzing, or hydrogenating the inorganic or organic molecules.

51. A method according to claim 50, wherein the oxidizing, hydrolyzing, or hydrogenating comprises:

exposing the inorganic or organic molecules to a gas comprising water, oxygen, hydrogen, or combination thereof.

52. A method according to claim 51, wherein said treating is carried out by oxidizing of hydrolyzing the inorganic or organic molecules and wherein the gas is ambient air.

53. A method according to claim 46, wherein the inorganic or organic molecules are inorganic molecules comprising metal atoms and ligands bonded thereto which can be cleaved from metal atoms by exposure to actinic radiation and wherein said treating comprises:

exposing the inorganic or organic molecules to actinic radiation under conditions effective to cleave the ligands from the metal atoms and

treating the metal atoms having ligands cleaved therefrom photochemically, chemically, electrochemically, or thermally under conditions effective to cause the metal atoms to interact with the polymer matrix'"'"'s functionality.

54. A method according to claim 38, wherein said infusing is carried out under non-supercritical conditions.

55. A method according to claim 38, wherein the inorganic or organic molecules are infused into natural free volume of the polymer matrix in a gaseous state.

56. A method according to claim 38, wherein said infusing comprises:

vaporizing the inorganic or organic molecules to produce an inorganic or organic molecule vapor; and

contacting the polymer matrix with the inorganic or organic molecule vapor.

57. A method according to claim 38, wherein the polymer matrix comprises a fluoropolymer.

58. A method according to claim 38, wherein the polymer matrix has a crystallinity of less than about 99%.

59. A method according to claim 38, wherein the polymer matrix has a glass transition temperature to Tg and a thermal decomposition temperature of Td and wherein said infusing is carried out at a temperature from about Tg-50°

C. to about Td and at which the inorganic or organic molecules have a non-zero vapor pressure.

60. A method according to claim 38, wherein the inorganic or organic molecules are selected from the group consisting of VOCl₃, W(CO)₆, Fe(CO)₅,TiCl₄, SiCl₄, AlCl₃, PCl₃, SbCl₅, As(C₂ H₅)₃, Ba(C₃ H₇)₂, borane pyridine and tetrahydrofuran complexes, Cd(BF₄)₂, Ca(OOCCH(C₂ H₅)C₄ H₉)₂, cerium (III) 2-ethylhexanoate, cesium 2-ethylhexoxide, chromium (III) naphthenate, CrO₂ Cl₂, Co(CO)₃ NO, copper (II) dimethylaminoethoxide, triethylgallium, GeCl₄, triethylindium, lead naphthenate, C₂ H₅ MgCl, (CH₃)₂ Hg, MoF₆, Ni(CO)₄, Nb(OC₂ H₅)₆, HReO₄, Ta(OC₂ H₅)₅, C₅ H₅ Tl, SnCl₄, pi-allyl compounds of Group IIIa, IVa, Va, VIa, or VIIa metals, pi-allyl compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, or Pt, and combination thereof.

61. A method of catalyzing a reaction of a reactant comprising:

providing a composite according to claim 1, wherein the inorganic or organic material is suitable for catalyzing the reaction of the reactant; and

contacting the composite with the reactant under conditions effective to catalyze the reaction.

62. A method according to claim 61, wherein the reactant is a gaseous reactant.

63. A method according to claim 62, wherein the reactant is SO₂ and the inorganic or organic material is an inorganic macromolecular network comprising vanadium.

64. A electroconductive imaging element comprising:

an insulating support;

an electrically-conductive layer overlaying the support, wherein said electrically-conductive layer comprises a composite of claim 1; and

a dielectric imaging layer overlaying the electrically-conductive layer.

65. A photographic element comprising:

a substrate;

a light-sensitive layer directly or indirectly disposed on the substrate; and

an antistatic layer directly or indirectly disposed on the substrate, wherein the antistatic layer comprises a composite of claim 1.

66. A electrolytic fuel cell comprising:

a composite of claim 1;

an anode in electrical contact with said composite; and

a cathode in electrical contact with said composite.

67. A method for shielding a material from electromagnetic radiation emitted from an electromagnetic radiation source comprising:

disposing between the material and the electromagnetic radiation source a composite according to claim 1, wherein the inorganic or organic material comprises a metal.

68. A method for shielding a material from heat or flame source comprising:

disposing between the material and the heat or flame source a composite according to claim 1, wherein the inorganic or organic material is a metal oxide.

18. A composite comprising:

a polymer matrix having natural free volume therein; and

an inorganic or organic material disposed in the natural free volume of said polymer matrix, wherein said polymer matrix is at least partially amorphous, wherein said polymer matrix is an organic polymer matrix, and wherein said inorganic or organic material is an inorganic or organic macromolecular network.

19. A composite according to claim 18, wherein said natural free volume contains substantially no carrier liquid.

20. A composite according to claim 18, wherein the natural free volume is defined by free volume surfaces and wherein said inorganic or organic material is present as a layer on or along the free volume surfaces.

21. A composite according to claim 18, wherein said polymer matrix comprises a functionality selected from the group consisting of a halogen atom, an amine group, an alkene group, an alkyne group, a carbonyl group, an alcohol group, a thiol group, and combinations thereof.

22. A composite according to claim 21, wherein the functionality is a halogen atom.

23. A composite according to claim 21, wherein the functionality is a fluorine atom.

24. A composite according to claim 18, wherein the inorganic or organic macromolecular network is an inorganic macromolecular network.

25. A composite according to claim 24, wherein the inorganic macromolecular network has the formula (X(O)_n --O_y --X(O)_n)_m, wherein m is an integer from about 1 to about 10,000;

X represents a metal ion having a charge of +s;

s is an integer from 1 to the metal'"'"'s highest attainable oxidation state;

y is an integer from 0 to s; and

n is between zero and s/2.

26. A composite according to claim 24, wherein said inorganic or organic material is a metal network containing a Group IIIa, IVa, Va, VIa, or VIIa metal or a metal selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt.

27. A composite according to claim 18, wherein the inorganic or organic macromolecular network is an organic macromolecular network.

28. A composite according to claim 27, wherein the organic macromolecular network has the formula .paren open-st.R--R.paren close-st._n, wherein n is an integer from about 1 to about 10,000 and R is a monomer radical.

29. A composite according to claim 27, wherein the organic macromolecular network comprises polyacetylene, polypyrrole, polyaniline, polythiophene, or combinations thereof.

30. A composite according to claim 18, wherein said polymer matrix comprises halopolymers, polyimides, polyamides, polyalkylenes, poly(phenylenediamine terephthalamide) filaments, polyethyleneterphthalates, modified cellulose derivatives, starch, polyesters, polymethacrylates, polyacrylates, polyvinyl alcohol, copolymers of vinyl alcohol with ethylenically unsaturated monomers, polyvinyl acetate, poly(alkylene oxides), vinyl chloride homopolymers and copolymers, terpolymers of ethylene with carbon monoxide and with an acrylic acid ester or vinyl monomer, polysiloxanes, homopolymers and copolymers of halodioxoles and substituted dioxoles, polyvinylpyrrolidone, or combinations thereof.

31. A composite according to claim 18, wherein said polymer matrix comprises a halopolymer.

32. A composite according to claim 31, wherein said polymer matrix comprises a fluoropolymer.

33. A composite according to claim 18, wherein said polymer matrix has a crystallinity of less than about 99%.

34. A composite according to claim 18 having a volume of V_c, wherein the natural free volume is greater than about 1×

10^-6 V_c.

35. A composite according to claim 18, wherein said inorganic or organic material is an inorganic material comprising a metal selected from the group consisting of V, W, Fe, Ti, Si, Al, P, Sb, As, Ba, B, Cd, Ca, Ce, Cs, Cr, Co, Cu, Ga, Ge, In, Pb, Mg, Hg, Mo, Ni, Nb, Re, Ta, Tl, Sn, Ir, Rh, Th, Ru, Os, Pd, Pt, Zn, Au, Ag, and combinations thereof.

69. A method for making a composite according to claim 18, said method comprising:

providing a polymer matrix having natural free volume therein, wherein the polymer matrix is at least partially amorphous and wherein the polymer matrix is an organic polymer matrix;

evacuating the natural free volume of the polymer matrix;

infusing inorganic or organic molecules into the evacuated natural free volume of the polymer matrix; and

polymerizing the inorganic or organic molecules under conditions effective to assemble the inorganic or organic molecules into a macromolecular network.

70. A method according to claim 69, wherein said polymerizing is carried out photochemically, chemically, or electrochemically.

71. A method according to claim 69, wherein said polymerizing is carried out by oxidizing, hydrolyzing, or hydrogenating the inorganic or organic molecules.

72. A method according to claim 71, wherein the oxidizing, hydrolyzing, or hydrogenating comprises:

exposing the inorganic or organic molecules to a gas comprising water, oxygen, hydrogen, or combinations thereof.

73. A method according to claim 72, wherein said treating is carried out by oxidizing of hydrolyzing the inorganic or organic molecules and wherein the gas is ambient air.

74. A method according to claim 69, wherein the inorganic or organic molecules are inorganic molecules comprising metal atoms and ligands bonded thereto which can be cleaved from metal atoms by exposure to actinic radiation and wherein said treating comprises:

exposing the inorganic or organic molecules to actinic radiation under conditions effective to cleave the ligands from the metal atoms and

exposing the metal atoms having ligands cleaved therefrom to an oxygen-containing or water-containing gas under conditions effective to cause the metal atoms to assemble into macromolecular networks.

75. A method according to claim 69, wherein the inorganic or organic molecules are pi-allyl compounds of a Group IIIa, IVa, Va, or VIIa metals or a metal selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, or Pt and wherein said polymerizing comprises:

contacting the pi-allyl compounds with hydrogen gas under conditions effective to cause the formation of a conductive metal network.

76. A method according to claim 69, wherein said infusing is carried out under non-supercritical conditions.

77. A method according to claim 69, wherein the inorganic or organic molecules are infused into the natural free volume of the polymer matrix in a gaseous state.

78. A method according to claim 69, wherein said infusing comprises:

vaporizing the inorganic or organic molecules to produce an inorganic or organic molecule vapor; and

contacting the polymer matrix with the inorganic or organic molecule vapor.

79. A method according to claim 69, wherein the polymer matrix comprises halopolymers, polyimides, polymides, polyalkylenes, poly(phenylenediamine terephthalamide) filaments, polyethyleneterphthalates, modified cellulose derivatives, starch, polyesters, polymethacrylates, polyacrylates, polyvinyl alcohol, copolymers of vinyl alcohol with ethylenically unsaturated monomers, polyvinyl acetate, poly(alkylene oxides), vinyl chloride homopolymers and copolymers, terpolymers of ethylene with carbon monoxide and with an acrylic acid ester or vinyl monomer, polysiloxanes, homopolymers, and copolymers of halodioxoles and substituted dioxoles, polyvinylpyrrolidone, or combination thereof.

80. A method according to claim 69, wherein the polymer matrix comprises a halopolymer.

81. A method according to claim 69, wherein the polymer matrix comprises a fluoropolymer.

82. A method according to claim 69, wherein the polymer matrix has a crystallinity of less than about 99%.

83. A method according to claim 69, wherein the polymer matrix has a glass transition temperature to Tg and a thermal decomposition temperature of Td and wherein said infusing is carried out at a temperature from about Tg-50°

C. to about Td and at which the inorganic or organic molecules have a non-zero vapor pressure.

84. A method according to claim 69, wherein the inorganic or organic molecules are selected from the group consisting of VOCl₃, W(CO)₆, Fe(CO)₅,TiCl₄, SiCl₄, AlCl₃, PCl₃, SbCl₅, As(C₂ H₅)₃, Ba(C₃ H₇)₂, borane pyridine and tetrahydrofuran complexes, Cd(BF₄)₂, Ca(OOCCH(C₂ H₅)C₄ H₉)₂, cerium (III) 2-ethylhexanoate, cesium 2-ethylhexoxide, chromium (III) naphthenate, CrO₂ Cl₂, Co(CO)₃ NO, copper (II) dimethylaminoethoxide, triethylgallium, GeCl₄, triethylindium, lead naphthenate, C₂ H₅ MgCl, (CH₃)₂ Hg, MoF₆, Ni(CO)₄, Nb(OC₂ H₅)₆, HReO₄, Ta(OC₂ H₅)₅, C₅ H₅ Tl, SnCl₄, pi-allyl compounds of Group IIIa, IVa, Va, VIa, or VIIa metals, pi-allyl compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, or Pt, and combination thereof.

85. A method of catalyzing a reaction of a reactant comprising:

providing a composite according to claim 18, wherein the inorganic or organic material is suitable for catalyzing the reaction of reactant; and

contacting the composite with the reactant under conditions effective to catalyze the reaction.

86. A method according to claim 85, wherein the reactant is a gaseous reactant.

87. A method according to claim 85, wherein the reactant is SO₂ and the inorganic or organic material is an inorganic macromolecular network comprising vanadium.

88. A electroconductive imaging element comprising:

an insulating support;

an electrically-conductive layer overlaying the support, wherein said electrically-conductive layer comprises a composite of claim 18; and

a dielectric imaging layer overlaying the electrically-conductive layer.

89. A photographic element comprising:

a substrate;

a light-sensitive layer directly or indirectly disposed on the substrate; and

an antistatic layer directly or indirectly disposed on the substrate, wherein the antistatic layer comprises a composite of claim 18.

90. A electrolytic fuel cell comprising:

a composite of claim 18;

an anode in electrical contact with said composite; and

a cathode in electrical contact with said composite.

91. A method for shielding a material from electromagnetic radiation emitted from an electromagnetic radiation source comprising:

disposing between the material and the electromagnetic radiation source a composite according to claim 18, wherein the inorganic or organic material comprises a metal.

92. A method for shielding a material from heat or flame source comprising:

disposing between the material and the heat or flame source a composite according to claim 18, wherein the inorganic or organic material is a metal oxide.

36. A composite comprising:

a polymer matrix having natural free volume therein; and

an inorganic or organic material disposed in the natural free volume of said polymer matrix, wherein said polymer matrix is at least partially amorphous and wherein said inorganic or organic material is an organic macromolecular network having the formula .paren open-st.R--R.paren close-st._n, wherein n is an integer from about 1 to about 10,000 and R is a monomer radical.

37. A composite according to claim 36, wherein the organic macromolecular network comprises polyacetylene, polypyrrole, polyaniline, polythiophene, or combinations thereof.

93. A method for making a composite according to claim 36, said method comprising:

providing a polymer matrix having natural free volume therein, wherein the polymer matrix is at least partially amorphous;

evacuating the natural free volume of the polymer matrix;

infusing organic molecules into the evacuated natural free volume of the polymer matrix; and

polymerizing the organic molecules under conditions effective to assemble the organic molecules into the organic macromolecular network having the formula .paren open-st.R-R.paren close-st._n, wherein n is an integer from about 1 to about 10,000 and R is a monomer radical.

94. A method according to claim 93, wherein said infusing is carried out under non-supercritical conditions.

95. A method according to claim 93, wherein the organic molecules are infused into the natural free volume of the polymer matrix in a gaseous state.

96. A method according to claim 93, wherein the polymer matrix comprises a halopolymer.

97. A method according to claim 93, wherein the polymer matrix comprises a fluoropolymer.

98. A method according to claim 93, wherein the organic molecules are selected from the group consisting of acetylene, pyrrole, aniline, thiophene, and combinations thereof.