Process for making organic-inorganic hybrid materials
View Patent ↗A process for forming an organic-inorganic hybrid material that can undergo a property change when exposed to an external stimulus, the process comprising providing a prepolymer; and attaching a functional organometal material to the prepolymer, where the functional organometal material comprises a functional moiety that is responsive to an external stimulus such that the organic-inorganic hybrid material exhibits a change in a property of the organic-inorganic hybrid material. The process can further include forming hydrogel particles from the organic-inorganic hybrid material.
1. A process for forming an organic-inorganic hybrid particle that can undergo a property change when exposed to an external stimulus, the process comprising:
forming an organic-inorganic material, the process of forming the material comprising:
providing a prepolymer oligomer; and
attaching a functional organometal material to the prepolymer oligomer, where the functional organometal material comprises (a) a metal component comprising a metal atom comprising a leaving group attached to the metal, and (b) an organic functional moiety attached to the metal atom, where the organic functional moiety is derived from a polyalkylene glycol alkyl ether, an amine-terminated polyalkylene glycol alkyl ether, an alkyl acrylamide, an alkyl methacrylamide, a benzalkonium chloride, a substituted benzalkonium chloride, a di(C6-C14)alkyl di short chain (C1-4 alkyl and/or hydroxyalkyl) quaternaryammonium salt, benzethonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, polymers thereof, or a combination of two or more thereof, and where the hybrid particle comprises a functional moiety and is responsive to an external stimulus, and
forming an organic-inorganic hybrid particle by reacting the organic-inorganic material in a solution comprising water and a base catalyst.
2. The process of claim 1 , wherein the prepolymer oligomer is a metalloxane.
3. The process of claim 1 , wherein the prepolymer oligomer comprises a metal chosen from Si, Ti, Fe, Al, Zr, Nb, Y, B, Ce, V, Zn, Cu, Ni, Co, Ge, Mn, Mg, Cr, Fe, V, a rare earth metal, or a combination of two or more thereof.
4. The process of claim 1 , wherein the prepolymer oligomer comprises the metal in an amount of about 25 percent by weight or greater.
5. The process of claim 1 , wherein the prepolymer oligomer comprises a siloxane.
6. The process of claim 5 , wherein the siloxane comprises a polyalkoxysiloxane.
7. The process of claim 6 , the siloxane is derived from tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropylorthosilicate (TPOS), tetramethoxy silane, tetrabutoxy silane, methyl trimethoxy silane (MTMS), methyl triethoxy silane (MTES), phenyl trimethoxy silane, isobutyl trimethoxy silane, tetraalkoxysilanes, siloxane oligomers derived from alkoxysilanes, and pre-polymerized alkoxysilanes, or a combination of two or more thereof.
8. The process of claim 1 , wherein the organometal material comprises a metal chosen from Si, Ti, Fe, Al, Zr, Nb, Y, B, Ce, V, Zn, Cu, Ni, Co, Ge, Mn, Mg, Cr, Fe, V, a rare earth metal, or a combination of two or more thereof.
9. The process of claim 1 , wherein the leaving group comprises an alkoxy group, a halogen, or a combination thereof.
10. The process of claim 1 , wherein organic functional moiety is derived from a polyalkylene glycol alkyl ether chosen from polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monoisopropyl ether, polyethylene glycol monobutyl ether, polyethylene glycol monooctyl ether, polyethylene glycol monodecyl ether, polyethylene glycol monohexadecyl ether, polyethylene glycol monooctadecyl ether, polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, polypropylene glycol monoisopropyl ether, polypropylene glycol monobutyl ether, polypropylene glycol monooctyl ether, polypropylene glycol monodecyl ether, polypropylene glycol monohexadecyl ether, polypropylene glycol monooctadecyl ether, nonophenyl ethoxylate, or a combination of two or more thereof.
11. The process of claim 1 , wherein providing the prepolymer oligomer comprises forming the prepolymer oligomer by:
adding a metal source to a reaction system comprising water, a first catalyst, and an oxygenated material, and reacting the mixture.
12. The process of claim 11 , wherein:
the first catalyst is chosen from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, fluoric acid, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, maleic acid, methylmalonic acid, adipic acid, p-toluenesulfonic acid, or combinations of two or more thereof; and
the oxygenated material is chosen from a primary alcohol, a secondary alcohol, or tertiary alcohol comprising one to eight carbon atoms; a hindered alcohol; a cyclic alcohol; methyltertiarybutylether, a substituted alcohol; a diol; tetrahydrofuran; pyrrolidone; a substituted pyrrolidone; dimethyl sulfoxide; furfural; or a combination of two or more thereof.
13. The process of claim 1 , wherein attaching the functional organometal material to the prepolymer oligomer comprises adding the functional organometal material and water to a solution comprising the prepolymer oligomer.
14. The process of claim 13 wherein adding the functional organometal material to the prepolymer oligomer can be carried out by continuous addition or intermittent addition.
15. The process of claim 1 , wherein a non-ionic or ionic surfactant is added to the organic-inorganic material, the water of the solution comprising water and the base catalyst, or both.
16. The process of claim 15 , wherein the surfactant comprises a polyglycol, an alkylene oxide, a cyclic hydrocarbon, a linear or branched aliphatic hydrocarbon having carbon numbers from 5 to 12 and alkyl derivatives thereof, or combinations of two or more thereof or a combination thereof.
17. The process of claim 15 , comprising adding a highly polar material to the organic-inorganic material, the water of the solution comprising water and the base catalyst, or both.
18. The process of claim 1 , wherein the base catalyst comprises a non-alkaline metal base material, an organic base material, a non-metal base material, or a combination of two or more thereof.
19. The process of claim 1 further comprising subjecting the organic-inorganic material to temperature and pressure conditions to remove volatile components from the material prior to particle formation.
20. A process for forming an organic-inorganic hybrid particle that exhibits a property change in response to an external stimulus, the process comprising:
(i) forming an organic-inorganic hybrid material, the process of forming the material comprising:
(a) forming a metaloxo polymer by adding a metal source to a solution comprising a water, an oxygenated material, and a first catalyst and reacting the components in the solution, the metaloxo polymer comprising a reactive site on the polymer chain; and
(b) grafting a functional moiety to the polymer by reacting a functional organometal material with the polymer via the reactive sites on the polymer chain, wherein the functional moiety comprises an organometal material comprising (a) a metal component comprising a metal atom comprising a labile leaving group attached to the metal, and (b) an organic functional moiety derived from a polyalkylene glycol alkyl ether, an amine-terminated polyalkylene glycol alkyl ether, an alkyl acrylamide, an alkyl methacrylamide, benzalkonium chlorides and/or substituted benzalkonium chlorides, di(C6-C14)alkyl di short chain (C1-4 alkyl and/or hydroxyalkyl) quaternaryammonium salts, N-(3-chloroallyl) hexaminium chlorides, benzethonium chloride, methylbenzethonium chloride, and cetylpyridinium chloride, or a combination of two or more thereof and attached to the metal of the metal component, and
(ii) reacting the organic-inorganic hybrid material in a solution comprising water and a base catalyst to form hydrogel particles.
21. The method of claim 20 , wherein the metal source comprises a metal alkoxide, a hydrolyzable organometallic compound, oxo metal oligomers, or mixtures of two or more thereof.
22. The method of claim 21 , wherein the metal source and organometal material individually comprise a metal chosen from Si, Ti, Fe, Al, Zr, Nb, Y, B, Ce, V, Zn, Cu, Ni, Co, Ge, Mn, Mg, Cr, Fe, V, a rare earth metal, or a combination of two or more thereof.
23. The method of claim 20 , wherein the metal source comprises a metal alkoxide, and the molar ratio of water to metal alkoxide source in a first phase is from about 0.1 to about 4.0.
24. The process of claim 20 , the metal source comprises a siloxane derived from tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropylorthosilicate (TPOS), tetramethoxy silane, tetrabutoxy silane, methyl trimethoxy silane (MTMS), methyl triethoxy silane (MTES), phenyl trimethoxy silane, isobutyl trimethoxy silane, a higher tetraalkoxysilane, a siloxane oligomer derived from an alkoxysilane, or a combination of two or more thereof.
25. The process of claim 20 , wherein the solution in (a) further comprises a non-polar material chosen from a linear or branched aliphatic hydrocarbon, a cyclic hydrocarbon, an aromatic hydrocarbon, a substituted aromatic hydrocarbon, or a combination of two or more thereof.
26. The process of claim 25 , wherein the non-polar material comprises cyclopentane, cyclohexane, cyclooctane, a linear or branched aliphatic hydrocarbon having 5 to 12 carbon atoms and alkyl derivatives thereof, or a combination of two or more thereof.
27. The process of claim 20 , wherein the labile leaving group comprises an alkoxy group, a halogen, or a combination of two or more thereof.
28. The process of claim 20 , wherein organic functional moiety is derived from a polyalkylene glycol alkyl ether chosen from polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monoisopropyl ether, polyethylene glycol monobutyl ether, polyethylene glycol monooctyl ether, polyethylene glycol monodecyl ether, polyethylene glycol monohexadecyl ether, polyethylene glycol monooctadecyl ether, polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, polypropylene glycol monoisopropyl ether, polypropylene glycol monobutyl ether, polypropylene glycol monooctyl ether, polypropylene glycol monodecyl ether, polypropylene glycol monohexadecyl ether, polypropylene glycol monooctadecyl ether, or a combination of two or more thereof.
29. The process of claim 20 , wherein the base catalyst comprises a surfactant chosen from a polyglycol, an alkylene oxide, a cyclic hydrocarbon, a linear or branched aliphatic hydrocarbon having carbon numbers from 5 to 12 and alkyl derivatives thereof, or combinations of two or more thereof or a combination thereof.
30. The process of claim 20 , comprising adding a highly polar material to the organic-inorganic hybrid material.
31. The process of claim 20 , wherein the base catalyst is added to maintain a pH of 2 to about 12.
32. The process of claim 20 , wherein the solution of (ii) is adjusted to maintain a pH of at least 3 and a temperature of at least 2° C.
33. The process of claim 20 , wherein the solution of (ii) is adjusted to have a pH of at least 7.
34. The process of claim 20 , wherein the solution of (ii) is adjusted to maintain a pH of at least 7 and a temperature of at least 5° C.
35. The process of claim 20 further comprising subjecting the organic-inorganic hybrid material to temperature conditions to remove volatile components from the material prior to particle formation.
36. The process of claim 35 wherein from about 2% to about 100% of the volatile components are removed from the material.
37. The process of claim 20 , wherein the hydrogel particles have a mono-modal particle size distribution of from about 1 micron to about 120 microns.
38. The process of claim 20 , wherein the hydrogel particles have a surface area of from about 5 m 2 /gram to about 1000 m 2 /gram.
39. The process of claim 20 , wherein the hydrogel particles have a surface area of from about 20 m 2 /gram to about 700 m 2 /gram.
40. The process of claim 20 , wherein the hydrogel particles have a surface area of from about 100 m 2 /gram to about 500 m 2 /gram.
41. The process of claim 20 , wherein the functional organometal material comprises a functional group that is responsive to an external stimulus such that the organic-inorganic hybrid material exhibits a change in a property of the organic-inorganic hybrid material upon exposure to the external stimulus.
42. The process of claim 41 , wherein the property change is swelling, light absorption, light reflection, index of refraction, electrical conductivity, or a combination of two or more thereof.
43. The process of claim 42 , wherein the property change results from exposure to an aqueous medium, a non-polar medium, or a polar medium.
44. The process of claim 43 , wherein the property change is in response to a change in the medium's concentration, pH, temperature, presence of a specific ion, or two or more thereof.
45. The process of claim 44 , wherein the organic-inorganic hybrid material further comprises a crosslinker disposed therein.
46. The process of claim 45 , wherein the crosslinker is chosen from an acrylic, a urethane, an isocyanate, a vinyl, an epoxy, an oxirane, or a combination of two or more thereof.
47. The process of claim 20 , wherein the hydrogel particles comprise about 5 percent by weight or greater of organic material.
48. The process of claim 47 , wherein the particles comprise about 15 percent by weight or greater of organic material.
49. Particles formed by the process of claim 1 .
50. The particles of claim 49 having an average pore size of from about 20 angstroms to about 2000 angstroms.
51. The particles of claim 49 comprising macropores of about 0.25 micron or greater.
52. Particles formed by the process of claim 20 .
53. The particles of claim 52 having an average pore size of from about 20 angstroms to about 2000 angstroms.
54. The particles of claim 52 comprising macropores of about 0.25 micron or greater.