Organopolysilsesquioxanes have recently gained much interest as materials for low-K dielectrics [... more Organopolysilsesquioxanes have recently gained much interest as materials for low-K dielectrics [1], ceramic precursors [2] and photoresists [3]. Typical sol-gel synthesis of polysilsesquioxanes involves the hydrolysis of organotricholorosilanes and/or organotrialkoxysilanes in the presence of acid or base catalysts and organic solvents. However, under sol-gel conditions most organotrialkoxysilanes do not afford silsesquioxane gels. This limits the range of organic functionalities that can be introduced into these hybrid organicinorganic materials.
Ring-opening polymerization (ROP) of disilaoxacyclopentanes has proven to be an excellent approac... more Ring-opening polymerization (ROP) of disilaoxacyclopentanes has proven to be an excellent approach to sol-gel type hybrid orgainc-inorganic materials [1]. These materials have shown promise as precursors for encapsulation and microelectronics applications (Figure 1). The polymers are highly crosslinked and are structurally similar to traditional sol-gels, but unlike typical sol-gels they are prepared by an organic base or Bronsted acid (formic or triflic acid), without the use of solvents and water, they have low VOC's and show little shrinkage during processing.
Abstract Silica aerogels were silated with coumarin functionalities to allow for strengthening th... more Abstract Silica aerogels were silated with coumarin functionalities to allow for strengthening through the photochemical dimerization of the coumarin groups. Coumarin modified silica gels were prepared by either co-polymerizing tetramethoxysilane (TMOS) with small amounts of 7-(3-triethoxysilylpropoxy)coumarin (TEPC) or by surface modifying the silica gel with 7-(3-trimethoxysilylpropoxy)coumarin (TMPC). Aerogels, prepared by supercritical carbon dioxide drying, were irradiated with ultraviolet light (365 nm) for varying lengths of time and the flexural strength of cylindrical samples was measured. Copolymerization of TEPC with TMOS resulted in aerogels that, while initially weaker than pure silica aerogels, showed a 41% increase in flexural strength with 20 min exposure to UV. In contrast, the surface modified aerogels, while stronger than pure silica aerogels, showed no influence on flexural strength with exposure to UV.
Silica and bridged polysilsesquioxane aerogels are low-density materials that are attractive for ... more Silica and bridged polysilsesquioxane aerogels are low-density materials that are attractive for applications such as thermal insulation, porous separation media or catalyst supports, adsorbents, and cometary dust capture agents. However, aerogels are notoriously weak and brittle making it difficult to handle and machine monoliths into desired forms. This complication prevents the development of many applications that would otherwise benefit from the use of the low-density materials. Here, we will describe our efforts to chemically modify and mechanically enhance silica-based aerogels using chemical vapor techniques without sacrificing their characteristic low densities. Monolithic silica and organic-bridged polysilsesquioxane aerogels were prepared by sol-gel polymerization of the respective methoxysilane monomers followed by supercritical carbon dioxide drying of the gels. Then the gels were reactively modified with silylating agents to demonstrate the viability of CVD modificatio...
ABSTRACTSol-gel processing of materials is plagued by shrinkage during polymerization of the alko... more ABSTRACTSol-gel processing of materials is plagued by shrinkage during polymerization of the alkoxide monomers and processing (aging and drying) of the resulting gels. We have developed a new class of hybrid organic-inorganic materials based on the solventless ring-opening polymerization (ROP) of monomers bearing the 2,2,5,5-tetramethyl-2,5-disilaoxacyclopentyl group, which permits us to drastically reduce shrinkage in sol-gel processed materials. Because the monomers are polymerized through a chain growth mechanism catalyzed by base rather than the step growth mechanism normally used in sol-gel systems, hydrolysis and condensation products are entirely eliminated. Furthermore, since water is not required for hydrolysis, an alcohol solvent is not necessary. Monomers with two disilaoxacyclopentyl groups, separated by a rigid phenylene group or a more flexible alkylene group, were prepared through disilylation of the corresponding diacetylenes, followed by ring closure and hydrogenati...
ABSTRACTPolymerization of organotrialkoxysilanes is a convenient method for introducing organic f... more ABSTRACTPolymerization of organotrialkoxysilanes is a convenient method for introducing organic functionality into hybrid organic-inorganic materials. However, not much is known about the effects of the organic substituent on the porosity of the resulting xerogels. In this study, we prepared a series of polysilsesquioxane xerogels from organotrialkoxysilanes, RSi(OR′)3, with different organic groups (R = H, Me, Et, dodecyl, hexadecyl, octadecyl, vinyl, chloromethyl, cyanoethyl). Polymerizations of the monomers were carried out under a variety of conditions, varying monomer concentration, type of catalyst, and alkoxide substituent. The effect of the organic substituent on the sol-gel process was often dramatic. In many cases, gels were formed only at very high monomer concentration and/or with only one type of catalyst. All of the gels were processed as xerogels and characterized by scanning electron microscopy and nitrogen sorption porosimetry to evaluate their pore structure.
ABSTRACTIn-situ filling through hydrolysis and condensation of silicon alkoxides dissolved into p... more ABSTRACTIn-situ filling through hydrolysis and condensation of silicon alkoxides dissolved into polymers has been utilized to generate nanocomposites in which the filler phase can be intimately associated with the polymer on relatively small length scales. One problem of the method has been achieving useful fill volumes without bulk phase separation of the growing inorganic component from the polymer. In this paper, we describe the preparation of a new class of nanocomposite materials in which the inorganic filler phase is pre-assembled before copolymerization with an organic monomer. Maleimide monomers, prepared from alkoxysilylpropyl amines and maleic anhydride, were protected against side reactions by forming the oxonorbornene Diels-Alder adduct with furan. The monomers were then reacted under solgel conditions to form oligomers or polymers making up the filler phase. The material was activated by thermal deprotection of the maleimide and reacted with organic monomers or polymers...
Organopolysilsesquioxanes have recently gained much interest as materials for low-K dielectrics [... more Organopolysilsesquioxanes have recently gained much interest as materials for low-K dielectrics [1], ceramic precursors [2] and photoresists [3]. Typical sol-gel synthesis of polysilsesquioxanes involves the hydrolysis of organotricholorosilanes and/or organotrialkoxysilanes in the presence of acid or base catalysts and organic solvents. However, under sol-gel conditions most organotrialkoxysilanes do not afford silsesquioxane gels. This limits the range of organic functionalities that can be introduced into these hybrid organicinorganic materials.
Ring-opening polymerization (ROP) of disilaoxacyclopentanes has proven to be an excellent approac... more Ring-opening polymerization (ROP) of disilaoxacyclopentanes has proven to be an excellent approach to sol-gel type hybrid orgainc-inorganic materials [1]. These materials have shown promise as precursors for encapsulation and microelectronics applications (Figure 1). The polymers are highly crosslinked and are structurally similar to traditional sol-gels, but unlike typical sol-gels they are prepared by an organic base or Bronsted acid (formic or triflic acid), without the use of solvents and water, they have low VOC's and show little shrinkage during processing.
Abstract Silica aerogels were silated with coumarin functionalities to allow for strengthening th... more Abstract Silica aerogels were silated with coumarin functionalities to allow for strengthening through the photochemical dimerization of the coumarin groups. Coumarin modified silica gels were prepared by either co-polymerizing tetramethoxysilane (TMOS) with small amounts of 7-(3-triethoxysilylpropoxy)coumarin (TEPC) or by surface modifying the silica gel with 7-(3-trimethoxysilylpropoxy)coumarin (TMPC). Aerogels, prepared by supercritical carbon dioxide drying, were irradiated with ultraviolet light (365 nm) for varying lengths of time and the flexural strength of cylindrical samples was measured. Copolymerization of TEPC with TMOS resulted in aerogels that, while initially weaker than pure silica aerogels, showed a 41% increase in flexural strength with 20 min exposure to UV. In contrast, the surface modified aerogels, while stronger than pure silica aerogels, showed no influence on flexural strength with exposure to UV.
Silica and bridged polysilsesquioxane aerogels are low-density materials that are attractive for ... more Silica and bridged polysilsesquioxane aerogels are low-density materials that are attractive for applications such as thermal insulation, porous separation media or catalyst supports, adsorbents, and cometary dust capture agents. However, aerogels are notoriously weak and brittle making it difficult to handle and machine monoliths into desired forms. This complication prevents the development of many applications that would otherwise benefit from the use of the low-density materials. Here, we will describe our efforts to chemically modify and mechanically enhance silica-based aerogels using chemical vapor techniques without sacrificing their characteristic low densities. Monolithic silica and organic-bridged polysilsesquioxane aerogels were prepared by sol-gel polymerization of the respective methoxysilane monomers followed by supercritical carbon dioxide drying of the gels. Then the gels were reactively modified with silylating agents to demonstrate the viability of CVD modificatio...
ABSTRACTSol-gel processing of materials is plagued by shrinkage during polymerization of the alko... more ABSTRACTSol-gel processing of materials is plagued by shrinkage during polymerization of the alkoxide monomers and processing (aging and drying) of the resulting gels. We have developed a new class of hybrid organic-inorganic materials based on the solventless ring-opening polymerization (ROP) of monomers bearing the 2,2,5,5-tetramethyl-2,5-disilaoxacyclopentyl group, which permits us to drastically reduce shrinkage in sol-gel processed materials. Because the monomers are polymerized through a chain growth mechanism catalyzed by base rather than the step growth mechanism normally used in sol-gel systems, hydrolysis and condensation products are entirely eliminated. Furthermore, since water is not required for hydrolysis, an alcohol solvent is not necessary. Monomers with two disilaoxacyclopentyl groups, separated by a rigid phenylene group or a more flexible alkylene group, were prepared through disilylation of the corresponding diacetylenes, followed by ring closure and hydrogenati...
ABSTRACTPolymerization of organotrialkoxysilanes is a convenient method for introducing organic f... more ABSTRACTPolymerization of organotrialkoxysilanes is a convenient method for introducing organic functionality into hybrid organic-inorganic materials. However, not much is known about the effects of the organic substituent on the porosity of the resulting xerogels. In this study, we prepared a series of polysilsesquioxane xerogels from organotrialkoxysilanes, RSi(OR′)3, with different organic groups (R = H, Me, Et, dodecyl, hexadecyl, octadecyl, vinyl, chloromethyl, cyanoethyl). Polymerizations of the monomers were carried out under a variety of conditions, varying monomer concentration, type of catalyst, and alkoxide substituent. The effect of the organic substituent on the sol-gel process was often dramatic. In many cases, gels were formed only at very high monomer concentration and/or with only one type of catalyst. All of the gels were processed as xerogels and characterized by scanning electron microscopy and nitrogen sorption porosimetry to evaluate their pore structure.
ABSTRACTIn-situ filling through hydrolysis and condensation of silicon alkoxides dissolved into p... more ABSTRACTIn-situ filling through hydrolysis and condensation of silicon alkoxides dissolved into polymers has been utilized to generate nanocomposites in which the filler phase can be intimately associated with the polymer on relatively small length scales. One problem of the method has been achieving useful fill volumes without bulk phase separation of the growing inorganic component from the polymer. In this paper, we describe the preparation of a new class of nanocomposite materials in which the inorganic filler phase is pre-assembled before copolymerization with an organic monomer. Maleimide monomers, prepared from alkoxysilylpropyl amines and maleic anhydride, were protected against side reactions by forming the oxonorbornene Diels-Alder adduct with furan. The monomers were then reacted under solgel conditions to form oligomers or polymers making up the filler phase. The material was activated by thermal deprotection of the maleimide and reacted with organic monomers or polymers...
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Papers by Douglas Loy