Publications

Sol-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 hydrogenation. Anionic polymerization of these materials, either neat or with 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane as a copolymer, affords thermally stable transparent gels with no visible shrinkage. These materials provide an easy route to the introduction of sol-gel type materials in encapsulation of microelectronics, which we have successfully demonstrated.

Sol-gel chemistry has been the focus of much attention in the design and preparation of highly crosslinked polysiloxane gels. Preparation of sol-gel processed silica or polysilesquioxane gels is carried out by the hydrolysis and condensation of alkoxysilyl monomers, usually in the presence of catalytic acid or base and an excess of water. Removal of the alcohol and water byproducts of the condensation reactions, in addition to the alcohol needed to co-dissolve the hydrophobic monomers with water, leads to substantial shrinkage during drying of the resulting gels. This limits the utility of sol-gel processing for applications requiring net-shape casting of artifacts, crack free coatings, or low vaporous organic contaminants (VOCs). It would be advantageous to have a sol-gel process based on an organosilicon monomer that would not require water as a reactant or produce water and alcohol condensation products and still result in siloxane network polymers capable of forming gels. Here, the authors show the synthesis and preparation of a novel sol-gel monomer which can easily be polymerized by ring opening polymerization to give highly crosslinked polysiloxane gels with no condensation byproducts.

The sol-gel chemistry of a variety of trialkoxysilanes with different organic substituents, with methoxide or ethoxide substituents on silicon was examined at varying monomer concentrations ranging up to neat monomer and with different catalysts. Gels were prepared from tetramethoxysilane and tetraethoxysilane at identical concentrations for purposes of comparison. The polymerization reactions were monitored for the formation of gels, insoluble precipitates, soluble polymers, or polyhedral oligosilsesquioxanes.

Non-shrinking polymers are desirable as encapsulants for strain-free packaging for electronics. Ring-opening polymerizations of cyclic monomers such as lactams, cyclic ethers, and cyclic oligosiloxanes have proven an effective strategy for reducing shrinkage. In this report the authors examined the loss of volume during the ring-opening polymerization of neat 2,2,5,5-tetramethyl-l-oxa-2,5-disilacyclopentane to give poly(1,2-ethylene-bis(dimethyl-siloxane)). Monomer 1 is under sufficient strain (8--12 kcal/mole) to permit its facile base-catalyzed polymerization to afford high molecular polymer. Monomer 1 was prepared by hydrolyzing and condensing either 1,2-bis(chlorodimethylsilyl)ethane or 1,m2-bis(dimethylethoxysilyl)ethane to give a low molecular weight oligomer. Pyrolysis of this oligomer with potassium hydroxide at 280 C afforded the cyclic monomer in good yield (60--70%). The ease with which the oligomer can be converted to monomer also led the authors to investigate the potential for recycling the high molecular weight polymer.

A new approach to the fabrication of porous, amorphous inorganic membranes using organic pore templates was investigated. The pore templates were a new family of hybrid organic-inorganic monomers. As background for membrane work, the monomers were polymerized by sol-gel techniques to make crosslinked polymers. Molecular modeling was used to create computer simulations of the materials and provide insight into their composites, were then converted into porous silicas using low temperature oxygen plasma techniques. A select few of the monomers were copolymerized with silica monomers to form non-porous thin films on mesoporous substrates. The films were converted into porous silica thin films with thermal oxidations and the resulting membranes were tested for gas selectivities and flux.

Under acidic sol-gel polymerization conditions, 1,3-bis(triethoxysilyl)-propane (1) and 1,4-bis(triethoxysilyl)butane (2) were shown to preferentially form cyclic disilsesquioxanes 3 and 4 rather than the expected 1,3-propylene- and 1,4-butylene-bridged polysilsesquioxane gels. Formation of 3 and 4 is driven by a combination of an intramolecular cyclization to six and seven membered rings, and a pronounced reduction in reactivity under acidic conditions as a function of increasing degree of condensation. The ease with which these relatively unreactive cyclic monomers and dimers are formed (under acidic conditions) helps to explain the difficulties in forming gels from 1 and 2. The stability of cyclic disilsesquioxanes was confirmed withe the synthesis of 3 and 4 in gram quantities; the cyclic disilsesquioxanes react slowly to give tricyclic dimers containing a thermodynamically stable eight membered siloxane ring. Continued reactions were shown to perserve the cyclic structure, opening up the possibility of utilizing cyclic disilsesquioxanes as sol-gel monomers. Preliminary polymerization studies with these new, carbohydrate-like monomers revealed the formation of network poly(cyclic disilsesquioxanes) under acidic conditions and polymerization with ring-opening under basic conditions.

Sol-gel polymerication of {alpha}, {omega}-bis(triethoxysilyl)alkanes normally leads to alkylene-bridged polysilsesquioxanes in the form of insoluble, highly crosslinked polymeric gels. Hydrolysis of the six ethoxide groups on each monomer gives silanols that then condense to form a network of siloxane bonds. Unlike most Sol-gel precursors, these flexible hydrocarbon-bridged monomers can participate not only in intermolecular condensation reactions that lead to polymeric networks, but in intramolecular condensation reactions leading to cyclic disilsesquioxanes as well. Partitioning between these two reaction manifolds should be an important determinant of the manner in which the network polymer is assembled and, be an important determinant of the manner in which the network polymer is assembled and, ultimately, the final morphologies of the crosslinked gels. The relative importance of the two pathways should be dependent on a variety of factors, including the reaction mechanism (acid or base catalysis), the concentration of {alpha}, {omega}(triethoxysilyl)alkane and, most importantly for this study, the length of the alkylene bridging group.

Polyxylylenes are thermoplastics used as encapsulants for electronic devices. Five polyxylylenes were prepared by pyrolysis of [2.2]paracyclophanes and characterized by solid state {sup 13}C NMR spectroscopy. The chemical shift data, in combination with interrupted decoupling experiments, allowed assignment of resonances to their carbon sources in the polymers. This confirmed the integrity of the xylylene building block in the polymers and is consistent with linear polymers. No crosslinking could be detected within the NMR sensitivity limits. Residual paracyclophane was detected by {sup 13}C CP MAS NMR spectroscopy in the polyxylylene samples prepared at room temperature; however discrete {sup 13}C resonances due to amorphous and crystalline phases in the polymers were not resolved.

Bridged polysilsesquioxanes represent an interesting family of hybrid organic-inorganic composite materials. It has been shown that manipulation of the organic bridging component offers the potential for the synthesis of a variety of materials with a range of surface areas and porosities. In addition, incorporation of a heteroatom within the bridging organic component allows for further chemical transformation of the polysilsesquioxane material.

Poly (1, 4 bis(triethoxysilyl)benzene) (PTESB), a representative of a new type of organic-inorganic hybrid polysilsesquioxane material, was characterized by fluorescence spectroscopy for both microenvironmental polarity and solvent accessibility. A dansyl fluorescent molecule was incorporated into the bulk as well as onto the surface of both PTESB and silica materials. Information about the microenvironment polarity and accessibility of PTESB to various organic solvents was determined and compared to that of silica gel. This study found that both the bulk and surface of PTESB are less polar than that of the silica material. The silica material is accessible to polar solvents and water, while YMB is accessible to polar solvents but not to water. The hydrophobicity of PTESB differentiates these new materials from silica gel.

Hexylene-bridged polysilsesquioxanes can be prepared as mesoporous or non-porous xerogels simply by switching from basic to acidic polymerization conditions. In this study, we looked at the effect of monomer concentration on porosity of hexylene-bridged xerogels prepared under acidic and basic conditions. 1, 6-Hexylene-bridged polysilsesquioxanes were prepared by sol-gel polymerizations of 1, 6-bis(triethoxysilyl)hexane 1 with concentrations between 0. 1 to 1.2 M in ethanol. Gelation times ranged from seconds for 1.2 M concentration to months for 0.2 M. The gels were processed into xerogels by an aqueous work-up and the dry gels characterized by scanning electron microscopy (SEM), solid state {sup 13}C and {sup 29}Si CP MAS NMR spectroscopy, and gas sorption porosimetry.

Hydrocarbon-bridged polysilsesquioxanes are prepared by the sol-gel polymerization of monomers with more than one trialkoxysilyl group attached directly to the bridging group by Si-C bonds. While the effects of varying the identity of the bridging group (length, rigidity, etc.), monomer concentration, and type of catalyst have been studied, the effect of different alkoxy ligands on the silicon atoms has not been investigated. For this study, 1, 6-- bis(triethoxysilyl)hexane 1 and 1, 6-bis(trimethoxysilyl)hexane 2 were polymerized under acidic and basic conditions in ethanol and methanol, respectively, and in tetrahydrofuran (THF). The resulting gels were processed to afford xerogels that were characterized by SEM, solid state {sup 13}C and {sup 29}Si Cross Polarization Magic Angle Spinning (CP MAS) NMR spectroscopy, and nitrogen sorption porosimetry.

Synthesis of hybrid organic-inorganic materials with ionic functionality within the polymer backbone has been achieved. A new family of hypervalent spiro anionic polysiliconates and polygermylates has been prepared. These materials were shown to be thermally stable to moderate temperatures and are completely air and moisture stable. Analysis by solution and solid state NMR verified the presence of the hypervalent functionality. We are currently examining the effect that alteration of the condensing reagent and/or the counterion may have on bulk properties of the ionomeric material.

Aryl-, ethynyl- and alkyl-bridged polysilsesquioxanes were prepared by the hydrolysis and condensation of the respective bridged triethoxysilanes under both acidic and basic conditions. Gelation of the resulting sols can take place at concentrations as low as 0.02 M in tetrahydrofuran. The gels can be air dried to afford xerogels or extracted with supercritical carbon dioxide to give high surface area aerogels. The materials were characterized by solid state {sup 13}C and {sup 29}Si CP MAS NMR spectroscopies, gas sorption porosimetry, and thermal gravimetric analysis. The bridged polysilsesquioxanes offer the opportunity to prepare hybrid organic-inorganic materials with properties unique from other siloxane network materials and silica gels.