Siloxane monomer synthesis

Figure 2. Siloxane monomer synthesis via Grignard chemistry.

In many cases, these cyclic siloxanes have to be removed from the system by distillation or fractionation, in order to obtain pure products. On the other hand, cyclic siloxanes where n = 3 and n = 4 are the two most important monomers used in the commercial production of various siloxane polymers or oligomers via the so-called equilibration or redistribution reactions which will be discussed in detail in Sect. 2.4. Therefore, in modern silicone technology, aqueous hydrolysis of chloro-silanes is usually employed for the preparation of cyclic siloxane monomers 122> more than for the direct synthesis of the (Si—X) functional oligomers. Equilibration reactions are the method of choice for the synthesis of functionally terminated siloxane oligomers. 

Pioneering work in living anionic copolymerization of siloxanes was reported by Morton and co-workers 139 140, who synthesized isoprene-dimethylsiloxane block copolymers utilizing D4 as the siloxane monomer. The use of D3 in the synthesis of siloxane block copolymers with controlled structures was demonstrated by Bostick and others. Excellent reviews of these earlier studies and subsequent developments are available in the literature 22 137 13S). 

Next-generation soft contact lenses, dental polymers, surface coatings, and similar materials are produced from compounds of varying structure and reactive functionality. For example, currently in development are new soft lenses that will be manufactured from monomers synthesized with dimethylsil-oxane backbones. The dimethylsiloxane backbone is terminated with a methacryloxy functionality that supplies the site for polymerization. The siloxane provides lens softness. Occasionally the functionality is formed on both ends of the monomer, resulting in undesired properties. The compound BisGMA is a monomer that is polymerized to form hard dental structures. In the monomer synthesis process impurities are coproduced that interfere with the polymerization. Finally, diacetone acrylamide used in a copolymerization process is another specialty monomer that is occasionally contaminated with difficult-to-remove impurities. These three monomers are quite reactive at modest temperature and cannot be purified by distillation. The three examples that are presented here derive from as yet unpublished research (Krukonis, 1982c). 

A similar class of siloxane polymers was created with imi-dazolium groups (Cl5). ° Monomer synthesis consisted of combining N-allylimidazole and methyldiethoxysilane at elevated temperature. Homopolymers were created by polycondensation. Polymers with dimethylsiloxane spacers were also created by anionic ring-opening polymerization. Both classes of imidazole polymers were then reacted with n-octyl bromide to create the imidazolium side chains. Bactericidal activities of these polymers were similar to the quaternary ammonium polymers. 

Ionic ring-opening polymerizations of cyclic ether, acetal, ester and siloxane monomers give polymers with controlled molecular weights and well-defined terminal structure that are thus suitable for the synthesis of block copolymers when coupled with controlled radical polymerizations. 

The original FeCl3-catalyzed condensation reaction strategy has been exploited recently by Patel and co-workers for the synthesis of poly(m-carborane-siloxane) rubbers (103) (Fig. 63) in the reactions between dimethoxy-m-carborane terminated monomers and dichlorodimethylsilane.131 They have also synthesized similar polymers... 

The initial transition of dissolved silicate molecules into solid nanoparticles is perhaps the least explored step in the synthesis of zeolites. One impediment to understanding this mysterious step is the poorly elucidated molecular composition of dissolved particles. The major mechanistic ideas for the formation of zeolites approach these structures differently i) many researchers believe that secondary building units (SBU) must be present to form initial nanoslabs [1,2] ii) some others prioritize the role of monomers to feed artificially introduced crystal nuclei or assume that even these nuclei form via appropriate aggregation of monomers [3] iii) silicate solutions are also frequently viewed as random mixtures of various siloxane polymers which condense first into an irregular gel configuration which can rearrange subsequently into a desired crystal nucleus at appropriate conditions [4,5],... 

The chemistry of silicone halides was recently reviewed by Collins.13 The primary use for SiCU is in the manufacturing of fumed silica, but it is also used in the manufacture of polycrystalline silicon for the semiconductor industry. It is also commonly used in the synthesis of silicate esters. T richlorosilane (another important product of the reaction of silicon or silicon alloys with chlorine) is primarily used in the manufacture of semiconductor-grade silicon, and in the synthesis of organotrichlorosilane by the hydrosilylation reactions. The silicon halohydrides are particularly useful intermediate chemicals because of their ability to add to alkenes, allowing the production of a broad range of alkyl- and functional alkyltrihalosilanes. These alkylsilanes have important commercial value as monomers, and are also used in the production of silicon fluids and resins. On the other hand, trichlorosilane is a basic precursor to the synthesis of functional silsesquioxanes and other highly branched siloxane structures. 

The additional complexity present in block copolymer synthesis is the order of monomer polymerization and/or the requirement in some cases to modify the reactivity of the propagating center during the transition from one block to the next block. This is due to the requirement that the nucleophilicity of the initiating block be equal or greater than the resulting propagating chain end of the second block. Therefore the synthesis of block copolymers by sequential polymerization generally follows the order dienes/styrenics before vinylpyridines before meth(acrylates) before oxiranes/siloxanes. As a consequence, styrene-MMA block copolymers should be prepared by initial polymerization of styrene followed by MMA, while PEO-MMA block copolymers should be prepared by... 

---