Siloxane oligomers, cyclic

Chlorosilanes are the most common precursor to siloxanes, cyclic or otherwise, because of their ready availability from the direct processing of alkyl chlorides with Si. Upon hydrolysis, chlorosilanes are converted to polysiloxanes and their cyclic oligomers. 

Table 6.11 shows the results of elementary analysis, physical chemical properties and the yield of ethylsiloxane oligomers containing cyclic fragments in the side chain. In the IR spectra of oligomers with cyclic fragments in the side chain one can observe the absorption bands characteristic of asymmetric valence oscillations of the =Si-0-Sis bonds in the region 1020 and 1080 cm characteristic of both linear siloxane links and cyclosiloxane rings. In the IR spectra one can also observe absorption bands for unreacted =Si-H bonds at 2160 cm. ... 

As has already been mentioned, divinyl silicon derivatives, similarly to monovinyl-substituted silicon compounds, are also completely inert to productive homometathesis, particularly as far as acyclic diene metathesis (ADMET) polymerization is concerned. However, we have shown in earlier reports that in the presence of ruthenium, rhodium and cobalt complexes containing or generating M-H and/or M-Si bonds, divinyl-substituted silicon compounds undergo de-ethenated (poly)condensation to yield a mixture of oligomers and cyclic unsaturated siloxanes, silazanes and caibosilanes, as shown in Scheme 2 [21-29]. 

In the presence of ruthenium, rhodium and cobalt complexes that initially contain or generate M-H and M-Si bonds, divinylderivatives of silicon compounds undergo de-ethenated silylative polycondensation to yield a mixture of oligomers and cyclic unsaturated siloxanes (silanes, silazanes) according to equation 3. 

During the aqueous hydrolysis of dichlorosilanes there is always a very important side reaction. It is the self-condensation of silanols which are formed initially during the hydrolysis. These reactions also give rise to the formation of cyclic siloxanes together with the linear oligomers or polymers (Reaction Scheme III). The amount of cyclic products usually depends on the hydrolysis conditions and the degree of the self-condensation attained as well as concentration considerations. 

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. 

An important advantage in the preparation of a,eo-functionally terminated siloxane oligomers, over the other telechelic systems, is the flexible polymerization chemistry of cyclic organosiloxane monomers and intermediates. This is mainly due to the partial... 

Detailed information on the copolymerization of cyclic trifluoropropylmethyl-siloxane trimer and octamethylcyclotetrasiloxane is also very limited in the open literature26 27 . Recently, preparation of various amine terminated (dimethyl-tri-fluoropropyl,methyl)siloxane oligomers with varying molecular weights and backbone compositions has been reported 69115 ll7). Table 11 shows various properties of the oligomers produced as a function of composition. These types of modification play very important roles in determining the solubility characteristics and hence the compatibility of resultant polysiloxanes with other conventional organic monomers... 

Silicone paints are formed by controlled hydrolysis and condensation of alkyl alkox-ysilanes, and may be encountered either alone or in formulations with other synthetic resins. The typical structural unit in the polymer chain is dimethyl siloxane, and pyrolysis of such resins takes place with random chain scission and the extended formation of stable cyclic fragments. In Figure 12.14 the pyrogram of a silicone resin is shown, with cyclic siloxane oligomers eluting at the shorter retention times, followed by the linear siloxane fragments. 

For the most common siloxanes, polydimethylsiloxanes (PDMS), R=Me. Thus, most common cyclic siloxanes would be referred to as Dn, for example, D3, D4, D5,. .. linear oligomers are often called MD M, for example, MM, MDM, MD2M,. .. and, T and Q units constitute parts of many highly branched oligomers and polymers, or cross-linked networks. 

Siloxane containing block or segmented copolymers can be synthesized either by living anionic polymerization of the cyclic organosiloxane trimers with appropriate vinyl monomer(, 4 ) or by step-growth or condensation copolymerization of preformed a,w-difunctional siloxane oligomers with conventional difunctional... 

As it is well known, the (Si-0) bond in organosiloxanes may be considered to be polar or partially ( 50%) ionic.(12) Therefore, it can be cleaved by the attack of strong acids or bases. This is the main rationale behind the "equilibration" route to the synthesis of a wide variety of functionally terminated siloxane oligomers(12-14) from cyclic siloxanes and a.ordifunctional disiloxanes as shown in Scheme 3. 

In their earlier studies on the synthesis of a, ajrhydroxyl terminated siloxane oligomers Marvel and co-workers (21) have utilized sulfuric acid as the catalyst in the equilibration of cyclic tetramer (D ) and l,3-bis(4-hydroxylbutyl)tetramethyldisilox-ane (DSX). However the molecular weights of the oligomers obtained were several times higher than the expected values. They have... 

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