Silicon backbone

In 1975 Wacker-Chemie introduced silicones under the name of m-polymers. These are also room temperature curing liquid polymers which give rubbery materials on cross-linking and are available both as one- and two-component systems. Their particular feature is that they contain dispersions of copolymers such as those of styrene and n-butyl acrylate in the shape of rods or rice grains in the fluid silicone polymer. A small amount of the organic copolymer is also grafted onto the silicone backbone. 

In addition to its uses for electronic devices, silicon is a major component of silicone polymers. The silicone backbone consists of alternating silicon and oxygen atoms. The synthesis of these polymers begins with an organic chloride such as methyl chloride and an alloy of silicon and copper ... 

The recent interest in substituted silane polymers has resulted in a number of theoretical (15-19) and spectroscopic (19-21) studies. Most of the theoretical studies have assumed an all-trans planar zig-zag backbone conformation for computational simplicity. However, early PES studies of a number of short chain silicon catenates strongly suggested that the electronic properties may also depend on the conformation of the silicon backbone (22). This was recently confirmed by spectroscopic studies of poly(di-n-hexylsilane) in the solid state (23-26). Complementary studies in solution have suggested that conformational changes in the polysilane backbone may also be responsible for the unusual thermochromic behavior of many derivatives (27,28). In order to avoid the additional complexities associated with this thermochromism and possible aggregation effects at low temperatures, we have limited this report to polymer solutions at room temperature. 

Our results show that the network density (vg - 1/Q Q = swelling degree) of the crosslinked polymers is a function of the light intensity, the exposure time, the acrylate content, the molecular weight of the uncrosslinked silicone, and also of the length of the spacer group between the acrylate or methacrylate unit and the silicone backbone. Oxygen influences only the polymerization kinetics, but it does not influence the network density. 

Only few attempts have been made recently to study the influence of the spacer between the silicone backbone and the hydrophilic head group on the interfacial properties of silicone surfactants [1,2,3]. Further the strong dispersion interactions caused by cyclic hydrocarbon sUuctures, especially the dicyclopentadienyl unit [4] have never been recognized to be an effective tool to counterbalance the known reverse effect of the methyl groups of the siloxanyl unit in coventional silicone surfactants. 

Nitrogen and oxygen can be Incorporated Into the backbone such that they are surrounded by different atom types. For example, organic peroxides contain two covalently bonded oxygen atoms that form the peroxide linkage. These molecules are Inherently unstable. Two covalently bonded nitrogen atoms are also similarly unstable. These unstable structures decompose to form smaller unstable molecules that are used to start the polymerization for some types of monomers. Thus, to be incorporated implies that the molecules are found only singularly in the backbone chain. Sulfur and silicon are considered to be chain formers. They can be found in the backbone in multiple units connected covalently to molecules of the same type or with carbon. Complete molecules with a silicon backbone are possible, and molecules with multiple sulfur links incorporated into the system are common, particularly in sulfur-crosslinked rubber. 

One of the most remarkable features of the all-silicon backbone is that it leads to the delocalisation of a-electrons, a phenomenon which is essentially unknown in carbon chemistry.This can be understood in terms of the nature of the molecular orbitals associated with the Si-Si a-bonds. These are more diffuse than those associated with C-C a-bonds as they are constructed from higher energy 3s and 3p atomic orbitals. This leads to significant... 

Examination of the absorption spectra of the new polysilane materials reveals a number of interesting features (14). As shown in Table III, simple alkyl substituted polymers show absorption maxima around 300-310 nm. Aryl substitution directly on the silicon backbone, however, results in a strong bathochromic shift to 335-345 nm. It is noteworthy that 4, which has a pendant aromatic side group that is buffered from the backbone by a saturated spacer atom, absorbs in the same region as the peralkyl derivatives. This red shift for the silane polymers with aromatic substituents directly bonded to the backbone is reminiscent of a similar observation for phenyl substituted and terminate silicon catenates relative to the corresponding permethyl derivatives... 

In the model compounds, this red shift has been ascribed to a combination of aromatic substituent coupled with a decrease in the LUMO energy due to x -(a, d) interactions (15,16). Further examination of the data in Table III shows that the absorption maximum of the cyclohexylmethyl derivative, 9, is also somewhat red-shifted relative to the other alkyl polymers suggesting that the steric bulk of the substituents and/or conformational effects may also influence the polysilane absorption spectrum. 

The present calculations on po1y di-/j-hexylsilylene) are consistent with the hypothesis that the origin of thermochromlc behavior in selected polysilane polymers resides in a change in population of conformational states along the silicon backbone with temperature. 

Polysilane high polymers possessing fully saturated all-silicon backbone have attracted remarkable attention recently because of their unique optoelectronic properties and their importance in possible applications as photoresists, photoconductors, polymerization initiators, nonlinear optical materials etc. A number of review articles have been published on this topic4-9. The studies in this field have stimulated both experimental and theoretical chemists to elaborate on understanding the excited state nature of polysilanes and oligosilanes and of their mechanistic photochemistry. 

Stronger effects than those of hyperconjugation can be expected for substituents with stronger interacting power. The effect of aryl substituents will depend on their orientation relative to the plane of the silicon backbone.63... 

Wurtz coupling of dibutylaminotrimethyl-l-2-dichlorodisilane forms a partially networked polymer.79 This networked polymer shows an absorption maximum at 360 nm, that is 30 nm red shifted relative to the absorption of poly (dialkylsilanes). The shift is due to the nonbonding electron pair of the amino substituents extending the a-conjugation of the silicon backbone. Two broad emission bands at 440 nm and 400 nm are observed and assigned to the network silicon units and the linear silicon chains, respectively. The unusual photophysical properties arise from both the amino side groups and the networked structure. 

In addition to these polar groups, many types of fluorocarbon and hydrocarbon groups have been attached to the silicone backbone, sometimes in combination with polar groups. Some of these materials are used as compatibilizing agents or for other surface active properties but they lie outside the scope of this chapter. 

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