Academic literature on the topic 'O-phenylenes'

The polysiloxane of greatest commercial importance and scientific interest is poly(dimethylsiloxane) (PDMS), [Si(CH3)2 –O –]x, a member of the symmetrical dialkyl polysiloxanes, with repeat unit [SiR2 –O –]x. This polymer is discussed extensively in the following chapters, particularly in chapter 5. Other members of this series are poly(diethylsiloxane) [Si(C2H5) –O–]x, and poly(di-n-propylsiloxane) [SiC3H7)2–O–]x. An example of an aryl member of the symmetrically substituted series is poly(diphenylsiloxane), with repeat unit [Si(C6H5)2–O–]x. This polymer is unusual because of its very high melting point and the mesophase it exhibits. The closely related polymer, poly(phenyl/tolylsiloxane), has also been prepared and studied. The unsymmetrically substituted polysiloxanes have the repeat unit [SiRR’O–]x, and are exemplified by poly(methylphenylsiloxane) [Si(CH3) (C6H5) –O–]xand poly(methylhydrosiloxane) [Si(CH3)(H) –O–]x. In some cases, one of the side chains has been unusually long, for example C6H13, C16H33, and C18H37, including a branched side chain—CH(CH3– (CH2)m–CH3. Another example has methoxy-substituted aromatic fragments as one of the two side chains in the repeat unit. Such chains have stereochemical variability in analogy with the vinyl polymers such as polypropylene [CH(CH3) –CH2–]xand vinylidene polymers such as poly(methyl methacrylate) [C(CH3)(C = OOCH3) –CH2–]xOne can also introduce optically active groups as side chains, the simplest example being the secondary butyl group—CH(CH3)(C2H5). Another example involves redox-active dendritic wedges containing ferrocenyl and carbonylchromium moieties. Other substituents have included phenylethenyl groups, cyclic siloxane groups, and Cr-bound carbazole chromophores. In a reversal of roles, some polymers were prepared to have PDMS side chains on a poly(phenylacetylene) main chain. Siloxane-terminated solubilizing side chains are used to improve the properties of thin-film transistors. Silalkylene polymers have methylene groups replacing the oxygen atoms in the backbone. Poly(dimethylsilmethylene) is an example, [Si(CH3)2–CH2]x. A variation on this theme is to include aryl groups, for example, in poly(dimethyldiphenylsilylenemethylene) [Si(CH3)2CH2Si(C6H5)2]x. Other aryl substituents, specifically tolyl groups, have also been included as side chains. It is also possible to insert a silphenylene group [Si(CH3)2–C6H4–] into the backbone of the polysiloxane repeat unit to give [Si(CH3)2–C6H4– Si(CH3)2O–], in which the phenylene can be para or ortho or meta. A specific example is poly(tetramethyl-p-silphenylene-siloxane).

Polysiloxanes are unique among inorganic and semi-inorganic polymers; they are also the most studied and the most important with regard to commercial applications. Thus, it’s not surprising that there is an extensive literature describing the synthesis, properties, and applications of these materials, including books, proceedings books, sections of books or encyclopedias, review articles, and historical articles. The purpose of this volume is not to give a comprehensive overview of these polymers but rather to focus on some novel and interesting aspects of polysiloxane science and engineering, including properties, work in progress, and important unsolved problems. The Si-O backbone endows polysiloxanes with a variety of intriguing properties. The strength of the Si-O bond, for example, imparts considerable thermal stability, which is important for high-temperature applications (e.g., as heat-transfer agents and high-performance elastomers). The nature of the bonding and the chemical characteristics of typical side groups impart low surface free energy and therefore desirable surface properties. Polysiloxanes, for example, are used as mold-release agents, waterproofing sprays, and biomedical materials. Structural features of the chains give rise to physical properties that are also of considerable scientific interest. For example, the substituted Si atom and the unsubstituted O atom differ greatly in size, giving the chain a nonuniform cross section. This characteristic affects the way the chains pack in the bulk, amorphous state, which explains the unusual equation-of-state properties (such as compressibility). Also, the bond angles around the O atom are much larger than those around the Si, which makes the planar all trans form of the chain approximate a series of closed polygons, as illustrated in figure 1.1. As a result, siloxane chains exhibit a number of interesting configurational characteristics that impact properties and associated applications. The major categories of homopolymers and copolymers to be discussed are (i) linear siloxane polymers -SiRR’O-] (with various alkyl and aryl R,R’ side groups), (ii) sesquisiloxane polymers possibly having a ladder structure, (iii) siloxane-silarylene polymers [–Si(CH3)2OSi(CH3)2(C6H4)m –] (where the skeletal phenylene units are either meta or para), (iv) silalkylene polymers [–Si(CH3)2(CH2)m–], and (v) random and block copolymers, and blends of some of the above.

At the present time, polysiloxanes are unique among inorganic and semi-inorganic polymers. They have been the most studied by far, and are the most important with regard to commercial applications. Thus, it is not surprising that a large number of review articles exist describing the synthesis, properties, and applications of these materials. The Si-O backbone of this class of polymers endows it with a variety of intriguing properties. For example, the strength of this bond gives the siloxane polymers considerable thermal stability, which is very important for their use in high-temperature application (for example as heat-transfer agents and high-performance elastomers). The nature of the bonding and the chemical characteristics of typical side groups give the chains a very low surface free energy and, therefore, highly unusual and desirable surface properties. Not surprising, polysiloxanes are much used, for example, as mold-release agents, for waterproofing garments, and as biomedical materials. Some unusual structural features of the chains give rise to physical properties that are also of considerable scientific interest. For example, the substituted Si atom and the unsubstituted O atom differ greatly in size, giving the chain a very irregular cross section. This influences the way the chains pack in the bulk, amorphous state, which, in turn, gives the chains very unusual equation-of-state properties (such as compressibilities). Also, the bond angles around the O atom are much larger than those around the Si, and this makes the planar all-trans form of the chain approximate a series of closed polygons. As a result, siloxane chains exhibit a number of interesting configurational characteristics. These structural features, and a number of properties and their associated applications, will be discussed in this chapter. The major categories of homopolymers and copolymers to be discussed are linear siloxane polymers [-SiRR'O-] (with various alkyl and aryl R,R' side groups), (ii) sesquisiloxane polymers possibly having a ladder structure, (iii) siloxane-silarylene polymers [-Si(CH3)2OSi(CH3)2(C6H4)m-] (where the skeletal phenylene units are either meta or para), (iv) silalkylene polymers [-Si(CH3)2(CH2)m-], and (v) random and block copolymers, and blends of some of the above. Topics of particular importance are the structure, flexibility, transition temperatures, permeability, and other physical properties.