Polycarbosilane

Polymetallocarbosilanes. PolymetaHocarbosilanes having a number-average molecular weight of 700—100,000 can be prepared by reaction of polycarbosilane, /2 2 fx where R is H, or lower alkyl, with a tetraalkyl titanate, to give a mono-, di-, tri-, or tetrafunctional polymer... 

Polycarbosilanes are an interesting class of polymers from a materials standpoint however, they do not occur naturally. A variety of synthetic methods can be employed to produce such polymers, but this part of the chapter will focus on using ADMET as a viable route to synthesize polycarbosilanes, siloxanes, and other silicon-containing polymers. 

The first type of polycarbosilane synthesized by using ADMET methodology was a poly[carbo(dimethyl)silane].14c Linear poly(carbosilanes) are an important class of silicon-containing polymers due to their thermal, electronic, and optical properties.41 They are also ceramic precursors to silicon carbide after pyrolysis. ADMET opens up a new route to synthesize poly(carbosilanes), one that avoids many of the limitations found in earlier synthetic methods.41... 

See also PBT degradation structure and properties of, 44-46 synthesis of, 106, 191 Polycaprolactam (PCA), 530, 541 Poly(e-caprolactone) (CAPA, PCL), 28, 42, 86. See also PCL degradation OH-terminated, 98-99 Polycaprolactones, 213 Poly(carbo[dimethyl]silane)s, 450, 451 Polycarbonate glycols, 207 Polycarbonate-polysulfone block copolymer, 360 Polycarbonates, 213 chemical structure of, 5 Polycarbosilanes, 450-456 Poly(chlorocarbosilanes), 454 Polycondensations, 57, 100 Poly(l,4-cyclohexylenedimethylene terephthalate) (PCT), 25 Polydimethyl siloxanes, 4 Poly(dioxanone) (PDO), 27 Poly (4,4 -dipheny lpheny lpho sphine oxide) (PAPO), 347 Polydispersity, 57 Polydispersity index, 444 Poly(D-lactic acid) (PDLA), 41 Poly(DL-lactic acid) (PDLLA), 42 Polyester amides, 18 Polyester-based networks, 58-60 Polyester carbonates, 18 Polyester-ether block copolymers, 20 Polyester-ethers, 26... 

There are, however, other classes of inorganic and organometallic polymers that deserve consideration due to their considerable scientific and applicative relevance, such as polysilanes [28-31], polycarbosilanes [32,33],polysilazanes [33],polyborazines [34,35],polythiazenes [36], and, as an example,polymetal-locenylsilanes [37]. 

West (p. 6), Miller (p. 43), Zeigler (10), and Sawan (p. 112) outline the synthesis of a wide variety of soluble, processable polydiorganosilanes, a class of polymers which not long ago was thought to be intractable. Matyjaszewski (p. 78) has found significant improvements in the synthetic method for polydiorganosilane synthesis as well as new synthetic routes to unusual substituted polydiorganosilanes. Seyferth (p. 21, 143) reports synthetic routes to a number of new polycarbosilanes and polysilazanes which may be used as precursors to ceramic materials. 

As these experiments indicate, polysilanes can in some cases be converted to silicon carbide directly, without the necessity for formation of polycarbosilane, fractionation, or oxidation. For example, polysilastyrene copolymers can be formed into films or fibers and then crosslinked by irradiation with UV light. The crosslinked polysilane forms silicon carbide when heated to 1100°C in vacuum. (1U This method can be used in a "printing" mode, if a film of polysilane is cast onto a ceramic or metal substrate, then... 

Polycarbosilanes, in their broadest definition, are organosilicon polymers whose backbone is composed of silicon atoms, appropriately substituted, and difunctional organic groups which bridge the silicon atoms, as shown in formula 1. The polycarbosilanes may be linear, or they can be cyclic or polycyclic -... 

Another process for silicon carbide fibers, developed by Verbeek and Winter of Bayer AG [45], also is based on polymeric precursors which contain [SiCH2] units, although linear polysilmethylenes are not involved. The pyrolysis of tetramethylsilane at 700°C, with provision for recycling of unconverted (CHg Si and lower boiling products, gave a polycarbosilane resin, yellow to red-brown in color, which was soluble in aromatic and in chlorinated hydrocarbons. Such resins could be melt-spun but required a cure-step to render them infusible before they were pyrolyzed to ceramic... 

In conclusion, the lesson learned from the research carried out to date on the subject of polycarbosilanes is that the general rule that linear, noncrosslinked polymers are not suitable preceramic polymers applies here as well. Crosslinked network-type polymers are needed. Such structures can be generated in more than one way, but in the case of the polycarbosilanes they have, to date, been obtained mainly by thermolytic routes thermal treatment (with or without other chemical additives) in the case of the Yajima polycarbosilanes and the thermolysis of tetramethylsilane in the case of the Bayer process-derived polycarbosilane. 

I acknowledge with thanks the generous support of our research in the polycarbosilane area by the Air Force Office of Scientific Research. 

The cyclotrisilazane (R = Me) produced in reaction (14) is recycled at 650°C [by reaction with MeNHo) the reverse of reaction (14)] to increase the yield of processible polymer. Physicochemical characterization of this material shows it to have a softening point at 190°C and a C Si ratio of 1 1.18. Filaments 5-18 pm in diameter can be spun at 315°C. The precursor fiber is then rendered infusible by exposure to air and transformed into a ceramic fiber by heating to 1200°C under N2- The ceramic yield is on the order of 54% although, the composition of the resulting amorphous product is not reported. The approach used by Verbeek is quite similar to that employed by Yajima et al. (13) in the pyrolytic preparation of polycarbosilane and its transformation into SiC fibers. 

The first useful organosilicon preceramic polymer, a silicon carbide fiber precursor, was developed by S. Yajima and his coworkers at Tohoku University in Japan [5]. As might be expected on the basis of the 2 C/l Si ratio of the (CH3)2SiCl2 starting material used in this process, the ceramic fibers contain free carbon as well as silicon carbide. A typical analysis [5] showed a composition 1 SiC/0.78 C/0.22 Si02- (The latter is introduced in the oxidative cure step of the polycarbosilane fiber). 

The Yajima polycarbosilane, while it was one of the first, is not the only polymeric precursor to silicon carbide which has been developed. 

Another useful system which merits mention is the polycarbosilane which resulted from research carried out by C.L. Schilling and his coworkers in the Union Carbide Laboratories in Tarrytown, New York [6]. More recently, a useful polymeric precursor for silicon nitride has been developed by workers at Dow Corning Corporation [7]. 

The chemistry which is involved in the "graft" and "in situ" procedures and the structures of the hybrid polymers which are formed remain to be elucidated. However, there is no doubt that these procedures are useful ones. We have used them also to form new and useful hybrid preceramic polymers from the Yajima polycarbosilane which contains a plurality of [CH3Si(H)CH2l units [14]. 

The incorporation of decaborane into polycarbosilane-based polymers has been used in the densification of the polymer-derived SiC fibers. Improved densifi-cation resulted in the formation of fibers with density as high as 2840 kg/m3 corresponding to an increase of 89%.154... 

The spectrum of silicon based polymers is enriched by high tech ceramics like silicon nitride and carbide, respectively. These materials are produced by pyrolysis of appropriate polymeric precursors such as polysilanes, polycarbosilanes and polysilazanes (preceramics). These synthetic ceramics display a certain analogy to silicates, having SiC, SiN, or Si(C,N) as structural subunits instead ofSiO. 

Other organosilicon polymer precursors for ceramics have either been prepared or improved by means of transition metal complex-catalyzed chemistry. For instance, the Nicalon silicon carbide-based ceramic fibers are fabricated from a polycarbosilane that is produced by thermal rearrangement of poly(dimethylsilylene) [18]. The CH3(H)SiCH2 group is the major constituent of this polycarbosilane. 

The earliest work on silicon carbide fibers was done by Yajima and co-workers [3]. Yajima applied the Kumada [4] rearrangement to Burkhard s [5] dimethylpolysilane - an insoluble and infusible compound - (Eq. 1) and obtained by thermolysis at 400 - 450°C or by catalysis with polyborodiphenyl-siloxane at 350°C a melt spinnable and soluble polycarbosilane (Eq. 2). 

---