Polystyrenes syndiotactic

In the late 1990s a crystalline form of polystyrene, syndiotactic polystyrene became commercially available but unless otherwise stated references to polystyrene in this chapter will refer to the traditional amorphous polymer. 

Syndiotactic Polystyrene. Syndiotactic polystyrene is an interesting material because it has a Tg of 95 °C and a Tm of 260 °C [38], Polystyrene made via radical polymerisation may show some syndiotacticity, but its heat distortion temperature is too low to allow its use in important applications requiring temperatures around 120 °C or higher, such as medical equipment which requires sterilization or hot water storage containers. Idemitsu and Dow have reported titanium-based catalysts such as the one shown in Figure 10.23. We presume that the mechanism is a chain-end controlled "2,1" insertion. 

In contrast to isotactic polystyrene, syndiotactic polystyrene crystallises very rapidly (it contains ca 72% crystalline domains) with a crystallisation rate... 

Pure amorphous polymers, being homogeneous materials, are transparent. Atactic polystyrene is a good example. The crystalline syndiotactic form is not transparent. Alack of transparency does not necessarily indicate crystallinity, however. It can also be caused by inorganic fillers, pigments, gas bubbles (as in a foam), a second polymer phase, etc. 

The regular syndiotactic and isotactic structures are capable of crystallisation whereas the atactic polymer carmot normally do so. In the case of polypropylene the isotactic material is a crystalline fibre-forming material. It is also an important thermoplastic which can withstand boiling water for prolonged periods. Atactic polypropylene is a dead amorphous material. Polystyrene as commonly encountered is atactic and glass-like but the syndiotactic material... 

Because of the chain-stiffening effect of the benzene ring the TgS of commercial materials are in the range 90-100°C and isotactic polymers have similar values (approx. 100°C). A consequence of this Tg value plus the amorphous nature of the polymer is that we have a material that is hard and transparent at room temperature. Isotactic polystyrenes have been known since 1955 but have not been of commercial importance. Syndiotactic polystyrene using metallocene catalysis has recently become of commercial interest. Both stereoregular polymers are crystalline with values of 230°C and 270°C for the isotactic and syndiotactic materials respectively. They are also somewhat brittle (see Section 16.3). 

The first production of syndiotactic polystyrene has been credited to research workers at Idemitsu Kosan in 1985 who used cyc/opentadienyl titanium compounds with methyl aluminoxane as catalyst. 

Whereas the isotactic polymer has not been commercialised Dow were scheduled to bring on stream plant with a nameplate capacity of 37 000 t.p.a. in 1999 to produce a syndiotactic polystyrene under the trade name Questra. The particular features of this material are ... 

Since the last edition several new materials have been aimounced. Many of these are based on metallocene catalyst technology. Besides the more obvious materials such as metallocene-catalysed polyethylene and polypropylene these also include syndiotactic polystyrenes, ethylene-styrene copolymers and cycloolefin polymers. Developments also continue with condensation polymers with several new polyester-type materials of interest for bottle-blowing and/or degradable plastics. New phenolic-type resins have also been announced. As with previous editions I have tried to explain the properties of these new materials in terms of their structure and morphology involving the principles laid down in the earlier chapters. 

Polystyrene (PS) is the fourth big-volume thermoplastic. Styrene can be polymerized alone or copolymerized with other monomers. It can be polymerized by free radical initiators or using coordination catalysts. Recent work using group 4 metallocene combined with methylalumi-noxane produce stereoregular polymer. When homogeneous titanium catalyst is used, the polymer was predominantly syndiotactic. The heterogeneous titanium catalyst gave predominantly the isotactic. Copolymers with butadiene in a ratio of approximately 1 3 produces SBR, the most important synthetic rubber. 

Fig. 1 a, b. Projection along the chain axis and side view of models of syndiotactic polystyrene in the a) trans-planar conformation b) s(2/l)2 helical conformation... 

It is typical, for instance, of syndiotactic polystyrene (s-PS) [7-9] and syndiotactic poly- p-methylstyrene (s-PPMS) [10] to present crystalline forms with a transplant conformation of the chains (shown for s-PS in Fig. 1) as well as crystalline forms with sequences of dihedral angles of the kind TTG+G+ (or the equivalent G G TT), corresponding to a s(2/l)2 helical symmetry of the chains (shown for s-PS in Fig. 1). 

As an example we report in this paper the conformational energy maps of two already cited stereoregular polymers, which have been obtained very recently, syndiotactic polystyrene s-PS and syndiotactic polybutene s-PB (Fig. 4 and 5, respectively). In fact, the energy map calculated for s-PS shows... 

Hong, B. K. and Jo, W. H. (2000) Effects of molecular weight of SEBS triblock copolymer on the morphology, impact strength, and rheological property of syndiotactic polystyrene/ ethylene-propylene rubber blends. Polymer, 41, 2069-2079. 

Polymers that incorporate steric centers into their backbones can display various types of tacticity. The three principal types of tacticity are isotactic, syndiotactic, and atactic, as illustrated in Fig. 1.8 for polypropylene. Other polymers that display tacticity include polystyrene and poly a-olefins,... 

---