Isotactic polystyrene blends

The brittleness of isotactic polystyrenes has hindered their commercial development. Quoted Izod impact strengths are only 20% that of conventional amorphous polymer. Impact strength double that of the amorphous material has, however, been claimed when isotactic polymer is blended with a synthetic rubber or a polyolefin. 

Isotactic Polystyrene. The familiar steam molding of pre-expanded particles has so far not been applied successfully to isotactic polystyrene. However, the polymer has been foamed, according to three disclosed methods. For example, finely divided acetone-insoluble polymer, with a melting point in excess of 200°C., is blended with a liquid selected from methylene chloride, aromatic hydrocarbons, or halogenated aromatic hydrocarbons. This blend is then heated (84). A mixture of molten polymer and methyl chloride, propane, or butane is suddenly depressurized (8). Foam may also be generated in a continuous manner directly from a butyllithium-initiated polymerization conducted in the presence of a 4/1 blend of benzene and petroleum ether (15). 

After having studied in our laboratory, polymer blends of amorphous polymers poly-c-caprolactone and poly (vinyl chloride) (1,2) (PCL/ PVC), blends with a crystalline component PCL/PVC (3,4), poly(2,6-dimethyl phenylene oxide) (PPO) with isotactic polystyrene (i-PS) (5) and atactic polystyrene (a-PS) with i-PS (6), we have now become involved in the study of a blend in which both polymers crystallize. The system chosen is the poly(1,4-butylene terephthalate)/poly(ethylene terephthalate) (PBT/PET) blend. The crystallization behavior of PBT has been studied extensively in our laboratory (7,8) this polymer has a... 

PEC, PPO, and PS are amorphous materials as normally melt processed, a fact which prevents the use of melting point depression analyses for experimentally determining AHnix or B for the blends with PS. Isotactic polystyrene, i-PS, is able to crystallize, is miscible with PPO, and has been successfully used to determine the parameters related to AHaix (7,12.18). This study shows that i-PS is also miscible with PEC copolymers which contain up to 20 moleX trimethyl comonomer. This fact permits the use of i-PS melting point depression analysis to determine the effect of comonomer content on AHaix with i-PS. 

Toughened Plastics of Isotactic Polystyrene and Isotactic Polypropylene Blends... 

FIGURE 11.18 Radial growth rates for pure isotactic polystyrene (PS) (M = 60,000 g mol" ) and two samples blended with atactic PS of molecular weight 41,700 and 247,000. (From Keith, H.D. and Padden, F.J., J. Appl. Phys., 35, 1286, 1964. With permission.)... 

Differential scanning calorimetry (DSC) experiments indicated that atactic polystyrene and polyvinyl methyl ether (PVME) form miscible blends [8,9]. Syndiotactic and isotactic polystyrene when blended with PVME, phase separate at aU temperatures above the glass transition temperature of PVME. Only weak van der Waals interactions between the phenyl rings in polystyrene with the methoxy group of PVME were detected using 2-dimensional nuclear magnetic resonance (NMR) spectroscopy. 

Fig. 2.2 DSC thermogram of pure isotactic polystyrene crystallized at 175 °C for 1 h. An exotherm feature appears between peak II and peak III (Scanning rate 1.25 °C/min). Adapted with permission from figure 3 in Plans J, MacKnight WJ and Karasz FE, Equilibrium Melting Point Depression for Blends of Isotactic Polystyrene with Poly(2,6-dimethylphenylene oxide). Macromolecules 17 810-814. Copyright (1984) American Chemical Society...

Blends of PPO with PS containing sulfonated and carboxylated groups have been reported in various studies [394-396]. The miscibility of sulfonated PS with PPO, sulfonated PPO with PS and blends of the sulfonated polymers was reported by Hseih and Peilfer [394]. Miscibility was maintained with sulfonation levels up to 2-4mol% for PS with sulfonated PPO and sulfonated PS with PPO. When both polymers were sulfonated, phase separation occurred at higher levels (> 10mol% sulfonation). The miscibility can be influenced by counter ion, as noted in a comparison of a Zn + neutralized sulfonic acid modified PS, which exhibited a larger miscibility window with PPO than the Na neutralized coimterpart [396]. Syndiotactic polystyrene was noted to be miscible over the entire composition range in amorphous blends with PPO, where the Tg versus composition followed the Fox equation predictions [397]. Isotactic polystyrene miscibility with PPO has also been observed, with crystallization and orientation data reported on the blend [398]. 

Poly(cyclohexyl acrylate) was shown to be miscible with PS with ucst behavior [720]. Random copolymers of cyclohexyl acrylate with n-butyl acrylate showed miscibility with PS above 50% cyclohexyl acrylate[721]. Poly(cyclohexyl methacrylate)/isotactic PS blends showed miscibility based on calorimetry and NMR studies [722]. The NMR results showed homogeneous behavior at a scale of 2.5-3.5 nm. Poly(4-trimethylsilyl styrene) miscibility with polyisoprene was observed with a lest behavior (critical temperature = 172 ° C at degree of polymerization of 370) [723]. The interaction parameter, showed the following relationship = 0.027—9.5/T. Isotactic and syndiotactic polystyrene both exhibit crystallinity, whereas atactic polystyrene is amorphous. Atactic PS/isotactic PS blends exhibited crystallization kinetics, which decreased linearly with atactic PS addition indicating miscibility [724]. The TgS of aPS and iPS are identical, thus Tg methods could not be employed to assess miscibility. Atactic PS/syndiotactic PS blends were also noted to be miscible with rejection of atactic PS in the interfibrillar region between the lamellar stacks of sPS [725]. 

In miscible binary blends, amorphous homopolymers are completely accommodated within amorphous layers of the lamellar morphology formed after the crystallization of crystalline homopolymers. Stein et al. [51], for example, observed the lamellar morphology formed in a miscible blend of PCL and poly(vinyl chloride) (PVC) using SAXS as a function of composition. They found that PVC existed in amorphous layers of the lamellar morphology to yield a linear increase in the amorphous layer thickness with increasing PVC composition, whereas the crystalline layer thickness remained constant irrespective of composition. Wenig et al. [52] obtained similar results for a miscible blend of poly(2,6-dimethylphenylene oxide) (PPO) and isotactic polystyrene (iPS). However, a different result was reported for a miscible blend of iPS and atactic polystyrene [53], where the amorphous layer thickness was almost constant irrespective of composition. Stein et al. [51] explained this difference in... 

Figure 16 Sheaf-like lamellar aggregates crystallized from the melt in (a) a blend of linear and low density polyethylene at 125 °C, (b) isotactic polystyrene at 220 °Q (c) isotactic polypropylene at 160 °C...

Figure 32 Dominant/subsidiary structure in polystyrene crystallized at 162 °C (a) isotactic polystyrene (b) 1 1 blend of...

Fig.l Differential scanning calorimetry (DSC) cooling scans from the melt, at 10°Cmin 1, of the following materials (from top to bottom) Isotactic polypropylene (iPP) iPP after self-nucleation treatment at TS = 162°C 80/20 polystyrene (PS)/iPP melt mixed blend 80/20 PS/iPP melt mixed blend after self nucleation treatment at Ts = 161 °C 80/20 PS/iPP unmixed blend (UB), see text and atactic PS homopolymer. (From [68] with permission)... 

This review summarizes our work at the University of Bayreuth over the last few years on improving the electret performance of the commodity polymer isotactic polypropylene (Sect. 3) and the commodity polymer blend system polystyrene/polyphenylene ether (Sect. 4) to provide electret materials based on inexpensive and easily processable polymers. To open up polymer materials for electret applications at elevated temperatures we concentrated our research on commercially available high performance thermoplastic polyetherimide resins and synthesized several fluorinaled polyetherimides to identify structure-property relations and to improve further the performance at elevated temperatures (Sect. 5). 

---