Polysulphonates

As the author pointed out in the first edition of this book, the likelihood of discovering new important general purpose materials was remote but special purpose materials could be expected to continue to be introduced. To date this prediction has proved correct and the 1960s saw the introduction of the polysulphones, the PPO-type materials, aromatic polyesters and polyamides, the ionomers and so on. In the 1970s the new plastics were even more specialised in their uses. On the other hand in the related fields of rubbers and fibres important new materials appeared, such as the aramid fibres and the various thermoplastic rubbers. Indeed the division between rubbers and plastics became more difficult to draw, with rubbery materials being handled on standard thermoplastics-processing equipment. 

ABS, polycarbonate and polysulphone) but large effects on crystalline polymers. It is particularly interesting, as well as being technically important, that for many crystalline polymers the unfilled polymer has a heat deflection temperature (at 1.82MPa stress) similar to the Tg, whereas the filled polymers have values close to the T (Table 9.2). 

Tension Above materials plus High-density polyethylene Polypropylene Acetal polymers Aliphatic polyamides (nylons) PPO Poly(ethylene terephthalate) Polysulphones... 

Figure 9.9. Curves for creep in tension of a commercial polysulphone (Polyethersulphone 300P-ICI) at 20°C. (From ICI Technical Service Note PES 101, reproduced permission of ICI Plastics...

A blow-moulded container, cylindrical in shape but with one spherical end, is prepared from the polysulphone whose creep curves at 20°C are illustrated in Figure 9.9. The cylindrical part of the container has an outside diameter of 200 mm and is required to withstand a constant internal pressure of 7 MPa at 20°C. It is estimated that the required service lifetime of the part will be one year and the maximum allowable strain is 2%. What will be the minimum wall thickness for satisfactory operation ... 

The process of blending with another glassy polymer to raise the heat distortion temperature is not restricted to polycarbonate, and the polysulphones are obvious candidates because of their higher Tg. One blend has been offered (Arylon T by USS Chemicals) which has a higher softening point than the ABS-polycarbonates. 

Although the nylons are not generally considered as outstanding electrical insulators, their toughness and, to some extent, their temperature resistance, have led to applications in coil formers and terminal blocks. Indeed, the new nylon 46 materials would appear to be of particular interest here. Acetal resins, polysulphones, modified PPO and polycarbonates, however, present a challenge to applications in this sphere. 

The transparent polyamides have increased significantly in importance in recent years. For transparent applications they are competitive with poly(methyl methacrylate), polycarbonates, polysulphones and MBS. In terms of toughness they are like polycarbonates, polysulphones and MBS and much better than the... 

The polyetherimides are competitive not only with other high-performance polymers such as the polysulphones and polyketones but also with polyphenylene sulphides, polyarylates, polyamide-imides and the polycarbonates. 

To enhance the resistance to heat softening his-phenol A is substituted by a stiffer molecule. Conventional bis-phenol A polycarbonates have lower heat distortion temperatures (deflection temperatures under load) than some of the somewhat newer aromatic thermoplastics described in the next chapter, such as the polysulphones. In 1979 a polycarbonate in which the bis-phenol A was replaced by tetramethylbis-phenol A was test marketed. This material had a Vicat softening point of 196 C, excellent resistance to hydrolysis, excellent resistance to tracking and a low density of about l.lg/cm-. Such improvements were obtained at the expense of impact strength and resistance to stress cracking. 

Another approach to increase the heat distortion temperature is to produce cocondensates of bisphenol A with bishydroxyphenyl fluorene. Some variations of this copolymer had heat distortion temperatures in excess of 200°C and with the potential to be produced at lower cost than such temperature-resistant thermoplastics as polysulphones and polyetherimides. Plans to develop this material were however abandoned when it was found, during trials of test materials, that workers developed skin rashes said to be similar to those encountered on contact with poison ivy. 

The successful development of polyfethylene terephthalate) fibres such as Dacron and Terylene stimulated extensive research into other polymers containing p-phenylene groups in the main chain. This led to not only the now well-established polycarbonates (see Chapter 20) but also to a wide range of other materials. These include the aromatic polyamides (already considered in Chapter 18), the polyphenylene ethers, the polyphenylene sulphides, the polysulphones and a range of linear aromatic polyesters. 

Property Units Polycarbonate Polysulphone Phenoxy PPO PPO-PS Blend PET PBT... 

The range of blends now available comprises a broad spectrum of materials superior in many respects, particularly heat deformation resistance, to the general purpose thermoplastics but at a lower price than the more heat-resistant materials such as the polycarbonates, polyphenylene sulphides and polysulphones. At the present time the materials that come closest to them in properties are the ABS/ polycarbonate blends. Some typical properties are given in Table 21.1. 

Although it is somewhat of an oversimplification, the polysulphones are best considered as a group of materials similar to the aromatic polycarbonates but which are able to withstand more rigorous conditions of use. Because of their higher price they are only considered when polycarbonates or other cheaper polymers are unsuitable. 

The simplest aromatic polysulphone, poly-(p-phenylene sulphone) (formula I of Table 21.3) does not show thermoplastic behaviour, melting with decomposition above 500°C. Hence in order to obtain a material capable of being processed on conventional equipment the polymer chain is made more flexible by incorporating ether links into the backbone. 

The first commercial polymer Table 21.3, II) was offered in 1965 by Union Carbide as Bakelite Polysulfone, now renamed Udel. In 1967 Minnesota Mining and Manufacturing introduced Astrel 360 Table 21.3, V), which they referred to as a polyarylsulfone. In 1972 ICI brought a third material onto the market which they called a polyethersulphone (III) and which they then marketed as Victrex. They also introduced a material intermediate between III and V known as Polyethersulphone 720P (IV) but which has now been withdrawn. In the late 1970s Union Carbide introduced Radel (VI), which has a higher level of toughness. Around 1986 Union Carbide sold their interest in polysulphones to Amoco. In addition the Astrel materials were produced by Carborundum under licence from ICI. 

In 1992 ICI withdrew from the polysulphone market, with BASF (Ultrason) joining Amoco as manufacturers whilst a small plant operated by Sumitomo was due to come on stream in the mid-1990s. 

In principle there are two main routes to the preparation of polysulphones ... 

The Ar and/or Ar group(s) will contain sulphone groups and if Ar = Ar then identical products may be obtained by the two routes. Polyetherification processes form the basis of current commercial polysulphone production methods. These will be discussed further below. 

A consequence of the reaction is that it is possible to produce a range of polymers by reacting bisphenates with appropriately activated aromatic dihalides. In the case when the dihalide is activated by the presence of a sulphone —SO,— group the polymers may be referred to as polysulphones. The Amoco materials are prepared in this way. 

A range of polysulphones has been prepared with a variety of bis-phenols other than bis-phenol A. As might be expected from the discussion in Chapter 4 and from experience with the range of polycarbonates (Chapter 20), replacement of the isopropylidene link with a methylene, sulphide or oxygen link depresses the Tg whilst —C(CgH5)2— and sulphone links raise it. The bis-phenol derived from norcamphor leads to a polysulphone with a Tg of 250°C (195°C for a Udel-type polymer). 

The differences between the main types of polysulphone are quite small. The polyethersulphones (Type III in Table 21.3) have markedly better creep resistance at elevated temperatures, e.g. 150°C, significantly higher heat distortion temperatures and marginally superior room temperature meehanical properties than the Type II materials. They also exhibit higher water absotption, dielectric constant and specific gravity. 

Table 21.4 Comparison of glass-filled with unfilled polysulphone ...

Glass-fibre-filled polysulphones are also available. These show significantly increased creep resistance and lower coefficients of thermal expansion (Table 21.4). 

When processing polysulphones there are four main points to bear in mind ... 

For extrusion and blow moulding the polysulphones used are of higher molecular weight. Melt temperatures for blow moulding are of the order of 300-360°C with mould temperatures about 70-95°C. 

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