Polystyrene glass transition

Substitute natural gas (SNG), 73 692, 768 Substituted phenols, 18 757-758 Substituted polystyrene, glass-transition temperatures of, 23 367t Substituted pyridines... 

Thomas LC, Boiler A, Okazaki I, Wunderlich B (1997) Modulated Differential Scanning Calorimetry in the Glass Transition Region, IV. Pseudo-isothermal Analysis of the Polystyrene Glass Transition, Thermochim Acta 291 85-94. 

Block copolymers as they are made today are not suitable for tire rubbers even when vulcanized because of the excessive hysteretic losses present at temperatures approaching the polystyrene glass transition. 

One way to approach the problem with the hysteretic loss associated with the onset of the polystyrene glass transition in vulcanized S-I-S polymers is with block copolymers having small random styrene-isoprene copolymer end-blocks, and a pure polyisoprene center block, IS-I-IS. The copolymer composition is chosen to produce a Tg of 40-45 C, at about 60% styrene content. At temperatures experienced in "green processing or tire building the block copolymer would be below Tg and strong, while at the elevated temperatures typically experienced by the vulcanized product in actual use, the end-blocks would be above their glass transition temperature... 

Fig. 2. Glass-transition temperature, T, for two commercially available, miscible blend systems (a) poly(phenylene oxide) (PPO) and polystyrene (PS) (42) ...

Carbon Cha.in Backbone Polymers. These polymers may be represented by (4) and considered derivatives of polyethylene, where n is the degree of polymeriza tion and R is (an alkyl group or) a functional group hydrogen (polyethylene), methyl (polypropylene), carboxyl (poly(acryhc acid)), chlorine (poly(vinyl chloride)), phenyl (polystyrene) hydroxyl (poly(vinyl alcohol)), ester (poly(vinyl acetate)), nitrile (polyacrylonitrile), vinyl (polybutadiene), etc. The functional groups and the molecular weight of the polymers, control thek properties which vary in hydrophobicity, solubiUty characteristics, glass-transition temperature, and crystallinity. 

Table 3. Glass-Transition Temperatures of Substituted Polystyrene...

The glass-transition temperature in amorphous polymers is also sensitive to copolymerization. Generally, T of a random copolymer falls between the glass-transition temperatures of the respective homopolymers. For example, T for solution-polymerized polybutadiene is —that for solution-polymerized polystyrene is -HlOO°C. A commercial solution random copolymer of butadiene and styrene (Firestone s Stereon) shows an intermediate T of —(48). The glass-transition temperature of the random copolymer can sometimes be related simply as follows ... 

In the crystalline region isotactic polystyrene molecules take a helical form with three monomer residues per turn and an identity period of 6.65 A. One hundred percent crystalline polymer has a density of 1.12 compared with 1.05 for amorphous polymer and is also translucent. The melting point of the polymer is as high as 230°C. Below the glass transition temperature of 97°C the polymer is rather brittle. 

We present here a simple experiment, conceived to test both the reptation model and the minor chain model, by Welp et al. [50] and Agrawal et al. [51-53]. Consider the HDH/DHD interface formed with two layers of polystyrene with chain architectures shown in Fig. 5. In one of the layers, the central 50% of the chain is deuterated. This constitutes a triblock copolymer of labeled and normal polystyrene, which is, denoted HDH. In the second layer, the labeling has been reversed so that the two end fractions of the chain are deuterated, denoted by DHD. At temperatures above the glass transition temperature of the polystyrene ( 100°C), the polymer chains begin to interdiffuse across the... 

With plastics there is a certain temperature, called the glass transition temperature, Tg, below which the material behaves like glass i.e. it is hard and rigid. As can be seen from Table 1.8 the value for Tg for a particular plastic is not necessarily a low temperature. This immediately helps to explain some of the differences which we observe in plastics. For example, at room temperature polystyrene and acrylic are below their respective Tg values and hence we observe these materials in their glassy state. Note, however, that in contrast, at room temperature, polyethylene is above its glass transition temperature and so we observe a very flexible matoial. When cooled below its Tg it then becomes a hard, brittle solid. Plastics can have several transitions. 

Molecular Motion in amorphous atactic polystyrene (PS) is more complicated and a number of relaxation processes, a through 5 have been detected by various techniques as reviewed recently by Sillescu74). Of course, motions above and below the glass transition temperature Tg have to be treated separately, as well as chain and side group mobility, respectively. Motion well above Tg as well as phenyl motion in the glassy state, involving rapid 180° jumps around their axes to the backbone has been discussed in detail in Ref.17). Here we will concentrate on chain mobility in the vicinity of the glass transition. 

The most common backbone structure found in commercial polymers is the saturated carbon-carbon structure. Polymers with saturated carbon-carbon backbones, such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyacrylates, are produced using chain-growth polymerizations. The saturated carbon-carbon backbone of polyethylene with no side groups is a relatively flexible polymer chain. The glass transition temperature is low at -20°C for high-density polyethylene. Side groups on the carbon-carbon backbone influence thermal transitions, solubility, and other polymer properties. 

In contrast to the applications previously described in which alkanesulfonates are used in polymers with a high glass transition temperature (PVC, polystyrene, and ABS), in antistatic-modified polyethylene articles the antistatic agent is able to continue migrating to the surface over a long period of time. Thus, a more permanent antistatic effect is achieved. 

---