Poly rubber extensibility

In Chapters 3 and 11 reference was made to thermoplastic elastomers of the triblock type. The most well known consist of a block of butadiene units joined at each end to a block of styrene units. At room temperature the styrene blocks congregate into glassy domains which act effectively to link the butadiene segments into a rubbery network. Above the Tg of the polystyrene these domains disappear and the polymer begins to flow like a thermoplastic. Because of the relatively low Tg of the short polystyrene blocks such rubbers have very limited heat resistance. Whilst in principle it may be possible to use end-blocks with a higher Tg an alternative approach is to use a block copolymer in which one of the blocks is capable of crystallisation and with a well above room temperature. Using what may be considered to be an extension of the chemical technology of poly(ethylene terephthalate) this approach has led to the availability of thermoplastic polyester elastomers (Hytrel—Du Pont Amitel—Akzo). 

For applications where only mechanical properties are relevant, it is often sufficient to use resins for the filling and we end up with carbon-reinforced polymer structures. Such materials [23] can be soft, like the family of poly-butadiene materials leading to rubber or tires. The transport properties of the carbon fibers lead to some limited improvement of the transport properties of the polymer. If carbon nanotubes with their extensive propensity of percolation are used [24], then a compromise between mechanical reinforcement and improvement of electrical and thermal stability is possible provided one solves the severe challenge of homogeneous mixing of binder and filler phases. For the macroscopic carbon fibers this is less of a problem, in particular when advanced techniques of vacuum infiltration of the fluid resin precursor and suitable chemical functionalization of the carbon fiber are applied. 

Production of mechano-radical in Nylons by either larger deformations or fractures were extensively investigated by DeVries and his collaborators (17,18,53), Peterlin and his coworkers (54, 55) and Becht and Fischer (22). ESR studies on mechano-radicals of other pol3rmers, including polystyrene (49, 56, 57), pol)ndnylacetate (49,57—59) poly o-methylstyrene (11), polyisobutyrene (11), Natural Rubber (22), other elasttxners (60-62), polysaccharides (6ii), and cellulose (63, 64). 

Molecular weights are not often measured directly for control of production of polymers because other product properties are more convenient experimentally or are thought to be more directly related to various end uses. Solution and melt viscosities are examples of the latter properties. Poly(vinyl chloride) (PVC) production is controlled aceording to the viscosity of a solution of arbitrary concentration relative to that of the pure solvent. Polyolefin polymers are made to specific values of a melt flow parameter called melt index, whereas rubber is characterized by its Mooney viscosity, which is a different measure related more or less to melt viscosity. These parameters are obviously of some practical utility, or they would not be used so extensively. They are unfortunately specific to particular polymers and are of little or no use in bringing experience with one polymer to bear on problems associated with another. 

Previous investigations have shown that polyisobutene and poly(isobutene-co-iso-prene), i. e. butyl rubber, are unable to cross-link in the presence of free radicals, since extensive chain scissions occur and thus low molecular weight products are formed The degradation mechanism proposed by Loan involves, in the case of polyisobutene, the H abstraction from methyl groups followed by chain scission. Apparently, the formation of secondary alkyl radicals, which are believed to be responsible of polyolefin radical curing is prevented for steric reasons by the presence of two adjacent dimethyl substituted carbon atoms and hence j3 scission reactions prevail. 

Three homopolymer (diblock copolymer) phase boundary systems have been studied extensively the system of polystyrene (PS) and poly(2-vinylpyridine) (PVP) reinforced with diblock copolymers ofPS-PVP [22,25,28,31-33], the system of poly(methyl methacrylate) (PMMA) and PS reinforced with diblock copolymers of PMMA-PS [17,24,34,35] and the system of PMMA and poly(phe-nylene oxide) (PPO) reinforced by diblock copolymers of PMMA-PS [ 14,36,37]. Phase boundaries between PS and a crosslinked epoxy (XEp) were reinforced with carboxy-terminated PS chains whose -COOH ends reacted with either excess amines or epoxy to form a grafted brush at the interface [38,39]. In a similar manner, interfaces between rubber-modified PS (HIPS) and XEp reinforced with grafted PS-COOH chains have been investigated [40]. 

Ratna (2001) examined the cure and phase separation of carboxy-terminated poly(2-ethyl hexyl acrylate) (CTPEHA) liquid modifler in DGEBA/diethyltoluene diamine (DEED). It was found that the CTPEHA liquid rubber causes a delay in the polymerization of the epoxy-resin matrix due to chain extension during pre-reaction and the viscosity effect. The Tg decreases with increasing rubber concentration. 

Most of the research effort on the ionomers has been devoted to only a small number of materials, notably the ethylenes the styrenes, the rubbers(9)5 and those based on poly(tetra-fluoroethylene), the last of which is the subject of the present volume. As a result of these extensive investigations, it has become clear that the reason for the dramatic effects which are obsverved on ion incorporation is, not unexpectedly, the aggregation of ionic groups in media of low dielectric constant. Small angle X-ray and neutron scattering, backed up by a wide range of other techniques, have demonstrated clearly the existence of ionic... 

Although the dynamic mechanical properties and the stress-strain behavior iV of block copolymers have been studied extensively, very little creep data are available on these materials (1-17). A number of block copolymers are now commercially available as thermoplastic elastomers to replace crosslinked rubber formulations and other plastics (16). For applications in which the finished object must bear loads for extended periods of time, it is important to know how these new materials compare with conventional crosslinked rubbers and more rigid plastics in dimensional stability or creep behavior. The creep of five commercial block polymers was measured as a function of temperature and molding conditions. Four of the polymers had crystalline hard blocks, and one had a glassy polystyrene hard block. The soft blocks were various kinds of elastomeric materials. The creep of the block polymers was also compared with that of a normal, crosslinked natural rubber and crystalline poly(tetra-methylene terephthalate) (PTMT). 

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