Molecular weight rubbery polymers

T inear polyurethane block copolymers have been objects of considerable -L/ research interest over recent years. These materials are composed of three parts, a diisocyanate, a low molecular weight chain extender (usually a diol but sometimes a diamine), and a low molecular weight rubbery polymer, frequently a polyether or polyester. The soft segment consists of the rubbery polymer while the diisocyanate and the chain extender form the hard segment These materials are classified as thermo-... 

It is therefore not surprising that the early investigators saw no promise in this mechanism of polymerization of butadiene, isoprene, etc., either by pure thermal initiation or by the use of free radical initiators, such as the peroxides. Instead they turned to sodium polymerization, which, although also rather slow and difficult to reproduce, at least yielded high-molecular-weight rubbery polymers from the dienes. Later, in the 1930s, when emulsion polymerization was introduced, it was found that this system, even though it involves the free... 

Polybutylene n. Any of a family of low-molecular-weight polymers of mixed 1-butene, d5-2-butene, tran5-2-butene, and isobutene. Depending on molecular weight, these polymers range from oils through tacky waxes, crystalline waxes, and rubbery solids. Poly(l-butene) shown below See image). 

There are a number of polymers which in fact cannot be melt processed because of their high molecular weights. These include PTFE, very high molecular weight polyethylene and most grades of cast poly(methyl methacrylate). In such cases shaping in the rubbery phase is usually the best alternative. 

Very high molecular weight polyethylenes (A/ in the range 1-6 X 10 ) prepared by the Ziegler process have also become available. As might be expected from consideration of Figure 3.1 these polymers cannot be processed easily in the molten state without decomposition and it is therefore often necessary to process in the rubbery phase. 

The development of oil-extended SBR in which a rubbery polymer of very high molecular weight is blended with substantial amounts of hydrocarbon oil. This provides a lower cost alternative to a polymer of more conventional average molecular weight. 

Cast material is stated to have a number average molecular weight of about 10. Whilst the Tg is about 104°C the molecular entanglements are so extensive that the material is incapable of flow below its decomposition temperature (approx. 170°C). There is thus a reasonably wide rubbery range and it is in this phase that such material is normally shaped. For injection moulding and extrusion much lower molecular weight materials are employed. Such polymers have a reasonable melt viscosity but marginally lower heat distortion temperatures and mechanical properties. 

Cross-linkable rubbery polyesters have been produced but are now no longer produced. Rubbery polyester-amides were introduced by ICI under the trade name Vulcaprene as a leathercloth material but later were used primarily as leather adhesives and as flexible coatings for rubber goods. A typical polymer may be made by condensing ethylene glycol, adipic acid and ethanolamine to a wax with a molecular weight of about 5000. 

Among the different pressure sensitive adhesives, acrylates are unique because they are one of the few materials that can be synthesized to be inherently tacky. Indeed, polyvinylethers, some amorphous polyolefins, and some ethylene-vinyl acetate copolymers are the only other polymers that share this unique property. Because of the access to a wide range of commercial monomers, their relatively low cost, and their ease of polymerization, acrylates have become the dominant single component pressure sensitive adhesive materials used in the industry. Other PSAs, such as those based on natural rubber or synthetic block copolymers with rubbery midblock require compounding of the elastomer with low molecular weight additives such as tackifiers, oils, and/or plasticizers. The absence of these low molecular weight additives can have some desirable advantages, such as ... 

Addition cure silicones can be delivered from solvent, waterborne emulsions, or 100% solids systems. The solvent free versions employ base polymers of intermediate molecular weight to achieve processable viscosity. These base polymers can have reactive moieties in terminal and/or pendant positions. These lower molecular weight, more functional systems result in a tighter crosslink network which feels rubbery to the hand. Low amounts of high molecular weight additives are included in some formulations to provide a more slippery feel [51,52]. 

The solidity of gel electrolytes results from chain entanglements. At high temperatures they flow like liquids, but on cooling they show a small increase in the shear modulus at temperatures well above T. This is the liquid-to-rubber transition. The values of shear modulus and viscosity for rubbery solids are considerably lower than those for glass forming liquids at an equivalent structural relaxation time. The local or microscopic viscosity relaxation time of the rubbery material, which is reflected in the 7], obeys a VTF equation with a pre-exponential factor equivalent to that for small-molecule liquids. Above the liquid-to-rubber transition, the VTF equation is also obeyed but the pre-exponential term for viscosity is much larger than is typical for small-molecule liquids and is dependent on the polymer molecular weight. 

As early as 1895, the synthesis of polydichlorophosphazene was attempted by H.N. Stokes by thermal ring-opening polymerization of hexachloro-triphosphazene [(NPCl2)3]. The product obtained by H.N. Stokes was a high-molecular weight cross-linked rubbery material called inorganic rubber which is insoluble in all solvents and hydrolytically decomposes into phosphates, ammonia, and hydrochloric acid in the presence of moisture. Because of its insolubility and hydrolytic instability, the polymer found no technological application and remained as a laboratory curiosity. 

Tg=—2 Amorphous, rubbery if molecular weight is high. When prepared by controlled reaction at low temperatures, polymer is semicrystal-line ... 

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