Glass transition chemical structure

Table 1. Chemical Structures and Glass-Transition Temperatures, 7, of PSF, PES, and PPSF...

Polyisobutylene has a similar chemical backbone to butyl rubber, but does not contain double carbon-carbon bonds (only terminal unsaturation). Many of its characteristics are similar to butyl rubber (ageing and chemical resistance, low water absorption, low permeability). The polymers of the isobutylene family have very little tendency to crystallize. Their strength is reached by cross-linking instead of crystallization. The amorphous structure of these polymers is responsible for their flexibility, permanent tack and resistance to shock. Because the glass transition temperature is low (about —60°C), flexibility is maintained even at temperatures well below ambient temperature. 

Role of Chemical Structure 5.2.2.1 Glass Transition and Solubility... 

TABLE 5.1 Effect of Chemical Structure on Solubility and Glass Transition... 

This chapter is concerned with aspects of the structure of polymeric materials outside those of simple chemical composition. The main topics covered are polymer stereochemistry, crystallinity, and the character of amorphous polymers including the glass transition. These may be thought of as arising from the primary structure of the constituent molecules in ways that will become clearer as the chapter progresses. 

Features of chemical structure that affect the degree of molecular freedom influence both the crystalline melting point and the glass transition temperature. Moreover, such features have roughly similar effects on both properties, so that the empirical rule has been found that for many polymers ... 

Diamantane-based polymers are synthesized to take advantage of their stiffness, chemical and thermal stability, high glass transition temperature, improved solubility in organic solvents, and retention of their physical properties at high temperatures. All these special properties result from their diamantane-based molecular structure [90]. Polyamides are high-temperature polymers with a broad range of applications in different scientific and industrial fields. However, their process is very difficult because of poor solubility and lack of adequate thermal stability retention [90]. Incorporation of 1,6- or... 

Owing to multi-functionahty, physical properties such as solubihty and the glass transition temperature and chemical functionahty the hyperbranched (meth) acrylates can be controlled by the chemical modification of the functional groups. The modifications of the chain architecture and chemical structure by SCV(C)P of inimers and functional monomers, which may lead to a facile, one-pot synthesis of novel functionahzed hyperbranched polymers, is another attractive feature of the process. The procedure can be regarded as a convenient approach toward the preparation of the chemically sensitive interfaces. 

The self-similar spectrum is not valid at short times, X < X0, where the details of chemical structure become important (glass transition, entanglements, etc.). The cross-over to the glass transition at short times is typical for all polymeric materials, for both liquids and solids. The critical gel is no exception in that respect. X0 could be used as a characteristic time in the CW spectrum since it somehow characterizes the molecular building block of the critical gel however, it has no direct relation to the LST. At times shorter than X0, the LST has no immediate effect on the rheology. Indirect effects might be seen as a shift in the glass transition, for instance, but these will not be studied here. 

Several factors related to chemical structure are known to affect the glass transition tempera lure. The most important factor is chain stiffness or flexibility of the polymer. Main-chain aliphatic groups, ether linkages, and dimethylsiloxane groups build flexibility into a polymer and lower Tg Aliphatic side chains also lower Tg, (he effect of the length of aliphatic groups is illustrated by the methacrylate series (4,38) ... 

Chemical structure factors affect the melting point and glass transition temperature in much the same manner. A good empirical rale for many polymers is (142-144)... 

Despite the current lack of clarity regarding the relationship between glass transition and chemical reaction kinetics, it is still quite feasible that chemical and biochemical reaction rates may be governed by mobility, i.e., the mobility that is most rate limiting to a particular reaction scheme (e.g., water mobility, reactant mobility, molecular-level matrix mobility, local or microregion mobility), but perhaps not simply by an average amorphous solid mobility as reflected by the Tg. Ludescher et al. (2001) recommend the use of luminescence spectroscopy to investigate how rates of specific chemical and physical processes important in amorphous solid foods are influenced by specific modes of molecular mobility, as well as by molecular structure. 

A simple relationship was not found between shrinkage and glass - rubber transitions of both peach and apricot tissue (Campolongo, 2002 Riva et al., 2001, 2002). Even when sorbitol use increased AT (= T — 7g ) values, both the color and the structure showed the highest stability. The fact that sorbitol performed better than sucrose indicates that the chemical nature of the infused solute is more important than its glass transition temperature in preventing structural collapse, in accordance with the results reported by del Valle et al. (1998). 

SCHEME 3.9 Chemical structures of high glass transition temperature HTMs. 

As we discussed in the section on the structural properties of amorphous polymers, the relative size of the bond length and the Lennard-Jones scale is very different when comparing coarse-grained models with real polymers or chemically realistic models, which leads to observable differences in the packing. Furthermore, the dynamics in real polymer melts is, to a large extent, determined by the presence of dihedral angle barriers that inhibit free rotation. We will examine the consequences of these differences for the glass transition in the next section. 

PTT, with three methylene units in its glycol moiety, is called an odd-numbered polyester. It is often compared to the even-numbered polyesters such as PET and PBT for the odd-even effect on their properties. Although this effect is well established for many polycondensation polymers such as polyamides, where the number of methylene units in the chemical structures determines the extent of hydrogen bonding between neighboring chains and thus their polymer properties, neighboring chain interactions in polyesters are weak dispersive, dipole interactions. We have found that many PET, PTT and PBT properties do not follow the odd-even effect. While the PTT heat of fusion and glass transition temperature have values between those of PET and PBT, properties such as modulus... 

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