Polymer chain, microstructure

Polyethylene (PE) is the largest synthetic commodity polymer in terms of annual production and is widely used throughout the world in a variety of applications. Based on the density, PE is classified as LDPE at 0.910-0.930g/cm3, high-density polyethylene (HDPE) at 0.931-0.970g/cm3, and linear low-density polyethylene (LLDPE) based on the polymer chain microstructure. At present, processes that produce PE use the following raw materials ... 

Characteristic of these models of active sites is the appearance of the OZn O Zn(0)Et species. Considering the structural properties of the discussed catalysts as well as the polymer chain microstructure and the structure of the end groups of poly(propylene oxide) obtained with the PhOZnOCeHi ( -Bu)OZnEt catalyst, a concerted mechanism of epoxide ring-opening polymerisation with catalysts containing multinuclear species, including those with condensed zinc atoms, has been postulated [65,74] ... 

Polymer chain microstructure depends on polymerization mechanism and reactor conditions. The polymerization... 

Ttp 4 Chain microstructure and propagation reactions. Propagation reactions are mainly responsible for the development of polymer chain microstructure (and control chain composition and sequence length distribution in copolymerizations). In free radical polymerization, the stereoregularity of a high molecular weight homopolymer chain depends on polymerization temperature almost exclusively. It is usually independent of initiator type and monomer concentration. Calculations on stereoregularity... 

General effects of particle morphology and polymer chain microstructure on physical properties... 

Analysis of the acid catalyzed hydrolysis of PAM is complicated due to the possibility of intra- and inter-molecular Imide formation.(4) Perhaps for this reason, studies of the base catalyzed hydrolysis of PAM are more numerous. These investigations indicate that the base catalyzed hydrolysis of PAM may be influenced by a number of factors Including electrostatic Interactions (2,5), nearest neighbor effects (6), and Imide formation associated with specific polymer chain microstructure(s).(7)... 

The several aspects of polymer chain microstructure have been studied by both chemical and physical methods. Koenig (3) describes several of these methods, which are summarized in Tables 2.1 and 2.2. 

Table 2.1 Chemical methods of determining polymer chain microstructure (3)...

Amer and van Reenen [39] fractionated isotactic polypropylenes by TREE to get fractions with different molar masses but similar tacticities. The DSC results of the fractions indicated that the crystallization behaviour is strongly affected by the configuration (tacticity) and the molar mass of the PP. Soares et al. [40] proposed a new approach for identifying the number of active catalyst sites and the polymer chain microstructural parameters produced at each active site for ethylene/l-olefin copolymers synthesized with multiple-site catalysts. This method is based on the simultaneous deconvolution of bivariate MMD/CCD, which can be obtained by cross-fractionation techniques like SEC/TREE or TREE/SEC. The proposed approach was validated successfully with model ethylene/1-butene and ethylene/ 1-octene copolymers. Alamo and co-workers [41] studied the effects of molar mass and branching distribution on mechanical properties of ethylene/1-hexene copolymer film grade resins produced by a metallocene catalyst Molar mass fractions were obtained by solvent/non-solvent techniques while P-TREE was used for fractionation according to the 1-hexene content. 

Propagation reactions are responsible for the development of polymer chain microstructure that determines polymer material properties. For example, PVC chains can have head-to-tail and head-to-head structures. The head-to-tail structure is favored for its low-energy state. However, the head-to-head structure can also be formed particularly at high temperature. PVC materials with significant head-to-head structures have poor quality in application, are not stable, and are susceptible to polyene formation. 

Koenig, J. L., Chemical Microstructure of Polymer Chains, Wiley, New York, 1980. 

The formation of the microstructure involves the folding of linear segments of polymer chains in an orderly manner to form a crystalline lamellae, which tends to organize into a spherulite structure. The SCB hinder the formation of spherulite. However, the volume of spherulite/axialites increases if the branched segments participate in their formation [59]. Heterogeneity due to MW and SCB leads to segregation of PE molecules on solidification [59-65], The low MW species are accumulated in the peripheral parts of the spherulite/axialites [63]. The low-MW segregated material is brittle due to a low concentration of interlamellar tie chains [65] and... 

Many commercially important polymers are actually mixtures of two or more polymer components that differ from one another in composition (for copolymers) or in microstructure (for homopolymers). Such mixtures may be the deliberate result of polymer blending, polymer synthesis, or the presence of different types of initiators or catalytic sites that produce different polymer chains. The ung spectral data of the whole polymer in such systems would include contributions from all its components, and as such should be treated with care. 

Koenig JL (1980) Chemical microstructure of polymer chains. John Wiley Sons, New York... 

As mentioned previously, chemistry and physico-chemistry play major roles in polymer microstructure, and, as a consequence, on polymer properties. The characterisation of several chemical parameters of polymer chains is thus of paramount importance for controlling the final properties of polymer materials... 

The crystallization kinetics of commercial polyolefins is to a large extent determined by the chain microstructure [58-60]. The kinetics and the regime [60] of the crystallization process determine not only the crystalline content, but also the structure of the interfaces of the polymer crystals (see also Chapter 7). This has a direct bearing on the mechanical properties like the modulus, toughness, and other end use properties of the polymer in fabricated items such as impact resistance and tear resistance. Such structure-property relationships are particularly important for polymers with high commercial importance in terms of the shear tonnage of polymer produced globally, like polyethylene and polyethylene-based copolymers. It is seen that in the case of LLDPE, which is... 

On the basis of the microstructure of the prevailing isotactic polymer chains, it is well established that the steric control of the heterogeneous Ziegler-Natta catalysts is due to the chirality of the catalytic site and not to the configuration of the last inserted monomer unit.28,29,95... 

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