Olefinic copolymers Tacticity

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. 

The initial use of analytical TREF was to characterize polyethylene fractions [120]. Mirabella and Ford used TREF to fractionate LDPE and LLDPE for further characterization using SEC, X-ray C-NMR, DSC and viscosity measurements [121]. These investigators determined that the melting behavior of LLDPE correlated well with a multimodal SCB distribution and the distribution became narrower with increasing molecular weight. Mingozzi and collaborators [122] have applied both analytical and preparative TREF to the analysis of tacticity distribution in polypropylene. The results showed that both methods could be used successfully analytical TREF gave faster qualitative results on the polymer microstructure, while preparative TREF, with subsequent analysis of the fractions, could yield detailed quantitative tacticity information. Hazlitt has described an automatic TREF instrument to measure SCB distributions for ethylene/ a-olefin copolymers [123]. 

The disadvantages of all biochemical routes is the lack of variable tacticity in the polymer and, even more important, the need for time-consuming purification. PHB materials of feasible properties are only achieved with high production costs. In the 1990s, ICl sold a copolymer of 3-HB and 3-HV (BIOPOL) for about 10-20 /kg whereas the price of PP was less than 2 /kg. Therefore, a fermentative synthesis is feasible for smaller applications but not cannot compete with packaging materials such as poly(olefin)s [43 5] (Fig. 10). 

Since the discovery of olefin polymerization using the Ziegler-Natta eatalyst, polyolefin has become one of the most important polymers produeed industrially. In particular, polyethylene, polypropylene and ethylene-propylene copolymers have been widely used as commercial products. High resolution solution NMR has become the most powerful analytieal method used to investigate the microstructures of these polymers. It is well known that the tacticity and comonomer sequence distribution are important factors for determining the mechanical properties of these copolymers. Furthermore, information on polymer microstructures from the analysis of solution NMR has added to an understanding of the mechanism of polymerization. 

The synthesis of alternating copolymers from carbon monoxide (CO) and olefins using palladium catalysts is currently an area of intense research. In cases where a-olefins are used, the regiochemistry (head/tail orientations) and stereochemistry (tacticity) of olefin insertion have a strong influence on the physical and mechanical properties of the polymers. Unlike regioregular a-olefins homopolymers, these copolymers have a directionality along the polymer backbone due to the incorporation of CO. Therefore isotactic, regioregular CO/a-olefin polymers are chiral by virtue of their main-chain stereochemistry (Scheme 11). 

The molar optical rotation of configurational copolymers of (S) and (R) isomers of the same monomer is generally, in the case of poly(a-olefins), a hyperbolic and not a linear function of the optical purity of the monomers. Thus, the molar optical rotation of the copolymers is always greater than that obtained by additivity rules. Whether this is caused by tactic blocks in the polymers or by mixtures of (S) and (R) unipolymers has not been established yet. 

Crystalline polyolefins as polypropylene (PP) with high tacticity and copolymers of propylene with ethylene and/or higher a-olefins containing sufficiently long isotactic PP blocks can only be dissolved under conditions (solvent/temperature) which cause complete melting of the crystalline domains. Therefore, SEC of PP and crystalline copolymers of propylene must be carried out at elevated temperatures which requires the special equipment of high-temperature SEC (HT-SEC) which is commercially available from several sources, e.g. Millipore-Waters Corp. (Milford, MA, USA) and Polymer Laboratories Ltd (Church Stretton, Shropshire, UK). 

Much less recognized is the possible influence of tacticity on copolymer properties when a-olefin monomer units are a minor component, and crystallinity is not based on a tactic a-olefin sequence but on a different comonomer such as ethylene. In this chapter, this tacticity effect is shown for ethylene-rich ethylene/propylene (EP) copolymers, where the crystallizable sequences are based on ethylene, that is, a comonomer that does not have tacticity requirements. In particular, this chapter describes in detail the microstructure of EP copolymers having industrially relevant compositions (ethylene content 80-55 mol%), with particular focus on the placement of propylene units along the ethylene-based macromolecular chains and their influence on copolymer properties. This subject is, of course, related to the industrial relevance of EP copolymers and ethylene/propylene/diene monomer terpolymers (EPDMs) (collectively referred to as EP(D)Ms), which presently represent the most widely produced saturated rubbers. ... 

This unified volume explains the mechanistic basics of tactic polymerizations, beginning with an extensive survey of the most important classes of metallocene and post-metallocene catalysts used to make polypropylenes. It also focuses on tactic stereoblock and ethylene/propylene copolymers and catalyst active site models, followed by chapters discussing the structure of more stereochemically complex polymers and polymerizations that proceed via non-vinyl-addition mechanisms. Individual chapters thoroughly describe tactic polymerizations of a-olefins, styrene, dienes, acetylenes, lactides, epoxides, acrylates, and cyclic monomers, as well as cyclopolymerizations and ditactic structures, olefin/CO copolymers, and metathesis polyalkenamers. 

The cooperative effect anticipated by the asymptotic dependence of chiroptical properties on the degree of tacticity is further evidenced by the study of the chiroptical properties of copolymers between optically active a-olefins and achiral comonomers. i Co-isotactic copolymers of (5)-4-methyl-l-hexene with 4-methyl-1-pentene show, at any composition, an optical rotation higher than the two homopolymer mixtures, thus indicating that 4-methyl-1-pentene (4MP) units in the copolymer contribute to optical rotation, the contribution being of the same sign as that of the (5)-4-methyl-l-hexene (4MH) units. By assuming that (Od )4mh is the same in the copolymer and in the homopolymer, the values of ( )4mp can be derived at each composition by the equation ... 

In chain reactions the different types of monomers can be added subsequently to an active chain end. The most important techniques here are sequential living polymerization techniques, such as anionic or cationic polymerization. Certain metallocenes can be used in coordination polymerization of olefins leading to stereo block copolymers, like polypropylene where crystalline and amorphous blocks alternate with each other due to the change of tacticity along the chain [34]. In comparison to living polymerization techniques, free radical and coordination polymerization lead to rather polydisperse materials in terms of the number of blocks and their degree of polymerization. 

Abstract The use of methylaluminoxane (MAO) as cocatalyst for the polymerization of olefins and some other vinyl compounds has widely increased the possibilities for more precisely controlling the polymer composition, polymer structure, tacticity, and special properties. Highly active catalysts are obtained by different transition metal complexes such as metallocenes, half-sandwich complexes, and bisimino complexes combined with MAO. These catalysts allow the synthesis of polyolefins with different tacticities and stereoregularities, new cycloolefins and other copolymers, and polyolefin composite materials of a purity that cannot be obtained by Ziegler-Natta catalysts. The single-site character of metaUocene/MAO or other transition metal/ MAO catalysts leads to a better understanding of the mechanism of olefin polymerization. 

Isotactic and syndiotactic polymers can crystallize, while atactic polymers cannot. Polymers other than polypropylene that have tacticity include polystyrene, polyfvinyl chloride), and poly(methyl methacrylate). Thus there are crystalline and non-crystalline forms of these polymers. By use of a copolymer, the number of side groups, and thus the crystallinity can be precisely controlled. An important example is the copolymerization of ethylene and a higher alpha-olefin, such as butene or octane, to make linear low-density polyethylene (LLDPE), in which the crystallinity is governed by the fraction of comonomer incorporated into the chain. Tacticity can affect important physical properties such as the intrinsic viscosity and thus must be taken into accoimt in characterization methods such as gel permeation chromatography. 

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