Block polymer tactic

Tactic block polymer n. A polymer whose molecules consist of tactic blocks connected linearly. 

A major 1981 lUPAC document (9) addresses polymer stereochemistry in depth. Key chapters of this document discuss basic definitions (configurational unit, configurational base and repeating units, stereorepeating imit, different types of tacticity, tactic block polymers, and stereoblock polymers) sequences conformations and supplementary definitions. Most of the illustrations use the rotated Fischer projections, but some three-dimensional representations are included. 

Note 1 Terms referring to the tacticity of polymers (tactic, ditactic, tritactic, isotactic, cistactic, etc.) can also be applied with similar significance to chains, sequences, blocks, etc. 

Block polymers can be envisaged in which the tacticity of the blocks alternates via an inversion reaction of the site. 

The Commission on Macromolecular Nomenclature defined 52 terms related to polymer structure, including polymer, constitutional units, monomer, polymerization, regular polymer, tactic polymer, block polymer, graft polymer, monomeric unit, degree of polymerization, addition polymerization, condensation polymerization, homopolymer. 

Stereoblock polymers are defined analogously to constitutional block polymers each block has a different species of stereorepeating unit to the block preceding it, but has the same constitutional monomeric units. Tactic... 

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. 

Tactic block n. In a polymer, a regular block that can be described by only one species of configurational repeating unit in a single sequential arrangement. 

An attempt was made to measure the sequence distribution of AMS and styrene in the block polymers by NMR. Because of the interference of the tacticity peaks, the diads and triads of AMS could not be identified. The styrene diads were detected in sample no. 4 which had an AMS to styrene ratio of 0.94, but not in sample no. 6 which had a higher AMS content. 

The results for arylsilanes are not fully understood, but the spectra may reflect partial tacticity in these polymers. Further work is needed studies of model compounds with known relative configuration would be particularly helpful. Silicon-29 NMR of polysilane copolymers also shows great promise, especially for distinguishing block-like from fully random copolymers. 

A common feature of catalysts based on 4 and 5f block elements is that of being able to polymerize both butadiene and isoprene to highly cistactic polymers, independently of the ligands involved. Butadiene, in particular, can reach a cistacticity as high as 99% with uranium based catalysts (3) and cistacticity of > 98% with neodymium based catalysts (4). This high tacticity does not change with the ligand nature (Fig. 1) in contrast to conventional catalysts based on 3-d block elements. A second feature of f-block catalysts is that the cis content of polymer is scarcely... 

Based on Chien s research results, Collins et al. modified the basic structure of the catalysts and also achieved elastic material [8,18,19]. In both cases the elastic properties of the polymers are justified in a block structure with isotactic and atactic sequences. In 1999 Rieger et al. presented a couple of asymmetric, highly active metallocene catalysts, e.g., the dual-side catalyst rac-[l-(9-r 5-fluorenyl)-2-(5,6-cyclo-penta-2-methyl-l-q5-indenyl)ethane]zirconium dichloride (Fig. 3). These catalysts allowed building of isolated stereoerrors in the polymer chain to control the tacticity and therefore the material properties of the polymers [9],... 

The first report of ROMP activity by a well-characterized Mo or W species was polymerization of norbornene initiated by W(CH-t-Bu)(NAr)(0-f-Bu)2 [122]. In the studies that followed, functionality tolerance, the synthesis of block copolymers, and ring-opening of other monomers were explored [30, 123]. Two important issues in ROMP concern the cis or trans nature of the double bond formed in the polymer and the polymer s tacticity. Tacticity is a consequence of the presence of two asymmetric carbons with opposite configuration in each monomer unit. The four ROMP polymers (using polynorbornene as an example) that have a regular structure are shown in Scheme 3. 

When the reaction is carried out with a racemic mixture of complexes, the product is a racemic mixture of the isotactic polymers. It was of interest to see what would happen if, after formation of a chiral block with one enantiomer of the bisoxazoline ligand, an equivalent of the other enantiomer was added. It was found that an excess of ligand changes the tacticity completely and the second block was syndiotactic In these diimine palladium complexes exchange of ligand is relatively fast and it can often be observed on the NMRtime scale as a broadening in the H NMR spectra. The process may well be associative. 

Macromolecular engineering is the ultimate goal of the polymer chemist when he has a monomer or a family of monomers at his disposal. Once each step of the polymerization process is carefully controlled, every molecular parameter of the polymer is predictable molecular weight, tacticity, molecular weight distribution, nature of the end groups, microstructure, and composition, and block... 

Although exhaustive efforts have been made in the search for biologically acceptable catalysts, there are only a few examples of low toxicity, which mainly lead to atactic polymers of little practical use. Another route to gain control over the tacticity of PHB is the transformation of cheap building blocks to enantiomericaUy pure p-BL, which can be distilled off from the catalyst and polymerized with retention of the stereochemistry by ecofriendly initiators. This route combines many advantages. At first, even toxic metal centers can be chosen since the product can easily be separated from the catalyst and secondly, any tacticity of the polymer will be available by simply mixing enantiopure p-BL with the racemic mixture in the desired ratio. In this manner a fine-tuning of the mechanical properties becomes possible and easily performable (Fig. 36). 

Block Copolymerization Cationic Polymerization Polymer Stereochemistry Tacticity Coordination Polymerization Living Radical Polymerizations... 

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