Polymers, stereocomplexes

Iso tactic poly(methyl methacrylate) (it-PMMA) can form a stereocomplex with st-PMMA. Recent X-ray studies 179) of this material indicate that the two polymer chains probably interact to form a double helical structure. The it-PMMA chain forms the inner helix and is surrounded by the st-PMMA helical chain which winds around it. If subsequent work confirms this model, this material would constitute a most unusual inclusion compound involving only one monomeric substance. 

Watanabe J, Eriguchi T, Ishihara K (2002) Stereocomplex formation by enantiomeric poly (lactic acid) graft-type phospholipid polymers for tissue engineering. Biomacromolecules 3 1109-1114... 

Since there was no pathway towards syndiotactic PHB or unnatural isotactic (5)-PHB available for a long time, a more detailed investigation on material properties with regards to tacticity and stereocomplex formation is stiU missing. To date, it is not known whether syndiotactic PHBs crystallize in a similar manner to isotactic stereoisomers and therefore possesses similar properties nor how they are influenced by blending of polymers with different stereochemistry. 

Many radical polymerization systems were examined hy Challa at a/. A number of papers were devoted to polymerization of methyl methacrylate, MM, in the presence of poly(methyl methacrylate). The role of tacticity of template was stressed. Isotactic PMM forms stereocomplex with syndiotactic PMM. Polymerizations of MM in the presence of isotactic PMM were carried out and the product (template + daughter polymer) was analyzed by NMR. When MM is polymerized in the polar solvent in the presence... 

In connection with the aforementioned study on polymerization mechanism of MMA77,78), Miyamoto et al. developed a preparatory method of separating blends of isotactic and syndiotactic PMMA82 The principle was based on a competitive adsorption of these different stereoisomeric polymers from a nonpolar solution (chloroform) onto an adsorbent surface (silica gel). The procedure was quite simple, as described below A given polymer blend was dissolved in chloroform, in which no stereocomplex formation usually occurs, and silica gel was then dispersed in this solution for adsorptive equilibration with the polymer species. The isotactic species could be isolated as the adsorbed component. In practice, its purity was ca. 80—90%, which depended on the added amount of silica gel. By repeating the same procedure, the purity could be enhanced. 

The tacticity of PLA influences the physical properties of the polymer, including the degree of crystallinity which impacts both thermo-mechanical performance and degradation properties. Heterotactic PLA is amorphous, whereas isotactic PLA (poly(AA-lactide) or poly (55-lac tide)) is crystalline with a melting point of 170-180°C [26]. The co-crystallization of poly (RR-lactide) and poly(55-lactide) results in the formation of a stereocomplex of PLA, which actually shows an elevated, and highly desirable, melting point at 220-230°C. Another interesting possibility is the formation of stereoblock PLA, by polymerization of rac-lactide, which can show enhanced properties compared to isotactic PLA and is more easily prepared than stereocomplex PLA [21]. 

Stereoblock PLA has short isotactic blocks (sequences) within the same polymer it can also undergo co-crystallization, although not to the same extent as stereocomplex PLA. Consequently, lower melting points are obtained for stereoblock PLA compared to stereocomplex PLA however, they exceed those of isotactic PLA. The melting points of stereocomplex PLA are dependent on the block length. 

PMMA added previously would depend on their structure. Indeed, when polymerization was carried out in the presence of isotactic PMMA, it influenced the formation of new macromolecules, affecting the rate of polymerization, the molecular weights of the polymer formed, and the structure of its molecules. It is natural to assume that these effects are caused by the appearance of a stereocomplex during polymerization between the polymer added beforehand and the growing macroradical. It is also characteristic that the ratio of polymerization rates in the presence and in the absence of the polymer is independent of the concentrations of monomer and polymer added, depending only on their ratio. Viscosity investigations revealed that these solutions are highly crosslinked. 

A secondary stereocomplex gel with the ratio [iso-PMMA]/[synd-PMMA] = 1/1 obtained from o-xylene solution showed an endothermic peak at 110 °C which was attributed to the melting point of the stereocomplex. The degree of crystallization was about 5-6%. Since this gel contained over 80% solvent, micro-Brownian motions of PMMA chains in the amorphous region were relatively unhindered. When the PMMA gel was cooled rapidly after melting above its Tm (i.e. above 145°C), first the loss modulus (c") changed relative to the viscosity of the system whereas the storage modulus began to increase after some time. This result confirms the assumption that first the polymer chains cannot be cross-linked but are weakly associated with one other, and then a... 

In a large number of investigations the possibility of the formation of polymer-polymer complexes with the participation of alternating and random copolymers has been shown. So, using the viscometric method58, the complex formation of iso-PMAA and methyl methacrylate and methacrylic add copolymer has been reported. The stability of the stereocomplex decreases with increasing add content in the copolymer. 

In bulk we may not forget the so called stereocomplexes between stereoregular polymers. In 1961 Watanabe reported that mixing syndiotactic poIy(methylmetha-crylate) (j-PMMA) and isotactic poly(methylmethacrylate) (/t-PMMA) leads to the... 

One of the cases of such complementarity may be the atactic polymer which can be considered as a copolymer of isotactic and syndiotactic links. Indeed, the composition and properties of the polyccanplex depend on the chain stereoregularity, for example in the case of poly(methyl methacrylate) stereocomplexes and poly(ethylene glycol) with isotactic or atactic PAA complexes ... 

Three possible stereoisomers of lactide (LA) exist d-, l- and me o-lactide (Figure 1). A racemic mixture of d- and L-lactide is referred to as rac-lactide (rac-LA)."° The stereochemistry of these monomers, when incorporated into a polymer chain, creates material with a certain stereocomplexity or tacticity. " The tacticity of a given PLA sample may be defined by two parameters P [probability of forming adjacent stereocenters with the same chirality or a meso (m) linkage] and P [probability of... 

Recently stereocomplexes of PLA appeared on the market and lead to promising applications in durable devices (see below PLA applications). The stereocomplexes are defined as the association of polymers with different tacticity or conformation. Three synthesis routes are used to produce a PLA stereocomplex, either in solution or in melt state during pol)nnerization or hydrolysis. The complexe formation is possible with (i) two monomers (L-lactide and D-lactide), (ii) polymer and monomer or (iii) two polymers (PLLA and PDLA). This synthesis is often performed with stannous tin and 1-dodecanol (lauryl alcohol) as initiator or co-initiator of the reaction [36-38]. According to Tsuji et al. [38], some other parameters affect the formation of stereocomplexes ... 

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