Branching in Polystyrene

SEC combined with viscometry has been used in branching studies on polystyrene (PS) [70]. Papanagopoulas and Dondos characterised branching in PS star polymers 

---

Wall and Brown (30) examined transfer to polymer and the general problem of branching in polystyrene by comparing results with the two monomers... 

The synthesis of comb-like polymers with regular branching (in contrast to random branching) has been performed in the following way 91) A linear polystyrene precursor fitted with carbanionic sites at both ends is reacted first with 1,1-diphenylethylene (to decrease the nucleophilicity of the sites) and then with a calculated amount of triallyloxytriazine to get chain extension. Each triazine residue still carries one allyloxy... 

Addition of rubber particles of 30% to 100% by weight to cement with a grain size of approximately 40 to 60 mesh (0.4 to 0.25 mm) will produce a lightweight cement. The addition of rubber particles also creates a low permeability. The compositions are advantageous for cementing zones subjected to extreme dynamic stresses such as perforation zones and the junctions of branches in a multi-sidetrack well. Recycled, expanded polystyrene lowers the density of a hydraulic cement formulation and is an environmentally friendly solution for downcycling waste materials. 

Fraction DII is a polystyrene containing 2.2 branches per molecule. DII has been prepared together with the absolutely linear fraction D IV by Henrici-Oliv and Oliv6 (120). Apparently, the effect of the poly-dispersity of sample D II prevails over the opposite effect of branching. In this respect the investigation of anionic star-molecules would be extremely interesting. 

A wide variety of polymers have been analyzed by gel-permeation, or size-exclusion, chromatography (sec) to determine molecular weight distribution of the polymer and additives (86—92). Some work has been completed on expanding this technique to determine branching in certain polymers (93). Combinations of sec with pyrolysis—gc systems have been used to show that the relative composition of polystyrene or acrylonitrile—polystyrene copolymer is independent of molecule size (94). Improvements in gpc include smaller cross-linked polystyrene beads having narrow particle size distributions, which allow higher column efficiency and new families of porous hydrophilic gels to be used for aqueous gpc (95). 

There are several remarkable features of these immobilized salens, notably the fact that the dendritic branches do not appear to decrease the catalytic activity with respect to the complexes in solution. Moreover, the reactions with dendritic catalysts incorporated in polystyrene gave products of essentially the same enantiopurity as those observed in homogeneous solution, with the dendritically substituted or with the original Jacobsen-Katsuki complexes. Some of the Mn-loaded beads were stored for a year without loss of activity. Especially, the biphenyl- and acetylene-linked salen polymers gave Mn complexes of excellent performance, which after ten catalytic rims showed no loss of enantioselectivity or degree of conversion. 

All polymers can be divided into two major groups thermoplastics and thermosets) based on their thermal processing behavior. Thermoplastics soften and flow when heated. Upon cooling, thermoplastic polymers harden and assume the shape of the mold. Examples of commercial thermoplastics include polystyrene, polyolefins (e.g. polyethylene and polypropylene), nylon, poly(vinyl) chloride (PVC), and poly (ethylene) terephthalate (PET). Thermoplastics make up 80% of the plastic produced today and these polymers are linear or branched in their structure. 

An atactic polymer is a regular polymer with macromolecules composed of a certain number of statistically distributed configurational units. The constitutional unit is a type of atom or group of atoms composing the macromolecule (e. g. —[CH2—CHPhJ- or —[CHPh— in polystyrene). The configurational unit is a constitutional unit with one or several stereoisomer-ic centres. These definitions would require a more detailed explanation. In this volume they will only rarely be used, the stereochemistry of jjolymers is a special branch of macromolecular chemistry. More information can be found in the original literature [2]. 

C. Characterization of Polystyrene Branches in PoIy(butadiene-g-Styrene)... 

An important objective of this research was to determine directly the molecular weights and the molecular weight distribution of polystyrene branches in poly(buta-diene-g-styrene). 

Tsitsilianis et al. recently published [245] preliminary results on the micelliza-tion behavior of anionically synthesized amphiphilic heteroarm star copolymers with polystyrene and poly(ethylene oxide) branches in THF and water. The former solvent is not very selective for one of the segments whereas the latter is strongly selective for PEO. The apparent molecular weights found for the micelles in THF were two orders of magnitude larger than the ones measured for the unimers. By increasing concentration an increase in the depolarization ratio was observed supporting the conclusion that multimolecular micelles are formed by this kind of miktoarm star copolymer. 

---