Polyisoprene Branching

Figure 2.15 Log of viscosity enhancement factor versus parameter measuring branch length for polyisoprene, [Data from W. W. Graessley, T. Masuda, J. E. I. Roovers, and N. Hadjichristidis, Afacromo/ecu/ej 9 127 (1976).]...

The physical properties of any polyisoprene depend not only on the microstmctural features but also on macro features such as molecular weight, crystallinity, linearity or branching of the polymer chains, and degree of cross-linking. For a polymer to be capable of crystallization, it must have long sequences where the stmcture is completely stereoregular. These stereoregular sequences must be linear stmctures composed exclusively of 1,4-, 1,2-, or 3,4-isoprene units. If the units are 1,4- then they must be either all cis or all trans. If 1,2- or 3,4- units are involved, they must be either syndiotactic or isotactic. In all cases, the monomer units must be linked in the head-to-tail manner (85). 

The study of acid-base interaction is an important branch of interfacial science. These interactions are widely exploited in several practical applications such as adhesion and adsorption processes. Most of the current studies in this area are based on calorimetric studies or wetting measurements or peel test measurements. While these studies have been instrumental in the understanding of these interfacial interactions, to a certain extent the interpretation of the results of these studies has been largely empirical. The recent advances in the theory and experiments of contact mechanics could be potentially employed to better understand and measure the molecular level acid-base interactions. One of the following two experimental procedures could be utilized (1) Polymers with different levels of acidic and basic chemical constitution can be coated on to elastomeric caps, as described in Section 4.2.1, and the adhesion between these layers can be measured using the JKR technique and Eqs. 11 or 30 as appropriate. For example, poly(p-amino styrene) and poly(p-hydroxy carbonyl styrene) can be coated on to PDMS-ox, and be used as acidic and basic surfaces, respectively, to study the acid-base interactions. (2) Another approach is to graft acidic or basic macromers onto a weakly crosslinked polyisoprene or polybutadiene elastomeric networks, and use these elastomeric networks in the JKR studies as described in Section 4.2.1. 

FIGURE S.4 Polystyrene (PS) branches grafted on to the multiple branch points along the polyisoprene backbone. 

Itarou H., Mays I.W., and Hadjichri-Stidis N., Regular comb polystyrene and graft polyisoprene/ polystyrene copolymers with double branches ( Centipedes ). Quality of (l,3-phenylene)bis(3-methyl-l-phenylpentylidene)dilithium initiator in the presence of polar additives. Macromolecules, 31,6697, 1998. 

Butadiene and isoprene have two double bonds, and they polymerize to polymers with one double bond per monomeric unit. Hence, these polymers have a high degree of unsaturation. Natural rubber is a linear cis-polyisoprene from 1,4-addition. The corresponding trans structure is that of gutta-percha. Synthetic polybutadienes and polyisoprenes and their copolymers usually contain numerous short-chain side branches, resulting from 1,2-additions during the polymerization. Polymers and copolymers of butadiene and isoprene as well as copolymers of butadiene with styrene (GR-S or Buna-S) and copolymers of butadiene with acrylonitrile (GR-N, Buna-N or Perbunan) have been found to cross-link under irradiation. 

Fig.5. The elastic modulus G (co) and dissipative modulus G (co) for linear top) and three-arm-star branched (bottom) polyisoprene from [5]. Note the broad range of relaxation times indicated by the width of the peak in the star-polymer...

Based on the results obtained to date, which have been summarized above for several different semicrystalline polymers— linear and low density (branched) polyethylene, polytrimethylene oxide, polyethylene oxide and cis polyisoprene—it is concluded that the relatively fast segmental motions, as manifested in Tq, are independent of all aspects of the crystallinity and are the same as the completely amorphous polymer at the same temperature. Furthermore, it has previously been shown that for polyethylene, the motions in the non-crystalline regions are essentially the same as those in the melts of low molecular weight ii-alkanes. (17)... 

The precise stereogeometry of molecules is important in determining the physical properties of a material and is critical in determining the biological properties of materials. Most synthetic and nonspecific natural polymers are a mix of stereoshapes with numerous stereocenters along the polymer chain. For polypropylene, every other backbone carbon is most likely a stereocenter. Even polyethylene has stereochemical sites wherever there is branching. The imprecise structures of most natural nonspecific polymers such as the polyisoprenes and polysaccharides have stereocenters at each branch. 

Naphthalene-terminated polyvinyl aromatics and polyisoprene were obtained successfully. These functional polymers were metalated by potassium in THF at 25°C. The formation of a stable dinegative ion is observed unless the naphthalene is directly attached to the end of the polyvinyl aromatics, in which case a few isoprene units can be advantageously inserted between the naphthalene end group and the polyvinyl aromatics. The polymeric and stable dinegative ion polymerizes oxirane by both anionic sites and forms three-branched starshaped block copolymers. 

A Chromatix low-angle light scattering G.P.C. detector was also employed for the determination of the weight average molecular weight (Mw), as well as a sensitive detector, in order to assay absolutely the Mw versus elution volume profile for a series of star-branched polyisoprenes and polybutadienes. The results indicate that under optimum conditions a relatively well defined number of arms can be achieved with DVB linking. 

In 1965, Milkovich (. ) reported that divinylbenzene could be utilized for the formation of star-branched macromolecules. Later, Rempp and coworkers (2, 3, 4) successfully applied this method for the synthesis of star-branched polystyrenes. Moreover, Fetters and coworkers (54 ) used this procedure for the synthesis of multi-arm star-branched polyisoprene homopolymers and poly-... 

In comparison to the polybutadiene stars under similar reaction conditions, the polyisoprene stars showed slightly lower degrees of branching. The added steric hindrance from the methyl group on the polyisoprene anion perhaps makes entry into the DVB "microgel" nodule difficult. 

The system Cl-buty 1-natural rubber (or cw-polyisoprene) could not be resolved by differential solvent techniques because the polymeric solubility parameters were too similar. At one end of the spectrum—i.e., with styrene at — 25 °C—natural rubber could be highly swollen while restricting the chlorobutyl swell, but the reverse was not possible, as indicated by the swelling volumes in the trimethylpentane. As displayed in Table II, attempts to use a highly symmetrically branched hydrocarbon with a very low solubility parameter, served only to reduce both the swelling of natural rubber and chlorobutyl. (Neopentane is a gas above 10°C and a solid below — 20°C). Therefore, for this report the use of differential solvents in the study of interfacial bonding in blends was limited to systems of Cl-butyl and cw-polybutadiene or SBR. 

Chain Free radical Polybutadiene Polyethylene (branched) Polyisoprene Polymethylmethacrylate Polyvinyl acetate Polystyrene... 

A frequency dependence of complex dielectric permittivity of polar polymer reveals two sets or two branches of relaxation processes (Adachi and Kotaka 1993), which correspond to the two branches of conformational relaxation, described in Section 4.2.4. The available empirical data on the molecular-weight dependencies are consistent with formulae (4.41) and (4.42). It was revealed for undiluted polyisoprene and poly(d, /-lactic acid) that the terminal (slow) dielectric relaxation time depends strongly on molecular weight of polymers (Adachi and Kotaka 1993 Ren et al. 2003). Two relaxation branches were discovered for i.s-polyisoprene melts in experiments by Imanishi et al. (1988) and Fodor and Hill (1994). The fast relaxation times do not depend on the length of the macromolecule, while the slow relaxation times do. For the latter, Imanishi et al. (1988) have found... 

---