Polypropylene Branching

Fractional precipitation of crystalline polymers must be conducted above the melting point of the crystals to eliminate the effects of crystallinity on solubility. In addition, with polypropylene branching and tacticity differences can cause a reversal in the order of fractionation. In most cases polyolefins are fractionated from dilute solutions in poor solvents to eliminate these effects. However, the direct extraction of powdered high density polyethylene with solvents has been reported [94]. 

Polypropylene branched hydrocarbons such as 2,4-dimethyl heptane... 

Major differences occur between the pyrograms of three similar polymers. Polyethylene produces major amounts of normal C2 to Cg alkanes and minor amounts of 2-methyl and 3-methyl compounds such as isopentane and 3-methylpentane, which are indicative of short chain branching on the polymer backbone. For polypropylene, branched alkanes predominate, these peaks occurring in regular patterns, e.g., 2-methyl, 3-ethyl and 2,4-dimethylpentane and 2,4-dimethylheptane which are almost absent in the polyethylene pyrolysate. Minor components obtained from polypropylene are normal paraffins present in decreasing amounts up to normal hexane. 

Polypropylene-derived branched alkyl (0 2) benzene (BAB) has been batch sulfonated using 60—70% oleum in Hquid SO2 solvent at temperatures of — 1 to —8°C, with SO2 serving as a self-refrigerant and viscosity reducer in the process. After sulfonation and digestion, SO2 is stripped, recovered, and recycled (256). 

Polyolefins such as polyethylene and polypropylene contain only C—C and C—H bonds and may be considered as high molecular weight paraffins. Like the simpler paraffins they are somewhat inert and their major chemical reaction is substitution, e.g. halogenation. In addition the branched polyethylenes and the higher polyolefins contain tertiary carbon atoms which are reactive sites for oxidation. Because of this it is necessary to add antioxidants to stabilise the polymers against oxidation Some polyolefins may be cross-linked by peroxides. 

Ziegler-Natta catalysts currently produce linear polyethylene (non-branched), stereoregular polypropylene, cis-polybutadiene, and other stereoregular polymers. 

Most commercial polymers are substantially linear. They have a single chain of mers that forms the backbone of the molecule. Side-chains can occur and can have a major affect on physical properties. An elemental analysis of any polyolefin, (e.g., polyethylene, polypropylene, poly(l-butene), etc.) gives the same empirical formula, CH2, and it is only the nature of the side-chains that distinguishes between the polyolefins. Polypropylene has methyl side-chains on every other carbon atom along the backbone. Side-chains at random locations are called branches. Branching and other polymer structures can be deduced using analytical techniques such as NMR. 

FIGURE 11.18 Tensile stress-strain responses of polypropylene/styrene-butadiene rubber (PP-SBR) blends at several ratios (where LL is linear low molecular weight LH is linear high molecular weight BL is branched low molecular weight and BH is branched high molecular weight). (From Cook, R.F., Koester, K.J., Macosko, C.W., and Ajbani, M., Polym. Eng. Sci., 45, 1487, 2005.)... 

Grafting to create long chain branches employs well-known organic reactions to incorporate polymer chains that have reactive end groups. When there is no suitable reactive group on the backbone that can be attacked directly (as is the case with polymers such as polypropylene,... 

The history of dendrimer chemistry can be traced to the foundations laid down by Flory [34] over fifty years ago, particularly his studies concerning macro-molecular networks and branched polymers. More than two decades after Flory s initial groundwork (1978) Vogtle et al. [28] reported the synthesis and characterization of the first example of a cascade molecule. Michael-type addition of a primary amine to acrylonitrile (the linear monomer) afforded a tertiary amine with two arms. Subsequent reduction of the nitriles afforded a new diamine, which, upon repetition of this simple synthetic sequence, provided the desired tetraamine (1, Fig. 2) thus the advent of the iterative synthetic process and the construction of branched macromolecular architectures was at hand. Further growth of Vogtle s original dendrimer was impeded due to difficulties associated with nitrile reduction, which was later circumvented [35, 36]. This procedure eventually led to DSM s commercially available polypropylene imine) dendrimers. 

All dendrimers consist of inner tertiary amines, located at the branching points of the various dendritic shells (layers). The amine-terminated dendrimers, furthermore, have basic primary amine end-groups. Basicity is therefore one of the most dramatic properties of the polypropylene imine) dendrimers, and has been studied via titration experiments and calculations. Titration experiments of the dendrimers have been performed in water using 1 M hydrochloric acid. Only two equivalence points are observed for DAB-J nJr-(NH2)4 in a ratio of 2 1. From these titrations, pKa values of 10.0 (primary amine groups) and 6.7 (tertiary... 

PTT is made by the melt polycondensation of PDO with either terephthalic acid or dimethyl terephthalate. The chemical structure is shown in Figure 11.1. It is also called 3GT in the polyester industry, with G and T standing for glycol and terephthalate, respectively. The number preceding G stands for the number of methylene units in the glycol moiety. In the literature, polypropylene terephthalate) (PPT) is also frequently encountered however, this nomenclature does not distinguish whether the glycol moiety is made from a branched 1,2-propanediol or a linear 1,3-propanediol. Another abbreviation sometimes used in the literature is PTMT, which could be confused with poly(tetramethylene terephthalate),... 

Crystallinity. Is one of the key factors influencing properties. You can think of crystallinity in terms of how well a polymer fits in an imaginary pipe, as in Figure 22-6. Linear, straight chains are highly crystalline and fit very well. Bulky groups, coiled chains, and branched chains are not able to line up to fit in the pipe. They are amorphous, the opposite of crystalline. In a spectrum from totally amorphous, to almost totally crystalline, there is methyl methacrylate, polypropylene, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and nylon. 

In this chapter, the big four thermoplastics are covered polyethylene, polypropylene, polyvinyl chloride, and polystyrene. Like most other thermoplastics, they are long-chain polymers that become soft when heated and can be molded under pressure. They are linear- or branch-chained and, except for some exotic copolymers, have little or no cross-linking. Technological advances continue. Research in copolymerization, catalysts, processing, blending, and fabricating continues even as you read this. 

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