Polyisoprene homopolymers

A diblock copolymer, 71% polyisoprene (1) by weight and 29% polybutadiene (B), was blended in different proportions into a 71%-29% mixture of the individual homopolymers. The loss tangent was measured as a function of temperature for various proportions of copolymer. Two peaks are observed ... 

The economic importance of copolymers can be cleady illustrated by a comparison of U.S. production of various homopolymer and copolymer elastomers and resins (102). Figure 5 shows the relative contribution of elastomeric copolymers (SBR, ethylene—propylene, nitrile mbber) and elastomeric homopolymers (polybutadiene, polyisoprene) to the total production of synthetic elastomers. Clearly, SBR, a random copolymer, constitutes the bulk of the entire U.S. production. Copolymers of ethylene and propylene, and nitrile mbber (a random copolymer of butadiene and acrylonitrile) are manufactured in smaller quantities. Nevertheless, the latter copolymers approach the volume of elastomeric butadiene homopolymers. 

Measurements of diffusion of tracer polymers in ordered block copolymer fluids is another potentially informative activity, since molecular diffusion is one of the most basic dynamic characteristics of a molecule. Balsara, et al. have measured the retardation of diffusion due to ordering in the diffusion of polystyrene tracer homopolymers in polystyrene-polyisoprene matrices of various domain sizes [167]. Measurement of the tracer diffusion of block copolymer molecules will also be important. Several interesting issues are directly addressable via measurements... 

During the last two decades, a number of diene homopolymers and copolymers have been developed to fill the diverse elastomer needs in the production of tires. The earliest developments were mainly concerned with the preparation of stereoregular cis-1,4-polyisoprene, as a substitute for natural rubber, using... 

Table 1 lists some of the homopolymers and diblock copolymers which have been employed in our experimental investigations (1-8). Particular emphasis has been placed on blends containing 1,4 polybutadiene (1,4B). In one case, 1,4B was blended with various amounts of 1,2 polybutadiene (1,2B) and the corresponding 1,2B/1,4B diblock copolymer. A second major set of samples was constructed from various combinations of 1,4B and cis 1,4 polyisoprene (1,41) and 1, 41/1,4B diblock copolymers. A large number of ternary blends were studied, the preponderence of which contained either 25%, 50% or 75% (by weight) of a selected diblock copolymer, the remainder of the blend being comprised of one or both of the corresponding homopolymers. Homopolymer blends (0% diblock) and the pure copolymers (100% diblock) were also studied in detail. 

The general correlations of structure and properties of homopolymers are summarized in Table 2.13. Some experiments which demonstrate the influence of the molecular weight or the structure on selected properties of polymers are described in Examples 3-6 (degree of polymerization of polystyrene and solution viscosity), 3-15, 3-21, 3-31 (stereoregularity of polyisoprene resp. polystyrene), 4-7 and 5-11 (influence of crosslinking) or Sects. 4.1.1 and 4.1.2 (stiffness of the main chain of aliphatic and aromatic polyesters and polyamides). 

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-... 

Polydienes. The most important diene homopolymers are polybutadiene and polyisoprene produced by anionic or coordination polymerization.184,186,187,487 189 Highly purified starting materials free from acetylenes, oxygen, and sulfur compounds are required. 

Natural Rubbers (NR). The chemical name for NR is polyisoprene, which is a homopolymer of isoprene. It has the cis-1,4 configuration. In addition, the polymer contains small amounts of non-rubber substances, notably fatty acids, proteins, and resinous materials that function as mild accelerators and activators for vulcanization. Raw materials for the production of NR must be derived from trees of the Hevea Brasiliensis species. NR is available in a variety of types and grades, including smoked sheets, air-dried sheets, and pale crepes. 

Functionalized polysiloxanes are attractive because, with only small modification of the polysiloxane properties (e.g. density, yield strength, etc.), they allow reduction in the interfacial tension thanks to better interactions with the other homopolymer. Two studies involving PB/PDMS and polyisoprene (PIP)/PDMS are of particular interest [19,20]. The PDMS end groups were either amine (-NH2) or acid (-COOH). It was first observed that the PB/PDMS-NH2 system exhibits a 30% reduction in interfacial tension compared to the equivalent PB/PDMS system. A preliminary reduction... 

A number of plants and some trees contain a white, milky liquid that is released when the stem or bark is cut. The liquid is called a latex from the Latin meaning liquid. Common sources include dandelions, milkweed, goldenrod, and potted rubber plants. Rubber trees, from which substantial quantities of latex can be harvested, grow in some tropical areas of the world. A major constituent of this latex is a homopolymer of isoprene (2-methyl-1,3-butadiene), called polyisoprene. Polyisoprene, as well as a number of other elastomers, has a carbon-carbon double bond in every repeat unit. The properties of polyisoprene are the result of the presence of these double bonds. Just as stereochemistry plays a critical role in both proteins and polysaccharides, we will see its importance here. 

Viscoelastic Properties of Homopolymers and Diblock Copolymers of Polybutadiene and Polyisoprene... 

Three diblock copolymers of cis-1,4 polyisoprene (IR) and 1,4-polybutadiene (BR) have been studied in dynamic mechanical experiments, transmission electron microscopy, and thermomechanical analysis. The block copolymers had molar ratios of 1/2, 1/1, and 2/1 for the isoprene and butadiene blocks. Homopolymers of polybutadiene and polyisoprene with various diene microstructures also were examined using similar experimental methods. Results indicate that in all three copolymers, the polybutadiene and polyisoprene blocks are essentially compatible whereas blends of homopolymers of similar molecular weights and microstructures were incompatible. 

Figure 2. Transmission electron micrographs of (a) a blend of polybutadiene (25 vot %) and polyisoprene (75 wt %) (b) polyisoprene homopolymer (c) diblock copolymer 2143. Magnifications as indicated.

Figure 4. Tan vs. temperature curves at 3.5 Hz for the diblocks and homopolymers. The scale on the ordinate corresponds to the bottom curve only, the other curves have been shifted upwards for clarity. The two arrows along the temperature scale indicate the polybutadiene (—82°C) and polyisoprene (—49°C) transitions.

For instance, in the field of elastomers, alkyllithium catalyst systems are used commercially for producing butadiene homopolymers and copolymers and, to a somewhat lesser extent, polyisoprene. Another class of important, industrial polymerization systems consists of those catalyzed by alkylaluminum compounds and various compounds of transition metals used as cocatalysts. The symposium papers reported several variations of these polymerization systems in which cocatalysts are titanium halides for isoprene or propylene and cobalt salts for butadiene. The stereospecificity and mechanism of polymerization with these monomers were compared using the above cocatalysts as well as vanadium trichloride. Also included is the application of Ziegler-Natta catalysts to the rather novel polymerization of 1,3-pentadiene to polymeric cis-1,4 stereoisomers which have potential interest as elastomers. 

Kawai and Inoue (49) recently explored the mechanical blend of poly-styrene/polyisoprene/poly(styrene-b-isoprene) polymer 1 and polymer 2 appear as both homopolymers and block components. 

Recent studies of blends of polyisoprene (PIP) with polybutadiene (PBD) have revealed a number of remarkable features [1-5]. Non-polar hydrocarbon polymers such as PIP and PBD are not expected to exhibit miscibility given the absence of specific interactions. When the polybutadiene is high in 1,2 microstructure, however, it has a remarkable degree of miscibility with PIP. This miscibility is the consequence of a close similarity in both the polarizability and the expansivity of the two polymers [3,4]. Their mixtures represent a very unusual instance of miscibility between chemically distinct, non-reacting homopolymers. As its 1,4- content increases, both the polarizability and the thermal expansivity of the PBD diverge from that of PIP, resulting in a reduced degree of miscibility. This effect of PBD microstructure on miscibility with PIP can be seen in the data in Table I [3]. ... 

Another homopolymer analyzed by Py-GC/MS and discussed below Is polyisoprene (c/s), with the formula [-CH2CH=C(CH3)CH2-]n and CAS 104389-31-3. The analyzed sample (0.4 mg) had M = 38,000 (synthetic material), and the experimental conditions were similar to those for other polymers previously discussed (see Table 4.2.2). The resulting pyrogram is given in Figure 7.1.3, and the peak identification that was done using MS spectral library searches only is given in Table 7.1.4. 

Along the same lines, Mandani et al.173 reacted a difunctional polyisoprene with silicon tetrachloride, to prepare bicyclic polyisoprenes. The only indication for the formation of the bicyclic homopolymer was the lower hydrodynamic volume obtained by SEC. However, the final polymer was not isolated for further characterization. 

For the case of homopolyisoprene/styrene-isoprene copolymer mixtures [364], it was shown that the miscibility increases in the order four-arm star-block < triblock < diblock. Increased incompatibility was observed in the pair poly(isoprene-g-styrene)/polyisoprene [365] even when the molecular weight of the homopolymer was much lower than the PI segment length between junction points of the graft copolymers. 

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