Polybutadiene-polyisoprene blends

Figure 10 shows a spectrum of butyl rubber gum stock obtained on the solid at 80°C using normal pulsed FT techniques. Clearly it could be identified as a component in fabricated materials by direct nmr spectral analysis. Figure 11 shows spectra obtained from various portions of typical rubber products. These samples were cut from the rubber product, placed in an nmr tube without solvent, and spectra obtained at an elevated temperature. The data show how polyisoprene, a polyisoprene/polybutadiene blend and a polyisobutylene/polyisoprene/polybutadiene rubber blend are quickly identified in the materials. Figure 11a shows processing oil was present, and which was confirmed by solvent extraction. 

Tg measurements have been performed on many other polymers and copolymers including phenol bark resins [71], PS [72-74], p-nitrobenzene substituted polymethacrylates [75], PC [76], polyimines [77], polyurethanes (PU) [78], Novolac resins [71], polyisoprene, polybutadiene, polychloroprene, nitrile rubber, ethylene-propylene-diene terpolymer and butyl rubber [79], bisphenol-A epoxy diacrylate-trimethylolpropane triacrylate [80], mono and dipolyphosphazenes [81], polyethylene glycol-polylactic acid entrapment polymers [82], polyether nitrile copolymers [83], polyacrylate-polyoxyethylene grafts [84], Novolak type thermosets [71], polyester carbonates [85], polyethylene naphthalene, 2,6, dicarboxylate [86], PET-polyethylene 2,6-naphthalone carboxylate blends [87], a-phenyl substituted aromatic-aliphatic polyamides [88], sodium acrylate-methyl methacrylate multiblock copolymers [89], telechelic sulfonate polyester ionomers [90], aromatic polyamides [91], polyimides [91], 4,4"-bis(4-oxyphenoxy)benzophenone diglycidyl ether - 3,4 epoxycyclohexyl methyl 3,4 epoxy cyclohexane carboxylate blends [92], PET [93], polyhydroxybutyrate [94], polyetherimides [95], macrocyclic aromatic disulfide oligomers [96], acrylics [97], PU urea elastomers [97], glass reinforced epoxy resin composites [98], PVOH [99], polymethyl methacrylate-N-phenyl maleimide, styrene copolymers [100], chiral... 

TMA has been applied to the determination of Tg in Neoprene, styrene-butadiene, polyisoprene, polybutadiene, polychloroprene, nitrile, ethylene-propylene-diene, and butyl rubbers [8], polyamide 6 [9], polyoxadiazoles, polyether arylenes [9], N(-2-biphenylene)-4-(2-phenylethynyl) phthalimide [10], polypropylene-sericite-tridymite cristohalite blends [11], and ether bridged aromatic dicarboxylic acid [9] and 2,5-bis (4-carboxy phenoxy)-p-terphenyl [12]. 

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 ... 

Other polymers used in the PSA industry include synthetic polyisoprenes and polybutadienes, styrene-butadiene rubbers, butadiene-acrylonitrile rubbers, polychloroprenes, and some polyisobutylenes. With the exception of pure polyisobutylenes, these polymer backbones retain some unsaturation, which makes them susceptible to oxidation and UV degradation. The rubbers require compounding with tackifiers and, if desired, plasticizers or oils to make them tacky. To improve performance and to make them more processible, diene-based polymers are typically compounded with additional stabilizers, chemical crosslinkers, and solvents for coating. Emulsion polymerized styrene butadiene rubbers (SBRs) are a common basis for PSA formulation [121]. The tackified SBR PSAs show improved cohesive strength as the Mooney viscosity and percent bound styrene in the rubber increases. The peel performance typically is best with 24—40% bound styrene in the rubber. To increase adhesion to polar surfaces, carboxylated SBRs have been used for PSA formulation. Blends of SBR and natural rubber are commonly used to improve long-term stability of the adhesives. 

Figure 4. BR + IR is a 50/50 (wt) blend of synthetic cis-1,4-polyisoprene and cis-1,4-polybutadiene. Bl copolymers are random cis-1,4-butadiene-isoprene copolymers with the same composition. Results obtained with Rheovibron on gum vulcanizates at 110 Hz frequency.

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 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. 

Other reported TG-MS applications concern polybutadiene [153], styrene-butadiene rubbers [153], gums [14], polyisoprenes [52], polyurethanes [144, 146, 147, 166], ABS [144], chlorosulphonated polyethylene elastomer [169, 170] and elastomer blends (NBR/SBR/ BR) [13]. Table 1.5 summarises the use of advanced TG-MS systems in elastomer analysis. 

Static H 2D NOE spectroscopy was applied in a first experiment showing that the technique can be used to measure inter-chain interactions [44], This work was then continued by applying the technique under MAS to investigate the inter-molecular interactions responsible for the miscibility in polybutadiene/polyisoprene blends above the Tg [45]. It was shown that intermolecular association can be probed by this technique and the results reveal the existence of weak intermolecular interactions between the polyisoprene methyl group and the vinyl side chain of the polybutadiene. 

The substantial work on polystyrene/polybutadiene and polystyrene/ polyisoprene blends and diblock and triblock copolymer systems has lead to a general understanding of the nature of phase separation in regular block copolymer systems (5,6). The additional complexities of multiblocks with variable block length as well as possible hard- and/or soft-phase crystallinity makes the morphological characterization of polyurethane systems a challenge. 

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.

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]. ... 

The polybutadienes and the -1,4-polyisoprenes used in this work were synthesized in house or obtained from commercial sources. The 1,2-polybutadienes were atactic. Blend compositions, prepared by dissolution in cyclohexane, precipitation into methanol, and vacuum drying, are listed by volume in Table II, along with the weight average degree of polymerization of the component. 

Polybutadiene, CAS 9003-17-2, is a common synthetic polymer with the formula (-CH2CH=CHCH2-)n- The cis form (CAS 40022-03-5) of the polymer can be obtained by coordination or anionic polymerization. It is used mainly in tires blended with natural rubber and synthetic copolymers. The trans form is less common. 1,4-Polyisoprene in cis form, CAS 9003-31-0, is commonly found in large quantities as natural rubber, but also can be obtained synthetically, for example, using the coordination or anionic polymerization of 2-methyl-1,3-butadiene. Stereoregular synthetic cis-polyisoprene has properties practically identical to natural rubber, but this material is not highly competitive in price with natural rubber, and its industrial production is lower than that of other unsaturated polyhydrocarbons. Synthetic frans-polyisoprene, CAS 104389-31-3, also is known. Pyrolysis and the thermal decomposition of these polymers has been studied frequently [1-18]. Some reports on thermal decomposition products of polybutadiene and polyisoprene reported in literature are summarized in Table 7.1.1 [19]. 

While earlier attempts to produce satisfactory synthetic rubber from iso-prene were unsuccessful, in 1955 American chemist Samuel Emmett Horne Jr. (b. 1924) prepared 98 percent czr-l,4-polyisoprene via the stereospecific polymerization of isoprene. Home s product differs from natural mbber only in that it contains a small amount of rfr-l,2-polyisoprene, but it is indistinguishable from natural mbber in physical properties. First produced in 1961, BR (for butadiene mbber), a mbberlike polymer that is almost ex-clnsively czr-1,4-polybutadiene, when blended with natural or SBR mbber, has been nsed for tire treads. 

Pentachlorthiofenol Renacit 7 RPA 6 USAF B-51. Peptizer for natural rubber, polyisoprene, styrene/butadiene rubber, polybutadiene, NBR, bu l, chloroprene and blends absorbed on clay, used as a peptizing agent facilitating open rnill and internal mixer mastication in rubber industry, Mildly toxic by ingestion severe eye irritant. Akrochem Chem. Co. Bayer AG Polysar. 

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