Poly butadiene crosslinking

Kramer, O., Carpenter, R. L., Ty, V., Ferry, J. D. Entanglement networks crosslinked in states of strain, paper presented at Society of Rheology Meeting, Montreal, October 1973. Part of this work is described in Entanglement networks of 1,2-poly butadiene crosslinked in states of strain. I. Cross-linking at 0° C. Macromolecules 7,79-84 (1974), by the same authors. 

Regioselective crosslinking of the core domain of cylindrically shaped, wormlike micelles composed of poly[(butadiene)45-b-(ethylene oxide)55] and assembled in aqueous solution at < 5% block copolymer concentrations, was performed using radical coupling of the double bonds throughout the poly(butadiene) phase [27] (Figure 6.3b). This resulted in a 13% reduction in the core diameter, from 14.2 to 12.4 nm, as measured by small-angle neutron scatter-... 

Core-shell polymers were commercially introduced as impact modifiers for poly(vinyl chloride) PVC, in the 1960s. They are produced by a two-stage latex emulsion polymerization technique (Cruz-Ramos, 2000). The core is a graftable elastomeric material, usually crosslinked, that is insoluble in the thermoset precursors. Typical elastomers used for these purposes are crosslinked poly(butadiene), random copolymers of styrene and butadiene,... 

Similarly, poly(butadiene-g-styrene) represents the graft copolymer in Equation 2, where it is understood that the symbol -g- means graft copolymer, the first indicated species forms the backbone, and the second the side chain. Similarly, the symbol -co- stands for a random copolymer, -a- for an alternating copolymer, and occasionally the symbol -cl- is used for crosslinked systems. 

Many authors elucidated functionalization of polymers containing reactive oxirane moieties. Epoxidized NR, BR, IR and/or the respective model hydrocarbons, poly (butadiene-co-isoprene, various epoxy resins, poly (2,3-epoxypro-pyl methacrylate) and its copolymers or grafted systems were mostly exploited. Stabilizers based on epoxidized unsaturated rubbers are of the top interest. The mechanism of the functionalization process was studied in details by means of 3,4-epoxy-4-methylheptane and 1,2-epoxy-3-ethyl-2-methylpentane as model compounds [289]. The ring opening of the asymmetric oxirane is regiospecific. Aliphatic primary amines attack the least substituted carbon atom and can be involved in crosslink formation. Aromatic primary and secondary amines are less reactive than aliphatic ones because of their lower basicity the attack on the least substituted carbon atom is however preferred too. 

If indeed supramolecular dusters are formed spontaneously in bulk films of appropriately designed rod-coil systems, by inclusion of appropriate reactive units it should be possible to convert these into molecular objects by crosslinking, while maintaining the predse size and shape of the cluster. In order to test this hypothesis, rod-coil triblock copolymers, with structures similar to those described previously, but with a few modifications to enable crosslinking, were prepared. Stupp and coworkers replaced the poly(isoprene) block with a poly( butadiene) (PB) block (which contains both 1,2- and 1,4-linked repeat units), which is known to undergo thermal crosslinking at high temperatures [70]. Additionally, the phenolic OH... 

Since this paper will be restricted to sequential IPN s based on cross-poly butadiene-inter-cross-polystyrene. PB/PS, it is valuable to examine the range of possible compositions, see Figure 2 ( ). The PB/PS IPN polymer pair models high-impact polystyrene, and in fact, many of the combinations made are actually more impact resistant than the commercial materials. In general, with the addition of crosslinks, especially in network I, the phase domains become smaller. The impact resistance of high-impact polystyrene, upper left, is about 80 J/ra. In the same experiment, the semi-I IPN, middle left is about 160 J/m, and the full IPN, lower left, is about 265 J/m (g). Since the commercial material had perhaps dozens of man-years of development, and the IPN composition was made simply for doctoral research with substantially no optimization, it was obvious that these materials warranted further study. 

Poly butadiene rapidly becomes crosslinked when irradiated in vacuo at 253.7 nm [54]. A decrease amounting to 80% of the original unsaturation is observed by infrared spectroscopy. Since no new unsaturation has been detected this decrease has been accounted for by cyclization. However, the absence of absorption at 1020 cm-1 implies that formation of cyclopropyl groups does not occur. Formation of a ladder polymer is also unlikely since all attempts to accomplish the free radical post-polymerization of 1,2-poly butadiene have been unsuccessful namely,... 

Figure 2. Dynamic Young s modulus E of polystyrene (PS), high impact polystyrene (HIPS), separated gel, and crosslinked poly-butadiene rubber. Data from Ref. 17.

The structures listed in Table 1.6 are divided into three categories Short sequences, Long sequences, and Networks. Within the first category a sequence of placement of individual CRU is considered, within the second the placement of long sequences of CRU defines the copolymer type, while to the third belong crosslinked networks, crosslinked polymers, and chemical-type interpenetrating polymer networks. The network is a crosslinked system in which macromolecules of polymer A are crosslinked by macromolecules of polymer B [Sperling, 1992]. The composition can be expressed as, e.g., Woc -co-poly(butadiene/styrene) (75 25 wt%), or gra/i-co-poly[isoprene/ (isoprene acrylonitrile)] (85 15 mole %). 

MBS with controlled size of the elastomeric particles transparent Copolymer of vinylchloride, alkyl acrylate, and vinyhdene chloride Butadiene-styrene-methylacrylate-ethylacrylate Core-shell crosslinked ABS with grafted onto it PMMA shell PB-grafted with MM A, styrene and vinyl acetate Poly(butadiene-co-butyl acrylate-co-styrene)... 

A special ion exchanger for the analysis of alkali and alkaline-earth ions in a single run is produced by coating silica with a crosslinked poly(butadiene-maleic acid) copolymer (7). 

Preformed particles are incorporated into the epoxy matrix by simple mechanical mixing. The dispersibility of the particles can be improved by 1) introducing crosslinking into the shell or 2) using comonomer-like acrylonitrile or GMA, which increases the interfacial adhesion by polar or chemical interaction [96, 97]. Quan and co-workers [98] reported that for poly (butadiene-co-styrene) core poly (methyl methacrylate) (PMMA) shell particles, the cluster size reduces from 3-5 pm to 1-3 pm as a result of using 5 wt% crosslinker (divinyl benzene). They also found that the cluster size could be further reduced to 1-2 pm by using a methyl methacrylate-acrylonitrile (MMA-AN) or methyl methacrylate-glycidyl methacrylate (MMA-GMA) copolymer shell composition. 

The backbone of poly (butadiene) has good flexibility which is an advantage for the final product. In addition, poly(butadiene) shows good reactivity due to the presence of reactive double bonds in the molecule. However, these reactive double bonds do not undergo a chain propagation, but take part in the formation of a crosslinked structure and, therefore, they never form an excess of crosslinked structures. 

The microencapsulation method utilized is as follows. An oil phase containing a catalyst (1,4-diazobicyclo [2,2,2] octane), MCR, diol and crosslinker trimethylol-propane (TMP) is dispersed in paraffin oil containing a steric polymeric stabiHzer (poly(butadiene-b-ethylene oxide)) in a reaction kettle maintained at 35 °C. The emulsion is stirred at 1200 rpm and TDI is added dropwise to the reaction mixture. After stirring the system at a specific stirring rate and temperature, PU microcapsules are formed which are then isolated by filtering the mixture, washing with hexane, and drying under vacuum. 

Synthetic rubbers are produced as commodities. Polybutadiene, polybutylene, polychloroprene and polyepichlorohydrin are examples of elastomeric homopolymers. Copolymeric rubbers comprise poly-(butadiene-co-styrene), poly(butadiene-co-acryloni-trile), poly(ethylene-co-propylene-co-diene), and poly-(epichlorohydrin-co-ethylene oxide). The unsaturated group in the comonomer provides reactive sites for the crosslinking reactions. Copolymers combine resilience with resistance to chemical attack, or resilience in a larger temperature range, and thermoplastic-like properties. There are several studies in the literature describing the preparation of blends and composites of elastomers and conductive polymers. A description of some significant examples is given in this section. 

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