Polybutadiene vulcanization

Table IV. Swelling Volumes and Extractable Contents of Networks of Cl—Butyl and cis-Polybutadiene-Vulcanized at 300°F—Sulfur, Zinc Oxide, TMTDS...

Figure 19. Proposed cross-linked structure of cis-polybutadiene vulcanized with dicumyl peroxide.

Gregg J., E. C., Jr. and Lattimer, R. R, Polybutadiene vulcanization. Chemical structures from sulfur-donor vulcanization of an accurate model. Rubber Chem. Technol, 57, 1056, 1984. 

Polybutadiene vulcanized with sulfur Polystyrene cross-linked with divinylbenzene to form a network... 

Dontsov A, Decandia F, Amelino L (1972) Elastic properties and structure of polybutadiene vulcanized with magnesium methaceylate. J Appl Polym Sci 16(2) 505-518... 

The principal mbbers, eg, natural, SBR, or polybutadiene, being unsaturated hydrocarbons, are subjected to sulfur vulcanization, and this process requires certain ingredients in the mbber compound, besides the sulfur, eg, accelerator, zinc oxide, and stearic acid. Accelerators are catalysts that accelerate the cross-linking reaction so that reaction time drops from many hours to perhaps 20—30 min at about 130°C. There are a large number of such accelerators, mainly organic compounds, but the most popular are of the thiol or disulfide type. Zinc oxide is required to activate the accelerator by forming zinc salts. Stearic acid, or another fatty acid, helps to solubilize the zinc compounds. 

Thermoplastic Elastomers. These represent a whole class of synthetic elastomers, developed siace the 1960s, that ate permanently and reversibly thermoplastic, but behave as cross-linked networks at ambient temperature. One of the first was the triblock copolymer of the polystyrene—polybutadiene—polystyrene type (SheU s Kraton) prepared by anionic polymerization with organoHthium initiator. The stmcture and morphology is shown schematically in Figure 3. The incompatibiHty of the polystyrene and polybutadiene blocks leads to a dispersion of the spherical polystyrene domains (ca 20—30 nm) in the mbbery matrix of polybutadiene. Since each polybutadiene chain is anchored at both ends to a polystyrene domain, a network results. However, at elevated temperatures where the polystyrene softens, the elastomer can be molded like any thermoplastic, yet behaves much like a vulcanized mbber on cooling (see Elastomers, synthetic-thermoplastic elastomers). 

This combination of monomers is unique in that the two are very different chemically, and in thek character in a polymer. Polybutadiene homopolymer has a low glass-transition temperature, remaining mbbery as low as —85° C, and is a very nonpolar substance with Htde resistance to hydrocarbon fluids such as oil or gasoline. Polyacrylonitrile, on the other hand, has a glass temperature of about 110°C, and is very polar and resistant to hydrocarbon fluids (see Acrylonitrile polymers). As a result, copolymerization of the two monomers at different ratios provides a wide choice of combinations of properties. In addition to providing the mbbery nature to the copolymer, butadiene also provides residual unsaturation, both in the main chain in the case of 1,4, or in a side chain in the case of 1,2 polymerization. This residual unsaturation is useful as a cure site for vulcanization by sulfur or by peroxides, but is also a weak point for chemical attack, such as oxidation, especially at elevated temperatures. As a result, all commercial NBR products contain small amounts ( 0.5-2.5%) of antioxidant to protect the polymer during its manufacture, storage, and use. 

A new process to develop interface vulcanization is grafting of selective accelerators onto a polymer chain, which in the subsequent process of vulcanization acts as an effective cure accelerator for the second polymer component in the blend. Beniska et al. [6] prepared SERFS blends where the polystyrene phase was grafted with the accelerator for curing SBR. Improved hardness, tensile strength, and abrasion resistance were obtained. Blends containing modified polystyrene and rw-1,4-polybutadiene showed similar characteristics as SBS triblock copolymers. 

Reactive compatibilization can also be accomplished by co-vulcanization at the interface of the component particles resulting in obliteration of phase boundary. For example, when cA-polybutadiene is blended with SBR (23.5% styrene), the two glass transition temperatures merge into one after vulcanization. Co-vulcanization may take place in two steps, namely generation of a block or graft copolymer during vulcanization at the phase interface and compatibilization of the components by thickening of the interface. However, this can only happen if the temperature of co-vulcanization is above the order-disorder transition and is between the upper and lower critical solution temperature (LCST) of the blend [20]. 

This most simple model for the relaxation time spectrum of materials near the liquid-solid transition is good for relating critical exponents (see Eq. 1-9), but it cannot be considered quantitatively correct. A detailed study of the evolution of the relaxation time spectrum from liquid to solid state is in progress [70], Preliminary results on vulcanizing polybutadienes indicate that the relaxation spectrum near the gel point is more complex than the simple spectrum presented in Eq. 3-6. In particular, the relation exponent n is not independent of the extent of reaction but decreases with increasing p. 

Fig. 14. Loss tangent of several stopped samples of vulcanizing polybutadiene (Mw = 18000) [31]. At the gel point, tan 3 is frequency independent (flat curve in the middle). The relaxation exponent n can be easily evaluated from the data (tan 3 = 1 yields n = 0.5)...

Time-cure superposition is valid for materials which do not change their relaxation exponent during the transition. This might be satisfied for chemical gelation of small and intermediate size molecules. However, it does not apply to macromolecular systems as Mours and Winter [70] showed on vulcanizing polybutadienes. 

Bis(nitrile oxides) obtained from dialkylbenzenes have been claimed as low-temperature rubber vulcanization agents (517). Curing of poly(butadiene-co-acrylonitrile) with 2,4,6-trimethylisophthalodinitrile N-oxide produces rubbery material of good quality, however, curing of (polybutadiene) was unsuccessful (518). The solubility of dinitrile oxides and stability of their ketone solutions has been studied for their application as vulcanizing agents in the production of mbberized materials (519). 

A typical tire rubber formulation for tire tread will contain various rubbers, mainly styrene-butadiene (50%) and cA-polybutadiene (12%), various processing aids (2%), softeners (3%), vulcanizing agent (mainly sulfur 1%), accelerators, and reinforcing filler (namely carbon black 30%) so that by bulk, carbon black is the second most used material. 

Crespi, G., and U. Flisi Contribution of the internal energy to the retractive force of vulcanized cis-l,4-polybutadiene. Makromol. Chem. 60, 191 (1963). 

The new absorptions in the spectra of crosslinked rubber are assigned on the basis of 13C solution NMR chemical shifts for a variety of model compounds, such as pentenes and mono-, di- and tri-sulfidic compounds, by using the 13C chemical shift substituent effect. From the calculated values for particular structural units, the experimental spectra of a sulfur vulcanized natural rubber 194,195,106), natural rubber cured by accelerated sulfur vulcanization 197 y-irradiation crosslinked natural rubber198 and peroxide crosslinked natural rubber and cis-polybutadiene 193 1991 are assigned. 

A large volume usage of S—B—S-based compounds is in footwear. Canvas footwear, such as sneakers and unit soles, can be made by injection molding. Frictional properties resemble those of conventionally vulcanized mbbers and are superior to those of the flexible thermoplastics, such as plasticized poly(vinyl chloride). The products remain flexible under cold conditions because of the good low temperature properties of the polybutadiene... 

The system Cl-butyl-cis-polybutadiene has been studied in some detail because it was suitable for the developed differential swelling technique and because this system of blends vulcanized with zinc oxide, sulfur, and thiuram disulfide first revealed the presence of interfacial bonds. This curative system has the feature of a flat cure —i.e.y the two homophases are vulcanized rapidly, and the crosslinked density does not increase radically as vulcanization time is prolonged. This is observed in Table IV by swelling and extractable levels of a series of crosslinked networks cured at increasing times and swollen in a common solvent, cyclohexane. 

Crystallization of oriented chains is, in various respects, important for the polymer properties. The fact has been mentioned before, that stereospecific rubbers such as cis-1,4 polybutadiene can crystallize when under strain. The spontaneously formed crystals contribute strongly to the strength of the vulcanizate. A vulcanized natural rubber has, without carbon black reinforcement, a tensile strength of about 40 MPa, whereas an unreinforced SBR breaks at about 3 MPa. (With SBR a high tensile strength can only be reached with carbon black.)... 

The desirability of segregation in block copolymers can be demonstrated by considering the behaviour of SBS, which is one of the oldest types. It has about the same chain composition as SBR, but, rather than SBR, it shows two glass-rubber transitions, namely that of polybutadiene and that of polystyrene. Between these two temperatures it behaves as a rubber, in which the PS domains act as cross-links it is, therefore, a self-vulcanizing rubber (see also Figure 3.8 see Qu. 9.14). Moreover, the hard domains play the role of a reinforcing filler. 

Unsaturated and Vulcanized Rubbers. Oxidation occurs most readily at polymers with structural double bonds, such as natural rubber, polybutadiene, or polyisoprene. Aromatic amines and sterically hindered phenols are effective antioxidants. From the rubber antioxidants, 96.8 million pounds were amines, and 20 million pounds were phenols. Amines act also as antiozonants whereas phenols are not effective. Furukawa shows that amines have a lower oxidation potential which is a prerequisite for antiozonant action. 

Block copolymers themselves are also finding rapidly expanding applications on an industrial scale. A sandwich copolymer (triblock) with an elastomeric core (polybutadiene, polyisoprene, etc.) and plastomeric ends (polystyrene, etc.) represents a physically vulcanizing rubber (plastomeric elastomer). It can be processed above the glass transition temperature of the plastomeric blocks by work-efficient technologies (injection molding, extrusion, etc.). At temperatures below the Tg of the plastic blocks, the copolymer behaves as vulcanized rubber. 

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