Polybutadiene rubber, dissolved

In process variants for HIPS ( 7, 28), the feed solution to the first reactor, besides styrene and ethylbenzene, will also contain dissolved polybutadiene rubber along with antioxidants, chain transfer agents, and possibly mineral oil. 

Impact Properties. Chemical Nature of the Rubber. If the rubber is too compatible with the matrix, it will dissolve in the rigid material and disperse on a molecular scale. Little or no reinforcement will occur since the rubber particles become smaller than the radius of the tip of a stress-induced propagating crack. However if it is highly incompatible, good adhesion between rubber and matrix cannot be obtained. For example polybutadiene rubber adheres poorly to a styrene/acrylonitrile copolymer, but a nitrile rubber adheres well to the SAN copolymer. If grafting techniques are used however, compatibility is less of a problem since the rubber is chemically bonded to the matrix. 

As a means to improve the rubber utilization, a bulk/suspension process evolved, whereby polybutadiene rubber was dissolved in styrene monomer and polymerized in bulk beyond phase inversion before being dropped into suspension. The HIPS produced this way had two distinct advantages over the compounded version styrene to rubber grafting and discrete rubber spheres or particles uniformly dispersed in a polystyrene matrix. This improved the impact strength dramatically per unit of rubber and gave better processing stability, because the rubber phase was dispersed instead of being co-continuous with the polystyrene. 

Unsaturated rubber polymers are especially important grafting vehicles. Consider, for example, the polymerization of styrene in the presence of l,4-poly(l,3-butadiene). A method consists of dissolving the polybutadiene rubber (about 5 to 10%) in monomeric styrene containing benzoyl peroxide initiator and applying heat. Polymer radicals, formed by (a) chain transfer between the propagating radical and polymer or (b) addition (copolymerization) of the propagating radical to the -double bonds of the polymer. 

Graft Copolymers. In graft copolymerization, a preformed polymer with residual double bonds or active hydrogens is either dispersed or dissolved in the monomer in the absence or presence of a solvent. On this backbone, the monomer is grafted in free-radical reaction. Impact polystyrene is made commercially in three steps first, solid polybutadiene rubber is cut and dispersed as small particles in styrene monomer. Secondly, bulk prepolymerization and thirdly, completion of the polymerization in either bulk or aqueous suspension is made. During the prepolymerization step, styrene starts to polymerize by itself forming droplets of polystyrene with phase separation. When equal phase volumes are attained, phase inversion occurs. The droplets of polystyrene become the continuous phase in which the rubber particles are dispersed. R. L. Kruse has determined the solubility parameter for the phase equilibrium. 

Rubber dissolving (1) Polybutadiene rubber, in bale form, is chopped into crumbs. To enhance dissolving, preheated styrene is introduced into a high-shear in-line mixer. This operation allows high capacity production of dissolved rubber at a high rubber concentration. 

Polyisoprenes and polybutadienes can also be modified by reactions with carbenes. Dichloro-carbene adds to natural rubber dissolved in chloiofoim in a phase transfer reaction with aqueous NaOH and a phase transfer reagent. Solid sodium hydroxide can be used without a phase transfer reagent. There is no evidence of cis-trans isomerization and the distribution of the substituents is random. ... 

According to the mass process, polybutadiene rubber is dissolved in the mixed solution of styrene and acrylonitrile monomers, and then the reaction proceeds to prepare the ABS resin. For polybutadiene rubber, the method for grinding and then adding the rubber is utihzed. Contrary to the emulsion process, the particles of polybutadiene rubber are not present before the reaction, and therefore, the shape and distribution of particles appear to be different from those of the emulsion process. The molecular weight of polybutadiene rubber to be used is about 200,000, with the cis-1,4 ratio being about 40%. The amoimt of polybutadiene rubber used should be kept to 20% due to the problem related to a viscosity of polymerization solution. 

Generally, the process is very similar to the GPPS process. The main difference is the addition of the rubber component. Polybutadiene rubber received in the form of 35 kg bales is ground into small chips. These rubber chips are added to the dissolving tank by gravity or pneumatic conveyor. There, with strong agitation, the chips are dissolved in styrene to obtain a rubber solution that can contain up to 15 % of rubber. 

Two types of networks were prepared (i) randomly crosslinked polybutadiene, and (ii) model urethane networks, (a) polybutadiene based, and (b) poly(e-caprolactone) based. The randomly crosslinked networks were prepared from polybutadiene (Duragen 1203 obtained from General Tire and Rubber Co.) crosslinked with di-cumyl peroxide. Specifications of the as obtained polybutadiene are given in Table I. Polybutadiene was purified by dissolving in benzene and precipitating in methanol. Precipitated polybutadiene was redissolved in benzene. Seven different weights of dicumyl... 

Normal rhombic sulphur has differing degrees of solubility in the different rubber types. In NR and SBR the required proportion for crosslinking dissolves relatively rapidly at room temperature. In stereospecific rubbers such as polybutadiene and nitrile it does not solubilise so readily. As one would expect, the solubility of the sulphur within the rubber increases with temperature increase. 

Another major use of butadiene polymer is in the manufacture of HIPS. Most HIPS has about 4%i-12%i polybutadiene in it so that HIPS is mainly a PS-intense material. Here, the polybutadiene polymer is dissolved in a liquid along with styrene monomer. The polymerization process is unusual in that both a matrix composition of PS and polybutadiene is formed as well as a graft between the growing PS onto the polybutadiene is formed. The grafting provides the needed compatibility between the matrix phase and the rubber phase. The grafting is also important in determining the structure and size of rubber particles that... 

Initially various rubbery butadiene and styrene-butadiene block polymers were screened as impact-modifying agents for polystyrene. Commercial polystyrene and various rubbers were blended by dissolving the polymers in benzene and by subsequently precipitating them with isopropyl alcohol. The solid polymer blends were dried and molded into test bars. Laboratory and commercial polybutadiene and polystyrene were used in several combinations with the block polymer prepared in our laboratory. 

The most important current graft copolymers include impact-resistant polystyrenes, in which a rubber, like polybutadiene (1-28) is dissolved in styrene ... 

Styrene and butadiene also form copolymers known as high impact polystyrene, or rubber-modified polystyrene, when the content of butadiene is 10%. This type of material has excellent mechanical properties, and it is widely used in practice for the manufacturing of numerous objects, including parts for household appliances, furniture, etc. Rubber-modified polystyrene is commonly used as wood replacement and also for packaging. The synthesis of this material typically is done by dissolving polybutadiene in styrene monomer, followed by free radical polymerization achieved using a peroxide catalyst. This procedure leads to block or graft type copolymers. 

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