Rubber phase, polymerization

Finch at (28), show three "stratifying polymerizers" rather than the design combinations described earlier by Ruffing et al (27). The reactors operate at inlet and outlet temperatures respectively of 120 to 135°C, 135 to 145°C, and 145 to 170 C. The first reactor effluent contains 18 to 20% polystyrene and a portion of this stream is recirculated back to the reactor inlet such that the inlet stream polystyrene concentration is as high as 13.5%. This recirculation is claimed to improve rubber phase particle size control and end use properties. 

By maintaining the first-stage reactor just beyond the phase inversion point, the dispersed rubber phase is relatively rich in dissolved styrene. As polymerization subsequently proceeds in the LFR s, the dissolved styrene will react to form either a graft copolymer with the rubber or a homopolymer. The latter will remain within the rubber droplet as a separate occluded phase. Achieving the first-stage reactor conversion and temperature by recycling a portion of the hot second reactor effluent may permit simplification of the first reactor temperature control system. 

The devolatilization of a component in an internal mixer can be described by a model based on the penetration theory [27,28]. The main characteristic of this model is the separation of the bulk of material into two parts A layer periodically wiped onto the wall of the mixing chamber, and a pool of material rotating in front of the rotor flights, as shown in Figure 29.15. This flow pattern results in a constant exposure time of the interface between the material and the vapor phase in the void space of the internal mixer. Devolatilization occurs according to two different mechanisms Molecular diffusion between the fluid elements in the surface layer of the wall film and the pool, and mass transport between the rubber phase and the vapor phase due to evaporation of the volatile component. As the diffusion rate of a liquid or a gas in a polymeric matrix is rather low, the main contribution to devolatilization is based on the mass transport between the surface layer of the polymeric material and the vapor phase. 

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... 

A polyacetylene coating applied on sulfur does not negatively influence its activity and speed as curing agent, but it can increase the scorch time. This effect is probably due to a delayed release of the sulfur out of the polymeric shell. In the SBR/EPDM blend, on the other hand, the plasma-treated sulfur results in higher torque values, an indication that the distribution of the plasma-treated sulfur over the different rubber phases is more homogenous, which is the main effect aimed for in the context of this study. 

For the polymerization of ethylene and propylene large-scale gas-phase processes are well established. The implementation of gas-phase technology to the production of sticky polymers such as the ethylene/propylene-based rubbers EPM and EPDM was pioneered by UCC [519]. In a series of patents, UCC describes various approaches to overcome the inherent stickiness of rubber granules in the gas-phase polymerization. These approaches include the use of anti-agglomerants such as carbon black, silica, inorganic salts or appropriate catalyst supports and antistatic voltage etc. [520-535]. The addition of fluidization or anti-agglomeration aids is described by Zollner et al., silica is used in particular [536,537]. 

Through polymerization of a styrene rubber solution, one obtains SB mass (styrene-butadiene). SB forms a twophase system in which the styrene is the continuous phase and the rubber, usually a butadiene base, is the discontinuous phase. The rubber phase also contains pockets of styrene. The SB polymer, because of its properties, is also known as impact resistant or high impact PS (HIPS). 

Figure 6. Microstructure of polymer, obtained by the polymerization of the rubber phase, separated from the prepolymer, increase X8000. Occlusions of the Il-type are seen.

Rubber-modified polystyrene was the next logical evolution after general-purpose polystyrene. Very early on it was apparent that the Achilles heel of polystyrene was its inherent brittleness. Rubber-modified polystyrene is a two-phase system consisting of a dispersed rubber phase and a continuous polystyrene phase (or matrix). Impact-modified polystyrene was invented as early as 1927 by Ostromislensky [15] by addition of natural rubber either polymerized with styrene or blended in polystyrene. 

The grafting is accomplished in the commercial mass polymerization process by polymerizing styrene in the presence of a dissolved rubber. Dissolving the elastomer in the styrene monomer before polymerization produces HIPS grades. Since the two polymer solutions are incompatible, the styrene-rubber system phase separates very early in conversion. Polystyrene forms the continuous phase, with the rubber phase existing as discrete particles having occlusions of polystyrene. Different production techniques and formulations allow the rubber phase to be tailored to a wide range of properties. Typically ... 

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. 

Styrenic block copolymers derive their useful properties from their ability to form distinct styrene (hard phase) and diene (rubber phase) domains, with well defined morphologies. To achieve this requires an unusual degree of control over the polymerization. The polymerization must yield discrete blocks of a uniform and controlled size, and the interface between the blocks must be sharp. This is best achieved by so-called living polymerization. For a polymerization to be classified as truly living, it is generally accepted that it must meet several criteria [3] ... 

The morphology of the rubber-modified polystyrenes system involves some complex aspects, such as particle size, size distribution, occlusions of polystyrene inside the rubber phase, interfacial bonding between the rubbery particles and the brittle matrix, etc. Many authors have observed that some of the most important factors in controlling the mechanical properties of HIPS and ABS are rubber particle size [49], volume fraction of the rubbery phase (rubber + occluded polystyrene) [50,51] and the degree of graft [52]. Grafting occurs during the polymerization of styrene when some of the free radicals react with the rubber... 

The successful utilization of Reaction Injection Molding (RIM) to fabricate complex polyurethane shapes In a single step from relatively low viscosity streams has led to a search for other chemical systems which can be fabricated by the RIM process. The rapid polymerization of molten caprolactam by anionic catalysis has been utilized to develop attractive nylon RIM systems. The incorporation of a rubber segment In the polymer chain allows the fabrication of high Impact or even elastomeric nylon parts. The combination of a rubber phase with the high melting (215°C) crystalline nylon phase provides useful properties at low temperatures as well as at elevated temperatures. 

Figure A. Formation of rubber particles by phase Inversion of polymeric oil-in-oil emulsion. Phase contrast micrograph (rubber phase is light) according to G. E. Molare and H. Keskkula.

Phillips Petroleum Company now manufactures the K-Resin family of optically transparent impact polystyrene (35). These resins, made via anionic polymerization techniques, owe their transparency to the extremely small size of the dispersed rubber phase. The principal use of K-Resin is in packaging applications. 

To make impact copolymers, the polypropylene resin formed in the first reactor (1) is transferred into the second reactor (5). Gaseous propylene and ethylene, with no additional catalyst, are fed into the second reactor to produce the polymeric rubber phase within the existing polypropylene particles. The second reactor operates in the same manner as the initial reactor, but at approximately half the pressure, with a centrifugal compressor (6) circulating gas through a heat exchanger (7) and back to the fluid-bed reactor. Polypropylene product is removed by product discharge tanks (8) and unreacted gas is returned to the reactor. 

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