Chain transfer agents processing

Rohm and Haas developed a new polymerisation process based on the use of a new chain transfer agent process C). Polymers made with this new process showed very good dispersing activity. 

Inhibitors slow or stop polymerization by reacting with the initiator or the growing polymer chain. The free radical formed from an inhibitor must be sufficiently unreactive that it does not function as a chain-transfer agent and begin another growing chain. Benzoquinone is a typical free-radical chain inhibitor. The resonance-stabilized free radical usually dimerizes or disproportionates to produce inert products and end the chain process. 

Emulsion Process. The emulsion polymerization process utilizes water as a continuous phase with the reactants suspended as microscopic particles. This low viscosity system allows facile mixing and heat transfer for control purposes. An emulsifier is generally employed to stabilize the water insoluble monomers and other reactants, and to prevent reactor fouling. With SAN the system is composed of water, monomers, chain-transfer agents for molecular weight control, emulsifiers, and initiators. Both batch and semibatch processes are employed. Copolymerization is normally carried out at 60 to 100°C to conversions of - 97%. Lower temperature polymerization can be achieved with redox-initiator systems (51). 

If a linear mbber is used as a feedstock for the mass process (85), the mbber becomes insoluble in the mixture of monomers and SAN polymer which is formed in the reactors, and discrete mbber particles are formed. This is referred to as phase inversion since the continuous phase shifts from mbber to SAN. Grafting of some of the SAN onto the mbber particles occurs as in the emulsion process. Typically, the mass-produced mbber particles are larger (0.5 to 5 llm) than those of emulsion-based ABS (0.1 to 1 llm) and contain much larger internal occlusions of SAN polymer. The reaction recipe can include polymerization initiators, chain-transfer agents, and other additives. Diluents are sometimes used to reduce the viscosity of the monomer and polymer mixture to faciUtate processing at high conversion. The product from the reactor system is devolatilized to remove the unreacted monomers and is then pelletized. Equipment used for devolatilization includes single- and twin-screw extmders, and flash and thin film evaporators. Unreacted monomers are recovered for recycle to the reactors to improve the process yield. 

An example of a commercial semibatch polymerization process is the early Union Carbide process for Dynel, one of the first flame-retardant modacryhc fibers (23,24). Dynel, a staple fiber that was wet spun from acetone, was introduced in 1951. The polymer is made up of 40% acrylonitrile and 60% vinyl chloride. The reactivity ratios for this monomer pair are 3.7 and 0.074 for acrylonitrile and vinyl chloride in solution at 60°C. Thus acrylonitrile is much more reactive than vinyl chloride in this copolymerization. In addition, vinyl chloride is a strong chain-transfer agent. To make the Dynel composition of 60% vinyl chloride, the monomer composition must be maintained at 82% vinyl chloride. Since acrylonitrile is consumed much more rapidly than vinyl chloride, if no control is exercised over the monomer composition, the acrylonitrile content of the monomer decreases to approximately 1% after only 25% conversion. The low acrylonitrile content of the monomer required for this process introduces yet another problem. That is, with an acrylonitrile weight fraction of only 0.18 in the unreacted monomer mixture, the low concentration of acrylonitrile becomes a rate-limiting reaction step. Therefore, the overall rate of chain growth is low and under normal conditions, with chain transfer and radical recombination, the molecular weight of the polymer is very low. 

Suspension polymerization of VDE in water are batch processes in autoclaves designed to limit scale formation (91). Most systems operate from 30 to 100°C and are initiated with monomer-soluble organic free-radical initiators such as diisopropyl peroxydicarbonate (92—96), tert-huty peroxypivalate (97), or / fZ-amyl peroxypivalate (98). Usually water-soluble polymers, eg, cellulose derivatives or poly(vinyl alcohol), are used as suspending agents to reduce coalescence of polymer particles. Organic solvents that may act as a reaction accelerator or chain-transfer agent are often employed. The reactor product is a slurry of suspended polymer particles, usually spheres of 30—100 pm in diameter they are separated from the water phase thoroughly washed and dried. Size and internal stmcture of beads, ie, porosity, and dispersant residues affect how the resin performs in appHcations. 

Molecular Weight. PE mol wt (melt index) is usually controlled by reaction temperature or chain-transfer agents. Reaction temperature is the principal control method in polymerization processes with Phillips catalysts. On the other hand, special chemical agents for chain transfer are requited for... 

The photopolymerization process taking place within a representative mixture of sensitizer, initiator, chain-transfer agent, and monomer, typical of positive Cromalin, has been studied in detail (41,42). The exact mechanism is still controversial, but a generalized reaction scheme can be postulated as follows, where L2 = biimidazole dimer, S = sensitizer, RH = chain-transfer agent, L2 = excited biimidazole dimer, L = biimidazole radical,... 

In mbber production, the thiol acts as a chain transfer agent, in which it functions as a hydrogen atom donor to one mbber chain, effectively finishing chain growth for that polymer chain. The sulfur-based radical then either terminates with another radical species or initiates another chain. The thiol is used up in this process. The length of the mbber polymer chain is a function of the thiol concentration. The higher the concentration, the shorter the mbber chain and the softer the mbber. An array of thiols have subsequendy been utilized in the production of many different polymers. Some of these apphcations are as foUow ... 

Enikolopyan et al.til found that certain Co11 porphyrin complexes (eg. 87) function as catalytic chain transfer agents. Later work has established that various square planar cobalt complexes (e.g. the cobaloximes 88-92) are effective transfer agents.Ij2 m The scope and utility of the process has been reviewed several times,1 lt>JM ns most recently by Hcuts et al,137 Gridnev,1 3X and Gridnev and Ittel."0 The latter two references1provide a historical perspective of the development of the technique. 

The effect of the initiation and termination processes on compositional heterogeneity can be seen in data presented in Figure 7.3 and Figure 7.4. The data come from a computer simulation of the synthesis of a hydroxy functional oligomer prepared from S, BA, and HEA with a thiol chain transfer agent. The recipe is similar to those used in some coatings applications. 

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. 

Morton and Salatiello have deduced the ratio kpp/kp for radical polymerization of butadiene by applying the above described procedure, appropriately modified for the emulsion system they used. The primary molecular weight was controlled by a mercaptan acting as chain transfer agent, as in the experiments of Bardwell and Winkler cited above. Measurement of the mercaptan concentration over the course of the reaction provided the necessary information for calculating % at any stage of the process, and in particular at the critical conversion 6c for the initial appearance of gel. The velocity constant ratios which they obtained from their results through the use of Eq. 

Amine sulfide terminal moieties can be imparted into vinyl polymers by using aminethiols as chain transfer agents in aqueous radical polymerization [1182]. The polymers are useful as mineral dispersants. Other uses are as water-treatment additives for boiler waters, cooling towers, reverse osmosis applications, and geothermal processes and oil wells and as detergent additives... 

The model has the capability to estimate a variety of process and product results for many different polymer processes, as shown in Figure 1. It can handle, simultaneously, eight monomers, four initiators and five solvents and chain transfer agents. It has been found to meet the need for solving problems mentioned previously. 

In a recent development, a new process of preparing borane-terminated isotactic polypropylene (z -PPs) via an in situ chain-transfer reaction was achieved by a styrene/hydrogen consecutive chain-transfer reagent, which avoids the use of a B—H containing chain-transfer agent.74 This has resulted in the utilization of milder polymerization conditions due to the use of the alkylaluminoxane cocatalyst (MAO) (50) (Fig. 33), which cannot normally be used in the presence of a B—H chain-transferring... 

Water soluble block copolymers consisting of N-isopropylacrylamidc, NIPA, and the zwitterionic monomer 3-[N-(3-methacrylamidopropyl)-N,N-dimethyl]ammoniopropane sulfonate, SPP, were prepared via the RAFT process [82] (Scheme 31). NIPA was polymerized first using AIBN as the initiator and benzyl dithiobenzoate as the chain transfer agent. To avoid the problem of incomplete end group functionalization the polymerization yield was kept very low (less than 30%). The block copolymerization was then performed... 

This is the simplest process and is widely used for synthesis of condensation polymers. The system is homogeneous and consists of monomer/polymer. In this process the monomer and initiator are kept in a reactor and heated to suitable temperature. The chain transfer agent whenever used for controlling the Molecular weight is also dissolved in the monomer. 

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