Polymerization processes polymer production

Due to the high importance of chain growth polymerization for polymer production, huge efforts have been undertaken to understand and elucidate the kinetics involved in the chain growth process and the parameters influencing molar mass, dispersity D, and the nature of Ihe resulting macromolecules. In Figure 3.4, the kinetic steps, exemplified for a free radical process, are outlined. 

Polycondensation of the monophosphazene Cl3P=NP(0)Cl2 occurs either in the bulk or in trichlorobiphenyl solution to afford the linear uncrosslinked polymer [NPC ln- A by-product viz., POCI3 is formed in this polymerization process. Polymers with molecular weights of up to 800,000 can be prepared by this method. 

The final system that is worth mentioning in this chapter on LRP in emulsion is the use of 1,1-diphenylethylene (DPE) (127). DPE adds to a growing radical and forms a radical with a reactivity too low for propagation. The exact mechanism is not elucidated, but the incorporation of DPE leads to a chain that allows chain extension or block copolymer formation. More or less similar to what was described about the xanthates in RAFT polymerization, here also the molar mass distributions are relatively broad. The greatest advantage of DPE-mediated polymerization is the fact that it results in minimal disturbance of the polymerization process. The product latex does not contain any unusual extractable material (like the catalyst in ATRP), or polymer-bound colored moieties (like the thiocar-bonylthio compound in RAFT). The obvious drawback is the limited control over chain architecture, and the limited understanding of the mechanistic details. 

The ruthenium initiators have also been used to conduct hydrogenations after the polymerization process. Polymers obtained from G1 or G3 have been shown to be readily hydrogenated upon addition of a base and hydrogen gas. This resulted in the decomposition of initiators and the formation of products acting as hydrogenation catalysts [152-155]. 

It is the third of these criteria that offers the most powerful insight into the nature of the polymerization process for this important class of materials. We shall frequently use the terms step-growth and condensation polymers as synonyms, although by the end of the chapter it will be apparent that step-growth polymerization encompasses a wider range of reactions and products than either criteria (1) or (2) above would indicate. 

Three bulk polymerization processes are commercially important for the production of methacrylate polymers batch cell casting, continuous casting, and continuous bulk polymerization. Approximately half the worldwide production of bulk polymerized methacrylates is in the form of molding and extmsion compounds, a quarter is in the form of cell cast sheets, and a quarter is in the form of continuous cast sheets. 

Solution Polymerization. In this process an inert solvent is added to the reaction mass. The solvent adds its heat capacity and reduces the viscosity, faciUtating convective heat transfer. The solvent can also be refluxed to remove heat. On the other hand, the solvent wastes reactor space and reduces both rate and molecular weight as compared to bulk polymerisation. Additional technology is needed to separate the polymer product and to recover and store the solvent. Both batch and continuous processes are used. 

Eig. 1. The key steps for the Phillips PPS process are (/) production of aqueous sodium sulfide from aqueous sodium hydrogen sulfide (or hydrogen sulfide) and aqueous sodium hydroxide 2) dehydration of the aqueous sodium sulfide and NMP feedstocks 5) polymerization of the dehydrated sulfur source with -dichlorobenzene to yield a slurry of PPS and by-product sodium chloride in the solvent (4) polymer recovery (5) polymer washing for the removal of by-product salt and residual solvent (6) polymer drying (7) optional curing, depending on the appHcation and (< ) packaging. 

Catalyst Development. Traditional slurry polypropylene homopolymer processes suffered from formation of excessive amounts of low grade amorphous polymer and catalyst residues. Introduction of catalysts with up to 30-fold higher activity together with better temperature control have almost eliminated these problems (7). Although low reactor volume and available heat-transfer surfaces ultimately limit further productivity increases, these limitations are less restrictive with the introduction of more finely suspended metallocene catalysts and the emergence of industrial gas-phase fluid-bed polymerization processes. 

The addition polymerization of diisocyanates with macroglycols to produce urethane polymers was pioneered in 1937 (1). The rapid formation of high molecular weight urethane polymers from Hquid monomers, which occurs even at ambient temperature, is a unique feature of the polyaddition process, yielding products that range from cross-linked networks to linear fibers and elastomers. The enormous versatility of the polyaddition process allowed the manufacture of a myriad of products for a wide variety of appHcations. 

Suspension Polymerization. At very low levels of stabilizer, eg, 0.1 wt %, the polymer does not form a creamy dispersion that stays indefinitely suspended in the aqueous phase but forms small beads that setde and may be easily separated by filtration (qv) (69). This suspension or pearl polymerization process has been used to prepare polymers for adhesive and coating appHcations and for conversion to poly(vinyl alcohol). Products in bead form are available from several commercial suppHers of PVAc resins. Suspension polymerizations are carried out with monomer-soluble initiators predominantly, with low levels of stabilizers. Suspension copolymerization processes for the production of vinyl acetate—ethylene bead products have been described and the properties of the copolymers determined (70). Continuous tubular polymerization of vinyl acetate in suspension (71,72) yields stable dispersions of beads with narrow particle size distributions at high yields. 

Poly(vinyl chloride). Poly(vinyl chloride) (PVC) [9002-86-2] is a thermoplastic for building products. It is prepared by either the bulk or the suspension polymerization process. In each process residual monomer is removed because it is carcinogenic. Oxygen must be avoided throughout the process (see Vinyl polymers). 

The ionic liquid process has a number of advantages over traditional cationic polymerization processes such as the Cosden process, which employs a liquid-phase aluminium(III) chloride catalyst to polymerize butene feedstocks [30]. The separation and removal of the product from the ionic liquid phase as the reaction proceeds allows the polymer to be obtained simply and in a highly pure state. Indeed, the polymer contains so little of the ionic liquid that an aqueous wash step can be dispensed with. This separation also means that further reaction (e.g., isomerization) of the polymer s unsaturated ot-terminus is minimized. In addition to the ease of isolation of the desired product, the ionic liquid is not destroyed by any aqueous washing procedure and so can be reused in subsequent polymerization reactions, resulting in a reduction of operating costs. The ionic liquid technology does not require massive capital investment and is reported to be easily retrofitted to existing Cosden process plants. 

Various novel applications in biotechnology, biomedical engineering, information industry, and microelectronics involve the use of polymeric microspheres with controlled size and surface properties [1-31. Traditionally, the polymer microspheres larger than 100 /urn with a certain size distribution have been produced by the suspension polymerization process, where the monomer droplets are broken into micron-size in the existence of a stabilizer and are subsequently polymerized within a continuous medium by using an oil-soluble initiator. Suspension polymerization is usually preferred for the production of polymeric particles in the size range of 50-1000 /Ltm. But, there is a wide size distribution in the product due to the inherent size distribution of the mechanical homogenization and due to the coalescence problem. The size distribution is measured with the standard deviation or the coefficient of variation (CV) and the suspension polymerization provides polymeric microspheres with CVs varying from 15-30%. 

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