Suspension polymerisation

The first study of this kind was carried out by Chinese researchers in 2003 [144]. They prepared MIP beads for the SPE of tyrosine by simple suspension in water as well as by two-step swelling and suspension polymerisation. They found no substantial difference in the rebinding capacity of the beads prepared by the two methods. A more thorough analysis of various synthetic approaches to MIP beads was conducted a year later by Perez-Moral and Mayes [145]. They took a standard monomer mixture with propranolol as the template molecule and polymerised it by bulk polymerisation, suspension polymerisation, precipitation polymerisation, two-step-swelling polymerisation and emulsion core-shell polymerisation (see also Sect. 2.2.3). Care was taken to keep the polymerisation... 

Polystyrene can be polymerised by foam processes, mass polymerisation, solution polymerisation, suspension polymerisation and emulsion polymerisation. Each contributes to the final characteristics of the plastics and the likely residues. A limit for styrene monomer may be imposed. Styrene can be readily analysed down to a 0.01% level. Polystyrene exhibits low shrinkage, hence is an excellent moulding material. 

Suspension polymerisation (49,298) is a heterogeneous polymerisation process that is related to, but is not the same as, emulsion polymerisation. Suspension polymerisation differs from conventional emulsion polymerisation in that the droplets are much larger, and an oil-soluble initiator is used to start polymerisation within the droplets. To prepare a suspension, monomers with relatively low water-solubility are dispersed along with a stabiliser in water by stirring. The stabiliser... 

About 0-1 per cent, of hydroquinone should be added as a stabiliser since n-hexaldehyde exhibits a great tendency to polymerise. To obtain perfectly pure n-/iexaldehyde, treat the 21 g. of the product with a solution of 42 g. of sodium bisulphite in 125 ml. of water and shake much bisulphite derivative will separate. Steam distil the suspension of the bisulphite compound until about 50 ml. of distillate have been collected this will remove any non-aldehydic impurities together with a little aldehyde. Cool the residual aldehyde bisulphite solution to 40-50 , and add slowly a solution of 32 g. of sodium bicarbonate in 80 ml. of water, and remove the free aldehyde by steam distillation. Separate the upper layer of n-hexaldehyde, wash it with a little water, dry with anhydrous magnesium sulphate and distil the pure aldehyde passes over at 128-128-5°. 

Suspension Polymerization. Suspension polymerisation yields polymer in the form of tiny beads, which ate primarily used as mol ding powders and ion-exchange resins. Most suspension polymers prepared as mol ding powders are poly(methyl methacrylate) copolymers containing up to 20% acrylate for reduced btittieness and improved processibiUty are also common. 

In a suspension polymerisation monomer is suspended in water as 0.1—5-mm droplets, stabilised by protective coUoids or suspending agents. Polymerisation is initiated by a monomer-soluble initiator and takes place within the monomer droplets. The water serves as both the dispersion medium and a heat-transfer agent. Particle sise is controlled primarily by the rate of agitation and the concentration and type of suspending aids. The polymer is obtained as small beads about 0.1—5 mm in diameter, which are isolated by filtration or centrifugation. 

Suitable protective coUoids for the preparation of acryhc suspension polymers include ceUulose derivatives, polyacrylate salts, starch, poly(vinyl alcohol), gelatin, talc, clay, and clay derivatives (95). These materials are added to prevent the monomer droplets from coalescing during polymerisation (110). Thickeners such as glycerol, glycols, polyglycols, and inorganic salts ate also often added to improve the quahty of acryhc suspension polymers (95). 

The synthesis of the high molecular weight polymer from chlorotrifluoroethylene [79-38-9] has been carried out in bulk (2 >—21 solution (28—30), suspension (31—36), and emulsion (37—41) polymerisation systems using free-radical initiators, uv, and gamma radiation. Emulsion and suspension polymers are more thermally stable than bulk-produced polymers. Polymerisations can be carried out in glass or stainless steel agitated reactors under conditions (pressure 0.34—1.03 MPa (50—150 psi) and temperature 21—53°C) that require no unique equipment. 

Free Radical Initiators for the Suspension Polymerisation of Vinyl Chloride, Technical Publication 30.90, Lucidol Division, Pennwalt Corp., Buffalo, N.Y., 1976. 

Chain transfer to monomer and to other small molecules leads to lower molecular weight products, but when polymerisation occurs ia the relative absence of monomer and other transfer agents, such as solvents, chain transfer to polymer becomes more important. As a result, toward the end of batch-suspension or batch-emulsion polymerisation reactions, branched polymer chains tend to form. In suspension and emulsion processes where monomer is fed continuously, the products tend to be more branched than when polymerisations are carried out ia the presence of a plentiful supply of monomer. 

For both suspension and mass polymerisations at less than 2% conversion, PVC precipitates from its monomer as stable primary particles, slightly below 1-p.m dia (4,10—12). These primary particles are stabilised by a negative chloride charge (4,13). Above 2% conversion, these primary particles agglomerate. Sectioning the PVC grains of either suspension or mass resins readily shows the skins primary particles at 1-p.m dia, and agglomerates of primary particles at 3—10-pm dia (4,7,8,14). 

Acrylate esters can be polymerised in a variety of ways. Among these is ionic polymerisation, which although possible (6—9), has not found industrial apphcation, and practically all commercial acryUc elastomers are produced by free-radical polymerisation. Of the four methods available, ie, bulk, solution, suspension, and emulsion polymerisation, only aqueous suspension and emulsion polymerisation are used to produce the ACMs present in the market. Bulk polymerisation of acrylate monomers is hasardous because it does not allow efficient heat exchange, requited by the extremely exothermic reaction. 

EPM and EPDM mbbers are produced in continuous processes. Most widely used are solution processes, in which the polymer produced is in the dissolved state in a hydrocarbon solvent (eg, hexane). These processes can be grouped into those in which the reactor is completely filled with the Hquid phase, and those in which the reactor contents consist pardy of gas and pardy of a Hquid phase. In the first case the heat of reaction, ca 2500 kJ (598 kcal)/kg EPDM, is removed by means of cooling systems, either external cooling of the reactor wall or deep-cooling of the reactor feed. In the second case the evaporation heat from unreacted monomers also removes most of the heat of reaction. In other processes using Hquid propylene as a dispersing agent, the polymer is present in the reactor as a suspension. In this case the heat of polymerisation is removed mainly by monomer evaporation. 

An alternative approach to solving the exotherm problem is to polymerise in suspension. In this case the monomer is vigorously stirred in water to form tiny droplets. To prevent these droplets from cohering at the stage when the droplet is a sticky mixture of polymer and monomer, suspension or dispersion agents... 

The final polymerised product is formed in particles much smaller (50-500 nm) than produced with suspension polymerisation. Emulsion polymerisation can lead to rapid production of high molecular weight polymers but the unavoidable occlusion of large quantities of soap adversely affects the electrical insulation properties and the clarity of the polymer. 

Although much less important in tonnage terms than processing in the molten and rubbery states, solution, suspension and polymerisation casting processes have a useful role in polymer technology. The main problem in such processes is to achieve a control of the setting of the shape once formed. 

A third type of suspension is that in which polymer particles are suspended in monomer which is then polymerised. This is, however, rather more a variant of the casting process in which monomer or low molecular weight polymer is cast into a mould and then polymerised in situ. 

In the suspension process, which was the first method to be commercially developed, propylene is charged into the polymerisation vessel under pressure whilst the catalyst solution and the reaction diluent (usually naphtha) are metered in separately. In batch processes reaction is carried out at temperatures of about 60°C for approximately 1-4 hours. In a typical process an 80-85% conversion to polymer is obtained. Since the reaction is carried out well below the polymer melting point the process involves a form of suspension rather than solution polymerisation. The polymer molecular weight can be controlled in a variety of... 

Figure 12.7. Typical polymerisation vessel suitable for suspension or emulsion polymerisation of...

The success of filler polymers used in increasing quantities in PVC technology paste can be considered as an extension of this principle. These filler polymers are made by suspension (granular, dispersion) polymerisation and by... 

Vinyl acetate may be easily polymerised in bulk, solution, emulsion and suspension. At conversions above 30%, ehain transfer to polymer or monomer may occur. In the case of both polymer and monomer transfer two mechanisms are possible, one at the tertiary carbon, the other (illustrated in Figure 14.4) at the acetate group. 

Poly(vinyl alcohol) will function as a non-ionic surface active agent and is used in suspension polymerisation as a protective colloid. In many applications it serves as a binder and thickener is addition to an emulsifying agent. The polymer is also employed in adhesives, binders, paper sizing, paper coatings, textile sizing, ceramics, cosmetics and as a steel quenchant. 

As a result the suspension polymerisation of methyl methacrylate was developed to produce commercial material such as Diakon made by ICI. Such a polymerisation can be carried out rapidly, usually in less than an hour, because there is no serious exotherm problem. 

Suspension polymerisation of styrene is widely practised commercially. In this process the monomer is suspended in droplets 5 -Min. in diameter in a fluid, usually water. The heat transfer distances for the dissipation of the exotherm are thus reduced to values in the range s-fisin. Removal of heat from the low-viscosity fluid medium presents little problem. The reaction is initiated by monomer-soluble initiators such as benzoyl peroxide. 

To produce the Type 2 polymers, styrene and acrylonitrile are added to polybutadiene latex and the mixture warmed to about 50°C to allow absorption of the monomers. A water-soluble initiator such as potassium persulphate is then added to polymerise the styrene and acrylonitrile. The resultant materials will be a mixture of polybutadiene, polybutadiene grafted with acrylonitrile and styrene, and styrene-acrylonitrile copolymer. The presence of graft polymer is essential since straightforwsird mixtures of polybutadiene and styrene-acrylonitrile copolymers are weak. In addition to emulsion processes such as those described above, mass and mass/suspension processes are also of importance. 

Bead Processes. These processes have generally replaced the above techniques. The styrene is polymerised by bead (suspension) polymerisation techniques. The blowing agent, typically 6% of low boiling petroleum ether fraction such as n-pentane, may be incorporated before polymerisation or used to impregnate the bead under heat and pressure in a post-polymerisation operation. 

The polymer may be prepared readily in bulk, emulsion and suspension, the latter technique apparently being preferred on an industrial scale. The monomer must be free from oxygen and metallic impurities. Peroxide such as benzoyl peroxide are used in suspension polymerisations which may be carried out at room temperature or at slightly elevated temperatures. Persulphate initiators and the conventional emulsifying soaps may be used in emulsion polymerisation. The polymerisation rate for vinylidene chloride-vinyl chloride copolymers is markedly less than for either monomer polymerised alone. 

Hydroxy propyl cellulose, like methyl cellulose, is soluble in cold water but not in hot, precipitating above 38°C. It was introduced by Hercules in 1968 (Klucel) for such uses as adhesive thickeners, binders, cosmetics and as protective colloids for suspension polymerisation. The Dow company market the related hydroxypropylmethyl cellulose (Methocel) and also produce in small quantities a hydroxyethylmethyl cellulose. 

Chain reactions are used to prepare a variety of high molar mass polymers of commericial importance and in practice may take one of four forms, namely bulk, solution, suspension, and emulsion methods. These four methods are described in the sections that follow, together with the loop modification which has become of commercial importance recently in producing latexes by emulsion polymerisation for the paint industry. 

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