Polymerization techniques

Polymerization reactions can occur in bulk (without solvent), in solution, in emulsion, in suspension, or in a gas-phase process. Interfacial polymerization is also used with reactive monomers, such as acid chlorides. 

Polymers obtained by the bulk technique are usually pure due to the absence of a solvent. The purity of the final polymer depends on the purity of the monomers. Heat and viscosity are not easily controlled, as in other polymerization techniques, due to absence of a solvent, suspension, or emulsion medium. This can be overcome by carrying the reaction to low conversions and strong agitation. Outside cooling can also control the exothermic heat. 

In solution polymerization, an organic solvent dissolves the monomer. Solvents should have low chain transfer activity to minimize chain transfer reactions that produce low-molecular-weight polymers. The presence of a solvent makes heat and viscosity control easier than in bulk polymerization. Removal of the solvent may not be necessary in certain applications such as coatings and adhesives. 

Emulsion polymerization is widely used to produce polymers in the form of emulsions, such as paints and floor polishes. It also used to polymerize many water insoluble vinyl monomers, such as styrene and vinyl chloride. In emulsion polymerization, an agent emulsifies the monomers. Emulsifying agents should have a finite solubility. They are either ionic, as in the case of alkylbenzene sulfonates, or nonionic, like polyvinyl alcohol. 

Water is extensively used to produce emulsion polymers with a sodium stearate emulsifrer. The emulsion concentration should allow micelles of large surface areas to form. The micelles absorb the monomer molecules activated by an initiator (such as a sulfate ion radical 80 4 ). X-ray and light scattering techniques show that the micelles start to increase in size by absorbing the macromolecules. For example, in the free radical polymerization of styrene, the micelles increased to 250 times their original size. 

The different polymerization classes discussed above can be implemented in several ways bulk polymerization, solution polymerization, gas-phase polymerization, slurry polymerization, suspension polymerization and emulsion polymerization. 

In bulk polymerization, the only components of the formulation are monomers and the catalyst or initiator. When the polymer is soluble in the monomer, the reaction mixture remains homogeneous for the whole process. Examples of homogeneous bulk polymerization are the production of low-density polyethylene (LDPE), general purpose polystyrene and poly(methyl methacrylate) produced by free-radical polymerization, and the manufacture of many polymers produced by step-growth polymerization including poly(ethylene terephthalate), polycarbonate and nylons. In some cases (e.g., in the production of HIPS and acrylonitrile-butadiene-styrene (ABS) resins), the reaction mixture contains a preformed 

The thermal control of the reactor is much easier if the monomer is polymerized in solution. The solvent lowers the monomer concentration, and consequently the heat generation rate per unit volume of the reactor. In addition, the lower viscosity allows a higher heat removal rate and the solvent allows for the use of reflux condensers. Reflux cooling removes the heat of polymerization by evaporation of solvent the condensed vapor is recycled to the reacting mass. Remixing of the condensed solvent with the viscous reacting mass may be difficult. Solution processes are used for the manufacture of LLDPE [19]. The main drawback is dealing with an environmentally unfriendly solvent, which makes solvent recovery a critical issue. 

Polymerization of ethylene is often carried out in gas-phase using a heterogeneous coordination catalyst [22]. Polymer is formed on the active sites of the catalyst forming an expanding catalyst-polymer particle. The gaseous monomer diffuses through the pores of the particle and through the polymer to reach the active sites. 

Slurry polymerization is often used in the manufacture of polyolefins. Initially, the reaction system consists of the catalyst dispersed (or dissolved as in the case of soluble metallocene catalysts) in a continuous medium, which may be a diluent in which the monomer is dissolved or pure monomer. The polymer is insoluble in the continuous medium, therefore it precipitates on the catalyst forming a slurry. High-density polyethylene (HOPE) is produced in a slurry of isobutane (Chevron-Phillips process) [22 ]. Liquid propylene is used in the Spheripol process to produce i-PP [22]. 

Polymers can be prepared by many different processes. Free radical polymerization can be accomplished in bulk, suspension, solution, or emulsion. Ionic and other nonradical polymerizations are usually produced in solution polymerizations. Each technique has characteristic advantages and disadvantages. 

Bulk polymerization. Bulk polymerization is the simplest and most direct method (from the standpoint of formulation and equipment) for converting monomer to polymer. It requires only monomer (and possibly monomer-soluble initiator or catalyst), and perhaps a chain transfer agent for molecular weight control, and as such gives the highest-purity polymer. However, extra care must be taken to control the process when the polymerization reaction is very exothermic and particularly when it is run on a large scale. Poly(methyl methacrylate), polystyrene, or low-density (high pressure) polyethylene, for example, can be produced from 

Another example of bulk (or melt) polymerization is the synthesis of polyamides through the direct interaction between a dicarboxylic acid and a diamine. Nylon 66, for example, can be produced from the reaction between hexamethylenediamine and adipic acid. In practice, it is preferable to ensure the existence of a 1 1 ratio of the two reactants by prior isolation of a 1 1 salt of the two. The overall procedure is summarized by the reaction scheme  

The major commercial uses of bulk vinyl polymerization are in casting formulations and low-molecular-weight polymers for use as adhesives, plasticizers, and lubricant adhesives. 

Solution polymerization. Solution polymerization involves polymerization of a monomer in a solvent in which both the monomer (reactant) and polymer (product) are soluble. Monomers are polymerized in a solution that can be homogeneous or heterogeneous. Many free radical polymerizations are conducted in solution. Ionic polymerizations are almost exclusively solution processes along with many Ziegler-Natta polymerizations. Important water-soluble polymers that can be prepared in aqueous solution include poly(acrylic acid), polyacrylamide, poly(vinyl alcohol), and poly(iV-vinylpyrrolidinone). Poly(methyl methacrylate), polystyrene, polybutadiene, poly(vinyl chloride), and poly(vinylidene fluoride) can be polymerized in organic solvents. 

The most common method to polymerize (meth)acrylate monomers is free radical polymerization. The mechanism of free radical 

PIB may be manufactured in at least two different major grades, namely (14), 

These two product grades have been made by different processes, but both often and commonly use a diluted isobutylene feedstock in which the isobutylene concentration varies from 40-60%. 

However, at least the high vinylidene PIB type may be produced using a concentrated feedstock with an isobutylene content of 90%. Non-reactive hydrocarbons, such as isobutane, n-butane or other lower alkanes commonly present in petroleum fractions, may also be included in the feedstock as diluents. Further, the feedstock 

Since the formation of the terminal double bonds is kinetically favored, short reactions times favor high amounts of vinylidene moieties. 

At a desired conversion, the reaction is quenched, usually with an aqueous base solution, such as, for example, NH4OH, before a significant isomerization into internal double bonds can take place. The molecular weights of high vinylidene PIB are comparatively low, i.e., in the range of 1 k Dalton (14). 

Conjugated polymers demonstrate reasonable electrical conductivity which can be used in antistatic coatings, electronic devices, batteries, electromagnetic interference (EMI) shielding, electrochromic devices, optical switching devices, sensors, and textiles.  

Conjugated polymers, such as polypyrrole, pol3d hiophene, polyaniline (PANl) and its derivatives, are the most promising class of organic-semiconducting materials due to their better electrochemical behavior, electrochromism, ease of doping, and synthesis. But, on the other hand the low processability due to its low solubility is a problem. 

Aniline was the first example of the conjugated polymers doped by proton, it can be chemically oxidized by ammonium peroxydisulfate (APS). PANI has the advantages of easy synthesis, low-cost, proton doping mechanism, and is controlled by both oxidation and protonation state. Polyanilines are commonly prepared by the chemical or electrochemical oxidative potymerization of the respective monomers in acidic solution. But, other potymerization techniques have also been developed, including  

Comparison to other film preparation methods, the solution preparation for the electrospinning method through chemical pol5mierization seems to be more convenient and efficient method. 

The synthesis of poly(3,4-ethylenedioxythiophene (PEDOT) derivatives can be classified into three different types of polymerization reactions  

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Several polymerization techniques are in widespread usage. Our discussion is biased in favor of methods that reveal additional aspects of addition polymerization and not on the relative importance of the methods in industrial practice. We shall discuss four polymerization techniques bulk, solution, suspension, and emulsion polymerization. 

The fourth and most interesting of the polymerization techniques we shall consider is called emulsion polymerization. It is important to distinguish between suspension and emulsion polymerization, since there is a superficial resemblance between the two and their terminology has potential for confusion A suspension of oil drops in water is called an emulsion. Water-insoluble monomers are used in the emulsion process also, and the polymerization is carried out in the presence of water however, the following significant differences also exist ... 

The discovery of PTFE (1) in 1938 opened the commercial field of perfluoropolymers. Initial production of PTFE was directed toward the World War II effort, and commercial production was delayed by Du Pont until 1947. Commercial PTFE is manufactured by two different polymerization techniques that result in two different types of chemically identical polymer. Suspension polymerization produces a granular resin, and emulsion polymerization produces the coagulated dispersion that is often referred to as a fine powder or PTFE dispersion. 

Hydrocarbon resins based on CPD are used heavily in the adhesive and road marking industries derivatives of these resins are used in the production of printing inks. These resins may be produced catalyticaHy using typical carbocationic polymerization techniques, but the large majority of these resins are synthesized under thermal polymerization conditions. The rate constants for the Diels-Alder based dimerization of CPD to DCPD are weU known (49). The abiHty to polymerize without Lewis acid catalysis reduces the amount of aluminous water or other catalyst effluents/emissions that must be addressed from an environmental standpoint. Both thermal and catalyticaHy polymerized DCPD/CPD-based resins contain a high degree of unsaturation. Therefore, many of these resins are hydrogenated for certain appHcations. 

Different types of PVC exist on the market. The two principle types are suspension and paste-forrning PVC the latter includes the majority of emulsion PVC polymers. The plasticizer appHcations technologies associated with these two forms are distinctly different and are discussed separately. Details of the polymerization techniques giving rise to these two distinct polymer types can be found in many review articles (5,28) (see ViNYLPOLYMERS, (VINYL Cm ORIDE POLYPffiRS)). 

The chemistry of polymerization of the oxetanes is much the same as for THE polymerization. The ring-opening polymerization of oxetanes is primarily accompHshed by cationic polymerization methods (283,313—318), but because of the added ring strain, other polymerization techniques, eg, iasertion polymerization (319), anionic polymerization (320), and free-radical ring-opening polymerization (321), have been successful with certain special oxetanes. 

VEs do not readily enter into copolymerization by simple cationic polymerization techniques instead, they can be mixed randomly or in blocks with the aid of living polymerization methods. This is on account of the differences in reactivity, resulting in significant rate differentials. Consequendy, reactivity ratios must be taken into account if random copolymers, instead of mixtures of homopolymers, are to be obtained by standard cationic polymeriza tion (50,51). Table 5 illustrates this situation for butyl vinyl ether (BVE) copolymerized with other VEs. The rate constants of polymerization (kp) can differ by one or two orders of magnitude, resulting in homopolymerization of each monomer or incorporation of the faster monomer, followed by the slower (assuming no chain transfer). 

The preparation and characterization of 1,3-butadiene monomer is discussed extensively elsewhere (1 4) (see Butadiene). Butadiene monomer can be purified by a variety of techniques. The technique used depends on the source of the butadiene and on the polymerization technique to be employed. Emulsion polymerization, which is used to make amorphous /n j -l,4-polybutadiene (75% trans-1 4 , 5% kj -l,4 20% 1,2), is unaffected by impurities during polymerization. However, both anionic and Ziegler polymerizations, which are used to prepare kj -l,4-polybutadiene, mixed cis-1 4 and... 

Standard Suspension Polymerization Techniques, Appendix (1980). In Polymer-Supported Reaction in Organic Synthesis (P. Hodge and D. C. Sherington eds.), Wiley Chichester. 

Much effort has been devoted to the development of a multi-step swelling polymerization technique using water as suspension medium [98]. This has resulted in polymers showing similar selectivities but slightly improved mass transfer characteristics compared with the corresponding monolithic polymers. Of particular rele-... 

GTP is a safe operation. A runaway polymerization can be quickly quenched with a protonic solvent. Since the group transfer polymerization goes to completion, no unwanted toxic monomer remains the silicone group on the living end after hydroxylation is removed as inactive siloxane. The living polymer in GTP is costlier than traditional polymerization techniques because of the stringent reaction conditions and requirements for pure and dry monomers and solvents. It can be used in fabrication of silicon chips, coating of optical fibers, etc. 

Polymerization of acrylamide is usually performed in aqueous solutions. The principal factors that determine popularity of this polymerization technique are a high rate of polymer formation and the possibility to obtain a polymer with a large molecular weight. The reason for a specific effect produced by water upon acrylamide polymerization lies in protonation of the macroradical, leading to localization of an unpaired electron, which leads to an increase in the reactivity of the macroradical ... 

A new process, from Norway, has filled the size gap between emulsion and suspension polymerization techniques [7,8]. This novel polymerization method, the so-called swollen emulsion polymerization has been developed by Ugelstad for producing uniform polymeric particles in the size range of 2-100 /nm. This process comprises successive swelling steps and repolymerizations for increasing the particle size of seed polymer particles by keeping the monodispersity of the seed latex. 

In this chapter, the polymerization methods used for the production of uniform latex particles in the size range of O.I-lOO /Ltm are described. Emulsion, swollen emulsion, and dispersion polymerization techniques and their modified forms for producing plain, functionalized, or porous uniform latex particles are reviewed. The general mechanisms and the kinetics of the polymerization methods, the developed synthesis procedures, the effect of process variables, and the product properties are discussed. 

Monomer-soluble initiators are used in this polymerization technique. The monomer phase containing an initiator is dissolved in an inert solvent or solvent mixture including a steric stabilizer. The polymers or oligomer... 

Multistage emulsion polymerization techniques are usually applied for (1) the synthesis of large uniform latex particles, (2) the introduction of functional groups into the uniform latex particles, or (3) the synthesis of macroporous uniform latex particles. 

Multistage emulsion polymerization has been proposed by Ugelstad et al. [108,109] for the synthesis of large uniform latex particles. In general, the multistage emulsion polymerization techniques include two main... 

When the polymer was prepared by the suspension polymerization technique, the product was crosslinked beads of unusually uniform size (see Fig. 16 for SEM picture of the beads) with hydrophobic surface characteristics. This shows that cardanyl acrylate/methacry-late can be used as comonomers-cum-cross-linking agents in vinyl polymerizations. This further gives rise to more opportunities to prepare polymer supports for synthesis particularly for experiments in solid-state peptide synthesis. Polymer supports based on activated acrylates have recently been reported to be useful in supported organic reactions, metal ion separation, etc. [198,199]. Copolymers are expected to give better performance and, hence, coplymers of CA and CM A with methyl methacrylate (MMA), styrene (St), and acrylonitrile (AN) were prepared and characterized [196,197]. 

As previously described, all microspheres discussed in this chapter were synthesized from AB type diblock copolymers. Precursor block copolymers, poly(styrene-b-4-vinyl pyridine) (P[S-b-4VP]) diblock copolymers, were synthesized using the additional anionic polymerization technique [13]. The basic properties of the block copolymers were determined elsewhere [24,25] and are listed... 

As these block copolymers were synthesized using the anionic polymerization technique, their molecular weight distributions were narrow. The microspheres with narrower size distribution are better for well-ordered self-organization. Actually, all block copolymers synthesized for these works formed poly(4-vinyl pyridine) (P4VP) spheres in the PS matrices with narrow size distributions. 

The poly(styrene-b-isoprene) (P(S-b-IP)) and poly(-styrene-b-2-vinyl pyridine) (P(S-b-2VP)) block copolymers with narrow molecular weight distributions for blending with the microspheres were also synthesized using the additional anionic polymerization technique. The number-average molecular weights (Mns) and PS contents are also shown in Table 1. 

The structure-property relationship of graft copolymers based on an elastomeric backbone poly(ethyl acry-late)-g-polystyrene was studied by Peiffer and Rabeony [321. The copolymer was prepared by the free radical polymerization technique and, it was found that the improvement in properties depends upon factors such as the number of grafts/chain, graft molecular weight, etc. It was shown that mutually grafted copolymers produce a variety of compatibilized ternary component blends. 

The creation of active sites as well as the graft polymerization of monomers may be carried out by using radiation procedures or free-radical initiators. This review is not devoted to the consideration of polymerization mechanisms on the surfaces of porous solids. Such information is presented in a number of excellent reviews [66-68]. However, it is necessary to focus attention on those peculiarities of polymerization that result in the formation of chromatographic sorbents. In spite of numerous publications devoted to problems of composite materials produced by means of polymerization techniques, articles concerning chromatographic sorbents are scarce. As mentioned above, there are two principle processes of sorbent preparation by graft polymerization radiation-induced polymerization or polymerization by radical initiators. We will also pay attention to advantages and deficiencies of the methods. 

The above results prove the potential of the graft polymerization technique for the preparation of composite sorbents. The next section will be devoted to the application of such materials in the chromatography of biopolymers. 

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