Vinyl homopolymerization

FIGURE 7.1 Schematic of a lab-scale 200 mm diameter iCVD reactor system. For a vinyl homopolymerization, a constant flow of monomer and initiator is metered into the pancake -style vacuum reaction chamber. An array of resistively heated wires, suspended a few centimeters above the substrate, heats the vapors. Laser interferometery provides real-time monitoring of the iC VD polymer thickness. The pressure of the chamber is controlled by a throttling value. Unreacted species and volatile reaction by-products are exhausted to a mechanical pump. For copolymerization, an additional monomer feed line would need to be added to the system (top image). Schematic cross-section of the iCVD reactor showing decomposition of the initiator by the heated filaments. Surface modification through polymerization of the monomer occurs on the actively cooled substrate (bottom image). 

Arcus [8] discussed the conditions of the optical activity of polymers in alternate copolymerizations and underlined that an asymmetry was brought into main chains in the polymerization between vinyl monomers and a,j3-substituted monomers. Accordingly, the main chains of the polymers obtained by vinyl homopolymerizations do not have optical activities since they are pseudo-asymmetric. 

Polyfunctional iniferters have also been employed to prepare branched, network and star polymers (8-10, Chart 3.3). For example, Ishizu et showed that functionalized iniferters ((A, A -diethyldithiocarbamyl) methyl styrene or 2-(A, A -diethyldithiocarbamyl)ethyl methacrylate) can be utilized for the synthesis of hyperbranched polymers (UV irradiation), star polymers (copolymerization of vinyl head with crosslinking agent in dark condition), and rigid polymer brushes (vinyl homopolymerization of macroiniferters and subsequent treatment by internal domain locking with diamine compounds). 

Note that this inquiry into copolymer propagation rates also increases our understanding of the differences in free-radical homopolymerization rates. It will be recalled that in Sec. 6.1 a discussion of this aspect of homopolymerization was deferred until copolymerization was introduced. The trends under consideration enable us to make some sense out of the rate constants for propagation in free-radical homopolymerization as well. For example, in Table 6.4 we see that kp values at 60°C for vinyl acetate and styrene are 2300 and 165 liter mol sec respectively. The relative magnitude of these constants can be understod in terms of the sequence above. 

DiaUyl fumarate polymerizes much more rapidly than diaUyl maleate. Because of its moderate reactivity, DAM is favored as a cross-linking and branching agent with some vinyl-type monomers (1). Cyclization from homopolymerizations in different concentrations in benzene has been investigated (91). DiaUyl itaconate and several other polyfunctional aUyl—vinyl monomers are available. 

Vinyhdene chloride copolymerizes randomly with methyl acrylate and nearly so with other acrylates. Very severe composition drift occurs, however, in copolymerizations with vinyl chloride or methacrylates. Several methods have been developed to produce homogeneous copolymers regardless of the reactivity ratio (43). These methods are appHcable mainly to emulsion and suspension processes where adequate stirring can be maintained. Copolymerization rates of VDC with small amounts of a second monomer are normally lower than its rate of homopolymerization. The kinetics of the copolymerization of VDC and VC have been studied (45—48). 

Continuous polymerization systems offer the possibiUty of several advantages including better heat transfer and cooling capacity, reduction in downtime, more uniform products, and less raw material handling (59,60). In some continuous emulsion homopolymerization processes, materials are added continuously to a first ketde and partially polymerized, then passed into a second reactor where, with additional initiator, the reaction is concluded. Continuous emulsion copolymerizations of vinyl acetate with ethylene have been described (61—64). Recirculating loop reactors which have high heat-transfer rates have found use for the manufacture of latexes for paint appHcations (59). 

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). 

Homopolymerization of butadiene can proceed via 1,2- or 1,4-additions. The 1,4-addition produces the geometrically distinguishable trans or cis stmctures with internal double bonds on the polymer chains, 1,2-Addition, on the other hand, yields either atactic, isotactic, or syndiotactic polymer stmctures with pendent vinyl groups (Eig. 2). Commercial production of these polymers started in 1960 in the United States. Eirestone and Goodyear account for more than 60% of the current production capacity (see Elastomers, synthetic-polybutadiene). 

Homopolymerization of macroazoinimers and co-polymerization of macroinimers with a vinyl monomer yield crosslinked polyethyleneglycol or polyethyleneglycol-vinyl polymer-crosslinked block copolymer, respectively. The homopolymers and block copolymers having PEG units with molecular weights of 1000 and 1500 still showed crystallinity of the PEG units in the network structure [48] and the second heating thermograms of polymers having PEG-1000 and PEG-1500 units showed that the recrystallization rates were very fast (Fig. 3). 

Note that in case of VTES (I) there is a chemical interaction via the vinyl group between silane and the filler, which results in a sufficiently rigid bond between the matrix and filler. The agent (II) undergoes homopolymerization so that an elastic sublayer ( shell ) is formed around each filler particle, the tensile and impact strength of the composition increase as a result. 

Several radical copolymerizations of vinyl 2-furoate with well-known monomers (50 50) were also studied. Complete inhibition was obtained with vinyl acetate, very strong retardation with styrene, vinyl chloride and acrylonitrile methyl methacrylate homopolymerized without appreciable decrease in rate. It is evident that the degree of retardation that vinyl 2-furoate imposes upon the other monomer depends on the stability of the latter s free radical. With styrene and vinyl chloride the small amounts of fairly low molecular-weight products contained units from vinyl 2-furoate which had entered the chain both through the vinyl bond and through the ring (infrared band at 1640 cm-1). 

A more complicated behaviour was obtained with divinyl ether due to the formation of both cyclic structures and pendent vinyl groups in the chain. The failure of such olefins as styrene and isopropenylbenzene to give copolymers with 2-fural-dehyde, and in fact to homopolymerize in its presence, was blamed on the strength of the complex formed between the initiator and the aldehyde, believed too stable to initiate polymerization. 

Since Ce4+ salts are capable of causing the homopolymerization of vinyl monomers starting after a certain induction period, the grafting process is carried out during a time period shorter than the period of induction so as to synthesize graft PAN copolymers without any homopolymer being formed68). 

For less polar monomers, the most extensively studied homopolymerizations are vinyl esters (e.g. VAc), acrylate and methacrylate esters and S. Most of these studies have focused wholly on the polymerization kinetics and only a few have examined the mierostructures of the polymers formed. Most of the early rate data in this area should be treated with caution because of the difficulties associated in separating effects of solvent on p, k and initiation rate and efficiency. 

The most important example of an addition polymerization is the homopolymerization of a vinyl monomer. The general formula for a vinyl monomer is... 

Vinyl chloride is used exclusively for the preparation of plastics, by homopolymerization to poly(vinyl chloride) (PVC) and by copolymerization with other vinyl (-CH2=CH-) compounds. 

PVPA was prepared by the free-radical homopolymerization of vinyl-phosphonyl dichloride using azobisisobutyronitrile as initiator in a chlorinated solvent. The poly(vinylphosphonyl chloride) formed was then hydrolysed to PVPA (Ellis, 1989). No values are available for the apparent pA s of PVPA, but unpolymerized dibasic phosphonic acids have and values similar to those of orthophosphoric acid, i.e. 2 and 8 (Van Wazer, 1958). They are thus stronger acids than acrylic acid, which as a pK of 4-25, and it is to be expected that PVPA will be a stronger and more reactive acid than poly(acrylic acid). 

General. In this section, a mathematical dynamic model will be developed for emulsion homopolymerization processes. The model derivation will be general enough to easily apply to several Case I monomer systems (e.g. vinyl acetate, vinyl chloride), i.e. to emulsion systems characterized by significant radical desorption rates, and therefore an average number of radicals per particle much less than 1/2, and to a variety of different modes of reactor operation. 

Other Monomer Systems. Very slight modifications are required to make the model applicable to emulsion homopolymerization of vinyl chloride (VCM). An initial study on PVC reactors has been reported in (69) and some more recent results following will finely illustrate the case. 

Homopolymerization of ethyl 4-vinyl-a-cyano-p-phenylcinnamate with AIBN in benzene gave a soluble polymer of inherent viscosity 0.2 djf,/g. There was no evidence for involvement of the tetra-substituted double bond in the polymerization. Copolymerizations with styrene and methyl methacrylate were also successful. 

The resulting complexes can be effectively employed as single component catalysts to homopolymerize ethylene or copolymerize ethylene with acrylates [50, 51] and a variety of other polar monomers including vinyl ethers, [51,52] vinyl fluoride [53], iV-vinyl-2-pyrrolidinone, and AMsopropylacrylamide [54], In fact, the resulting catalysts are so robust that they can be used as single component catalysts in aqueous emulsion homo-polymerization of ethylene and copolymerization of ethylene with norbomenes and acylates [55]. 

Many vinyl monomers were reported to have been grafted onto fluoropolymers, such as (meth)acrylic acid and (meth)acrylates, acrylamide, acrylonitryl, styrene, 4-vinyl pyridine, N-vinyl pyrrolidone, and vinyl acetate. Many fluoropolymers have been used as supports, such as PTFE, copolymers of TFE with HFP, PFAVE, VDF and ethylene, PCTFE, PVDF, polyvinyl fluoride, copolymers ofVDF with HFP, vinyl fluoride and chlorotrifluoroethylene (CTFE). The source of irradiation has been primarily y-rays and electron beams. The grafting can be carried out under either direct irradiation or through the use of preliminary irradiated fluoropolymers. Ordinary radical inhibitors can be added to the reaction mixture to avoid homopolymerization of functional monomers. 

Ethene, copolymerization of, 76 111 Ethene homopolymerization, 76 102-103 l-Ethenyl-2-pyrrolidinone. See AT-Vinyl-2-pyrrolidinone... 

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