Mechanisms vinyl acetate polymerization

Another mechanism, conceivable with most monomers, and believed to occur in vinyl acetate polymerization (see Section 10), is transfer with the monomer forming a polymer with an unsaturated end-group capable of copolymerizing, e.g. ... 

Most commonly, in the emulsion polymerization of vinyl acetate, anionic surfactants are used either alone or in combination with a protective colloid. Typical examples of surfactants which have found application are Aerosol OT (sodium dioctylsulfosuccinate), alkyl aryl sulfonate salts (e.g., Santomerse-3), sodium lauiyl sulfate, etc. A study of the kinetics of the vinyl acetate polymerization in the presence of sodium lauryl sulfate indicated that the rate of polymerization was proportional to the square root of the initiator concentration and the 0.25th power of the number of particles. The number of particles were proportional to the 0.5th 0.05 power of the surfactant concentration but independent of the level of potassium persulfate. The intrinsic viscosity of the final polymer was said to be independent of the initiator concentration and of the munber of polymer particles. These observations were said to suggest that the mechanism of the vinyl acetate polymerization in emulsion resembles that of vinyl chloride [153]. 

Vinyl acetate polymerizes very easily by radical mechanism the technical method of polymerization is also a radical process. First, a typical radical polymerization scheme of the vinyl monomer takes place in the presence of an initiator, I, to yield a pair of free radicals R ... 

M. K. Lindemann, The mechanism of vinyl acetate polymerization, in Vinyl Polymerization, Vol. 

The transfer coefficients of disulfides are extremely low for styrene and methyl methacrylate (see Table 4), but are close to one for the vinyl acetate polymerization. In general the xanthogens and thiurams have higher chain transfer ability, which has been attributed to the iniferter mechanism described above. Monosulfides have lower transfer coefficients in comparison to disulfides. This may refiect steric factors and the relative strength of the C—S bond, which is significantly stronger than the S—S bond. 

More recently, the alternating copolymerization of vinyl acetate with carbon monoxide via a palladium catalyzed coordination insertion mechanism has been reported. This is the first report of a nonradical pathway for vinyl acetate polymerization. 

FRP leads to the formation of statistical copolymers, where the arrangement of monomers within the chains is dictated purely by kinetic factors. However, reactivity of a monomer in copolymerization cannot be predicted from its behavior in homopolymerization. Vinyl acetate polymerizes about 30 times more quickly than styrene (see Table 4.2), yet the product is almost pure polystyrene if the two monomers are copolymerized together in a 50 50 mixture. a-Methylstyrene cannot be ho-mopolymerized to form high-MW polymer due to its low ceiling temperature (see Table 4.6), yet is readily incorporated into copolymer at elevated temperatures. These and other similar observations can be understood by considering copolymerization mechanisms and kinetics. 

Vinyl acetate polymerizes by a free-radical mechanism. Free radicals generated by the decomposition of organic peroxides such as benzoyl or hydrogen peroxide or of inorganic per salts such as potassium or ammonium persulfate are commonly used to initiate polymerization. Reactions ordinarily are accomplished at temperatures above room temperature. Other techniques of polymerization have been used to make novel products low temperature redox polymerization, irradiation, and ionic catalysis. 

Backbiting is an intramolecular chain transfer reaction. If transfer reactions occur between different chains, long-chain branched polymers are formed. Well-known examples include ethylene and vinyl acetate. Vinyl acetate polymerization could lead to gel formation under certain conditions. It should be pointed out that chain transfer to polymer reaction alone generates only T-type branch structures that do not result in gel formation. Theoretically, some mechanism such as radical termination by combination that brings two chains together to form H-type branch structures is an essential condition for gelation. 

Polyalkyl ring-substituted phenols, such as 2,4,6-trimethyl-phenol act as more powerful retarders than phenol toward vinyl acetate polymerization. The mechanism for retardation may involve hydrogen abstraction followed by coupling of the phenoxy radical with other polymer radicals ... 

Many different combinations of surfactant and protective coUoid are used in emulsion polymerizations of vinyl acetate as stabilizers. The properties of the emulsion and the polymeric film depend to a large extent on the identity and quantity of the stabilizers. The choice of stabilizer affects the mean and distribution of particle size which affects the rheology and film formation. The stabilizer system also impacts the stabiUty of the emulsion to mechanical shear, temperature change, and compounding. Characteristics of the coalesced resin affected by the stabilizer include tack, smoothness, opacity, water resistance, and film strength (41,42). 

Mechanisms. Because of its considerable industrial importance as well as its intrinsic interest, emulsion polymerization of vinyl acetate in the presence of surfactants has been extensively studied (75—77). The Smith-Ewart theory, which describes emulsion polymerization of monomers such as styrene, does not apply to vinyl acetate. Reasons for this are the substantial water solubiUty of vinyl acetate monomer, and the different reactivities of the vinyl acetate and styrene radicals the chain transfer to monomer is much higher for vinyl acetate. The kinetics of the polymerization of vinyl acetate has been studied and mechanisms have been proposed (78—82). 

Emulsion Polymerization. Poly(vinyl acetate) and poly(vinyl acetate) copolymer latexes prepared in the presence of PVA find wide appHcations in adhesives, paints, textile finishes, and coatings. The emulsions show exceUent stabiHty to mechanical shear as weU as to the addition of electrolytes, and possess exceUent machining characteristics. 

For composites with polymerization-modified filler it is typical that the physico-mechanical characteristics should increase symbatically with the quantity of polymer which becomes attached to the filler in the polymerization process. This effect has been observed for polyethylene [293, 321], poly(vinyl chloride) coats [316], and in [336, 337] for kaolin coated with poly(vinyl acetate) and introduced into the copolymer of ethylene and vinyl acetate. 

In a very recent development, Debuigne et at. of vinyl acetate at 30 °C mediated by Co"(acac)2 (121). They obtained predictable molecular weights up to Mn 100000 and dispersities < 1.3 and proposed a polymerization mechanism analogous to that shown in Scheme 9.27. The complex... 

Some obscurities. Each of the reactions mentioned has been identified in at least one system, but there are very many obscurities to be cleared up. For example, transfer by methyl vinyl ether, phenyl vinyl ether, vinyl acetate and some of the corresponding polymers in the polymerization of styrene by stannic chloride has been studied, but the mechanism is not at all clear [124]. 

The work function of the rubbing surfaces and the electron affinity of additives are interconnected on the molecular level. This mechanism has been discussed in terms of tribopolymerization models as a general approach to boundary lubrication (Kajdas 1994, 2001). To evaluate the validity of the anion-radical mechanism, two metal systems were investigated, a hard steel ball on a softer steel plate and a hard ball on an aluminum plate. Both metal plates emit electrons under friction, but aluminum produced more exoelectrons than steel. With aluminum, the addition of 1% styrene to the hexadecane lubricating fluid reduced the wear volume of the plate by over 65%. This effect considerably predominates that of steel on steel. Friction initiates polymerization of styrene, and this polymer formation was proven. It was also found that lauryl methacrylate, diallyl phthalate, and vinyl acetate reduced wear in an aluminum pin-on-disc test by 60-80% (Kajdas 1994). 

The template polymerization of methacrylic acid at 60 C in DMF was studied with atactic poly(vinyl acetate) M =66,400 used as a template. The effect of template, monomer, and initiator (AIBN) concentration on the kinetics of polymerization was studied dilatometrically. Viscometric measurements showed that complexation between poly(vinyl acetate) and poly(methacrylic acid) was maximized when the template to polymer ratio was 1 1, and for the same ratio of the monomer to the template, the rate of template polymerization also reached the maximum. The overall energy of activation was the same (115 kJ/mol) in the presence and absence of the template. The polymerization follows mechanism II ( pick up mechanism ). 

If mechanical degradation of a polymer solution by high speed stirring is carried out with a vinyl monomer in an inert atmosphere the monomer will be polymerized by the free macroradical. Goto and Fujiwara, for example, studied poly(vinyl acetate vinyl acetate) agitated in an Homomixer at 30000 rpm in a nitrogen atmosphere at 65° C (99). They found that the polymerization rate, Vp, is proportional to the square root of the initial concentration of poly(vinyl acetate) ... 

As a result, the formation of long branches in the polymerization of vinyl acetate by the free-radical mechanism is better understood than in the polymerization of any other monomer, though there is even so still some disagreement about the transfer coefficient with the polymer, and also in estimates of the proportion of the total branching that takes place through acetate groups in either monomer or polymer. However, the state of knowledge is still less satisfactory for other monomers such as ethylene or vinyl chloride. 

It might be expected that short-chain branches would be formed in the polymerization of vinyl acetate by a cyclic mechanism like that proposed by Roedel (6) for ethylene polymerization, and this possibility has been mentioned by several authors. There appears to be no evidence that such short-chain branches occur if they are absent this is perhaps attributable to steric repulsion between the substituents that might prevent the formation of the cyclic transition state required for the back-biting reaction. 

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