Vinyl polymers, depolymerization

Observations on the polymerization of readily polymerizable vinyl monomers such as styrene, vinyl chloride, and butadiene date back approximately to the first recorded isolation of the monomer in each case. Simon 2 reported in 1839 the conversion of styrene to a gelatinous mass, and Berthelot applied the term polymerization to the process in 1866. Bouchardat polymerized isoprene to a rubberlike substance. Depolymerization of a vinyl polymer to its monomer (and other products as well) by heating at elevated temperatures was frequently noted. Lemoine thought that these transformations of styrene could be likened to a reversible dissociation, a commonly held view. While the terms polymerization and depolymerization were quite generally applied in this sense, the constitution of the polymers was almost completely unknown. 

N. Grassie, Depolymerization Reactions in Vinyl Polymers. Chem. Ind. (London), p. 622, June 27 (1953). 

Much effort has been devoted to deriving expressions for the kinetics of depolymerization of vinyl polymers. The mechanisms are based mainly on four steps initiation, depropagation, transfer, and termination. By using different approaches, many investigators (29,36,37) have arrived at similar expressions for the reaction rate in terms of sample weight, molecular weight, and rate constants for each step. 

Polyester composition can be determined by hydrolytic depolymerization followed by gas chromatography (28) to analyze for monomers, comonomers, oligomers, and other components including side-reaction products (ie, DEG, vinyl groups, aldehydes), plasticizers, and finishes. Mass spectroscopy and infrared spectroscopy can provide valuable composition information, including end group analysis (47,101,102). X-ray fluorescence is commonly used to determine metals content of polymers, from sources including catalysts, delusterants, or tracer materials added for fiber identification purposes (28,102,103). 

High molecular weight polymers or gums are made from cyclotrisdoxane monomer and base catalyst. In order to achieve a good peroxide-curable gum, vinyl groups are added at 0.1 to 0.6% by copolymerization with methylvinylcyclosiloxanes. Gum polymers have a degree of polymerization (DP) of about 5000 and are useful for manufacture of fluorosiUcone mbber. In order to achieve the gum state, the polymerization must be conducted in a kineticaHy controlled manner because of the rapid depolymerization rate of fluorosiUcone. The expected thermodynamic end point of such a process is the conversion of cyclotrisdoxane to polymer and then rapid reversion of the polymer to cyclotetrasdoxane [429-67 ]. Careful control of the monomer purity, reaction time, reaction temperature, and method for quenching the base catalyst are essential for rehable gum production. 

Cross-linked polystyrene can be directly brominated in carbon tetrachloride using bromine in the presence of Lewis acids (Experimental Procedure 6.2 [55-58]). Thal-lium(III) acetate is a particularly suitable catalyst for this reaction [59]. Harsher bro-mination conditions should be avoided, because these can lead to decomposition of the polymer. Considering that isopropylbenzene is dealkylated when treated with bromine to yield hexabromobenzene [60], the expected products of the extensive bromi-nation of cross-linked polystyrene would be soluble poly(vinyl bromide) and hexabromobenzene. In fact, if the bromination of cross-linked polystyrene is attempted using bromine in acetic acid, the polymer dissolves and apparently depolymerizes [61]. 

This idea becomes even more pointed when we look at polymerization. Polyvinyl chloride is the familiar plastic PVC and is made by reaction of large numbers of monomeric vinyl chloride molecules. There is, of course, an enormous decrease in entropy in this reaction and any polymerization will not occur above a certain temperature. Some polymers can be depolymerized at high temperatures and this can be the basis for recycling, low... 

There are very few examples of direct hydroxylation of olefins using hydrogen peroxide, since these methods are limited to polymer applications or derivatization of natural products. Vinyl monomers have been hydroxy-lated in an alcoholic medium using acidic hydrogen peroxide 111 normally the acid is methanesulfonic. Natural rubber has also been hydroxylated, and simultaneously depolymerized by employing a hydrogen peroxide/UV system.112 The product distribution can be altered by varying the irradiation time. 

While condensation polymers such as PET and polyamides can be broken down into their monomer nnits by thermal depolymerization processes, vinyl (addition) polymers snch as polyethylene and polypropylene are very difficnlt to decompose to monomers. This is becanse of random scission of the carbon-carbon bonds of the polymer chains during thermal degradation, which prodnces a broad prodnct range. 

Depolymerization reactions can also be avoided when attaching reactive groups to the polymer backbone, which increase the cross-linking density of the polymeric precursor at ambient temperature. In this regard, the attachment of vinyl groups HC=CH2 was studied in much detail (see below). According to Scheme 18.17, vinyl-substituted polysilazanes are best synthesized by ammonolysis of chlorovinylsilanes (H2C=CH)Si(R)Cl2 (R = H, CH3). 

Faced with the shortcomings of the polyphthaldehyde resist (presented helow in chemical amplification resists based on depolymerization), the search for chemically amplified DUV resists resulted in a quick switch to more stable materials based on poly(p-hydroxystyrene), a phenolic polymer that Willson et al. were studying as a potential replacement for novolac. They observed that poly(p-tert-butoxycarbonyloxystyrene) (PBOCST), which is poly(vinyl phenol) protected with tert-butoxycarbonyl groups (t-BOC), is far more stable than the unprotected p-hydroxystyrene and could be purified and polymerized under controlled conditions. The resulting protected polymer could be easily deprotected thermally by heating it to 200°C or to a much lower temperature (100°C) by treatment with acid generated from the exposure of onium salts, just as in the poly(phthaldehyde)... 

In headspace analysis, the plastic is placed in a vial (at a raised temperature) and the volatiles formed are stripped by a flow of carrier gas. The stripped volatiles are trapped in a suitable sorbent (e.g., using a solid-phase microextraction device) and subsequently thermally desorbed into a gas chromatograph. Process gas chromatographs are used in industrial analysis of volatiles in plastics. An example of this technique is the determination of residual vinyl chloride monomer in plastics in the range of 5-50 g per kg. With direct injection of a polymer solution, there is a danger of side-effects (a loss of reactive monomers due to polymerization in the injection port or an increase in its content due to depolymerization at a high injection temperature). 

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