Polymerization hydroquinone

Chemical Reactivity - Reactivity with Water No reaction Reactivity with Common Materials No reaction Stability During Transport Stable when inhibited Neutralizing Agents for Acids and Caustics Not pertinent Polymerization Undergoes uncatalyzed polymerization reaction around 200°C. Light promotes polymerization Inhibitor of Polymerization Hydroquinone 0.10 to 0.25 %. 

An anti-oxygen such as catechol or hydroquinone is used to prevent polymerization. Hydroquinone should be added in the ratio of one part per thousand unless the phenylethylene is to be used immediately.1... 

If 4 < the overall rate will be decreased by chain transfer. This is degradative chain transfer. In fact, if is so small as to be negligible, chain transfer results in inhibition and the agent is a free-radical sink, or inhibitor. Almost all ethenic monomers are stored and shipped containing such a material to prevent adventitious polymerization. Hydroquinone and diphenylamine are compounds that at concentrations of 10-200 ppm are effective inhibitors. The radicals that result from these compounds are unreactive toward monomer. These inhibitors have many features in common with additives required for living radical polymerization, discussed later. 

Acrolein produced in the United States is stabilized against free-radical polymerization by 1000—2500 ppm of hydroquinone and is protected somewhat against base-catalyzed polymerization by about 100 ppm of acetic acid. To ensure stabiUty, the pH of a 10% v/v solution of acrolein in water should be below 6. 

Since the principal hazard of contamination of acrolein is base-catalyzed polymerization, a "buffer" solution to shortstop such a polymerization is often employed for emergency addition to a reacting tank. A typical composition of this solution is 78% acetic acid, 15% water, and 7% hydroquinone. The acetic acid is the primary active ingredient. Water is added to depress the freezing point and to increase the solubiUty of hydroquinone. Hydroquinone (HQ) prevents free-radical polymerization. Such polymerization is not expected to be a safety hazard, but there is no reason to exclude HQ from the formulation. Sodium acetate may be included as well to stop polymerization by very strong acids. There is, however, a temperature rise when it is added to acrolein due to catalysis of the acetic acid-acrolein addition reaction. 

The polymeric products can be made to vary widely in physical properties through controlled variation in the ratios of monomers employed in thek preparation, cross-linking, and control of molecular weight. They share common quaHties of high resistance to chemical and environmental attack, excellent clarity, and attractive strength properties (see Acrylic ester polymers). In addition to acryHc acid itself, methyl, ethyl, butyl, isobutyl, and 2-ethylhexyl acrylates are manufactured on a large scale and are available in better than 98—99% purity (4). They usually contain 10—200 ppm of hydroquinone monomethyl ether as polymerization inhibitor. 

In normal practice, inhibitors such as hydroquinone (HQ) [123-31 -9] or the monomethyl ether of hydroquinone (MEHQ) [150-76-5] are added to acrylic monomers to stabilize them during shipment and storage. Uninhibited acrylic monomers should be used prompdy or stored at 10°C or below for no longer than a few weeks. Improperly iahibited monomers have the potential for violent polymerizations. HQ and MEHQ require the presence of oxygen to be effective inhibitors therefore, these monomers should be stored in contact with air and not under inert atmosphere. Because of the low concentration of inhibitors present in most commercial grades of acrylic monomers (generally less than 100 ppm), removal before use is not normally required. However, procedures for removal of inhibitors are available (67). 

Acrylonitrile will polymerize violendy in the absence of oxygen if initiated by heat, light, pressure, peroxide, or strong acids and bases. It is unstable in the presence of bromine, ammonia, amines, and copper or copper alloys. Neat acrylonitrile is generally stabilized against polymerization with trace levels of hydroquinone monomethyl ether and water. 

Methyl Vinyl Ketone. Methyl vinyl ketone [78-94-4] (3-buten-2-one) is a colorless Hquid with a pungent odor. It is stable only below 0°C, and readily polymerizes on standing at room temperature. It can be inhibited for storage and transportation by a mixture of acetic or formic acid and hydroquinone or catechol (266). This ketone is completely soluble in water, and forms a binary azeotrope with water (85 MVK 15 H2O vol %) at 75.8°C. 

Sulfuric acid is also a very satisfactory catalyst aluminum alkoxides also are useful, especially when the alcohols would be adversely affected by strong acids. Sodium alkoxides produce undesirable side reactions and give lower yields. When alkaline catalysts are employed, an alkaline polymerization inhibitor, such as j j-phenylenediamine or phenyl-d-naphthylamine, should be used instead of hydroquinone. 

Polymerization inhibitors are key additives which prevent premature gelation of the adhesive. The foimulator must carefully balance shelf stability and the required cure on demand. Due to its high propagation rate, MMA is difficult to inhibit. Some comments on specific inhibitors follow. The most common inhibitor to be found in component monomers is 4-methoxyphenol, which is also called the methyl ether of hydroquinone. This inhibitor is effective only in the presence of oxygen. A mechanism has been proposed, and is illustrated in Scheme 13 [128]. 

Because they are acrylic monomers, alkyl cyanoacrylate esters still require the addition of radical polymerization inhibitors, such as hydroquinone or hindered phenols, to prevent radically induced polymerization over time [3j. Since basic initiation of alkyl cyanoacrylate monomers is the predominant polymerization mechanism, large quantities of free radical inhibitors can be added, with little or no effect on adhesive performance. 

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