Monomers acrylic

Acryhc acid and esters are stabilized with minimum amounts of inhibitors consistent with stabihty and safety. The acryhc monomers must be stable and there should be no polymer formation for prolonged periods with normal storage and shipping (4,106). The monomethyl ether of hydroquinone (MEHQ) is frequentiy used as inhibitor and low inhibitor grades of the acrylate monomers are available for bulk handling. MEHQ at 10—15 ppm is generally... 

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). 

Hie common acrylic ester monomers are combustible liquids. Commercially, acrylic monomers are shipped with DOT red labels in bulk quantities, tank cars, or tank tmcks. Mild steel is the usual material of choice for the constmction of bulk storage facilities for acrylic monomers. Moisture must be excluded to avoid msting of the tanks and contamination of the monomers. Copper or copper alloys must not be allowed to contact acrylic monomers intended for use in polymerization because copper is an inhibitor (67). 

The toxicides of acrylic monomers range from moderate to slight. In general, they can be handled safely and without difficulty by trained personnel following estabhshed safety practices. Table 5 summarizes investigations of the toxicity of the common acrylic monomers in animals under acute toxicity conditions (67). 

In normal practice, good ventilation to reduce exposure to vapors, splash-proof goggles to avoid eye contact, and protective clothing to avoid skin contact are required for the safe handling of acrylic monomers. A more extensive discussion of these factors should be consulted before handling these monomers (67). 

Usually, free-radical initiators such as azo compounds or peroxides are used to initiate the polymerization of acrylic monomers. Photochemical (72—74) and radiation-initiated (75) polymerizations are also well known. At a constant temperature, the initial rate of the bulk or solution radical polymerization of acrylic monomers is first order with respect to monomer concentration and one-half order with respect to the initiator concentration. Rate data for polymerization of several common acrylic monomers initiated with 2,2 -azobisisobutyronittile (AIBN) [78-67-1] have been determined and are shown in Table 6. The table also includes heats of polymerization and volume percent shrinkage data. 

The free-radical polymerization of acrylic monomers follows a classical chain mechanism in which the chain-propagation step entails the head-to-tail growth of the polymeric free radical by attack on the double bond of the monomer. 

In general, acryUc ester monomers copolymerize readily with each other or with most other types of vinyl monomers by free-radical processes. The relative ease of copolymerization for 1 1 mixtures of acrylate monomers with other common monomers is presented in Table 7. Values above 25 indicate that good copolymerization is expected. Low values can often be offset by a suitable adjustment in the proportion of comonomers or in the method of their introduction into the polymerization reaction (86). 

Table 9. Functional Monomers for Copolymerization with Acrylic Monomers...

Synthetic emulsion polymers account for approximately 70% of the U.S. consumption of acrylate monomers. Major end uses for these latex polymers are coatings (32%), textiles (17%), adhesives (7%), paper (5%), and floor poHshes (3%). The U.S. producers of acryflc copolymer emulsions include Rohm and Haas, Reichhold, National Starch, Union Carbide, Air Products, Unocal, B. F. Goodrich, and H. B. Fuller. 

Analytical Methodsfor the Acrylic Monomers, CM-18, Rohm and Haas Co., Philadelphia, Pa. 

Group-Transfer Polymerization. Living polymerization of acrylic monomers has been carried out using ketene silyl acetals as initiators. This chemistry can be used to make random, block, or graft copolymers of polar monomers. The following scheme demonstrates the synthesis of a methyl methacrylate—lauryl methacrylate (MMA—LMA) AB block copolymer (38). LMA is CH2=C(CH2)COO(CH2) CH2. 

Acrylate esters can be polymerised in a variety of ways. Among these is ionic polymerisation, which although possible (6—9), has not found industrial apphcation, and practically all commercial acryUc elastomers are produced by free-radical polymerisation. Of the four methods available, ie, bulk, solution, suspension, and emulsion polymerisation, only aqueous suspension and emulsion polymerisation are used to produce the ACMs present in the market. Bulk polymerisation of acrylate monomers is hasardous because it does not allow efficient heat exchange, requited by the extremely exothermic reaction. 

To improve the performance of acryUc elastomers, side chains are required where the 5 value is higher than with alkyl groups. Thus the use of polar groups, for instance heteroatoms, is suggested. The general formula for these acrylate monomers may be portrayed as follows ... 

Overexposure to acryhc mbbers is not likely to cause significant acute toxic effects. ACM however may contain residual monomers, mainly acrylate monomers, vapors of which are known to cause eye and/or skin irritation. 

In dry air and in the presence of polymerisation inhibitors methyl and ethyl 2-cyanoacrylates have a storage life of many months. Whilst they may be polymerised by free-radical methods, anionic polymerisation is of greater significance. A very weak base, such as water, can bring about rapid polymerisation and in practice a trace of moisture on a substrate is enough to allow polymerisation to occur within a few seconds of closing the joint and excluding the air. (As with many acrylic monomers air can inhibit or severely retard polymerisation). 

The reluctance of acrylic monomers to polymerise in the presence of air has been made a virtue with the anaerobic acrylic adhesives. These are usually dimethacrylates such as tetramethylene glycol dimethacrylate. The monomers are supplied with a curing system comprising a peroxide and an amine as part of a one-part pack. When the adhesive is placed between mild steel surfaces air is excluded, which prevents air inhibition, and the iron present acts as a polymerisation promoter. The effectiveness as a promoter varies from one metal to another and it may be necessary to use a primer such as cobalt naphthenate. The anaerobic adhesives have been widely used for sealing nuts and bolts and for a variety of engineering purposes. Small tube containers are also available for domestic use. 

The ease with which acrylic monomers may polymerise with each other and with other monomers has led to a host of compositions, frequently of undisclosed nature, being offered for use as moulding materials, casting resins, coating resins, finishing agents and in other applications. 

Over the years many blends of polyurethanes with other polymers have been prepared. One recent example is the blending of polyurethane intermediates with methyl methacrylate monomer and some unsaturated polyester resin. With a suitable balance of catalysts and initiators, addition and rearrangement reactions occur simultaneously but independently to give interpenetrating polymer networks. The use of the acrylic monomer lowers cost and viscosity whilst blends with 20% (MMA + polyester) have a superior impact strength. 

Acrylic PSAs are obtained by polymerizing acrylate monomers having the following general structure ... 

The amount of polar monomer one would copolymerize with the alkyl acrylate monomer(s) very much depends on the type of polar monomer and the desired change in rheological properties one would like to achieve. Strong hydrogen bonding monomers, such as acrylic acid, methacrylic acid, acrylamide, or methacrylamide are typically used at levels of 12% or less of the total monomers. 

About 60-99 parts of one or more alkyl acrylate monomer. This can also include lower levels of one or more methacrylate monomer. 

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