Poly(methyl 2-methylpropenoate), often known as polymethyl methacrylate or PMMA, is one of the best known polymers, used widely under trade names such as Lucite, Perspex and Altuglas.
Uses of poly(methyl 2-methylpropenoate) (polymethyl methacrylate)
Poly(methyl 2-methylpropenoate) is better known as Lucite, Perspex and Altuglas (when in sheet form) and as Diakon (when in powder form).
The cast sheet is used in baths and other sanitary ware, which along with illuminated signs, is the largest use of the polymer. High molecular mass cast sheet (Perspex) is also used as a lightweight replacement for glass. Lower molecular mass products, made by suspension or solution polymerization (Diakon), are used in car lights and domestic lighting.
Special grades are used in diverse applications such as false teeth and eyes and as a major component of bone cements.
The monomer is used in adhesives, surface coatings and in paints.
Figure 1 Uses of poly(methyl-2-methylpropenoate).
Annual production of poly(methyl 2-methylpropenoate) (polymethyl methacrylate)
The monomer is the methyl ester of 2-methylpropenoic acid, methyl 2-methylpropenoate (methyl methacrylate):
Currently, most of the monomer is made by two processes
(i) From propanone (acetone)
Propanone and hydrogen cyanide form 2-hydroxy-2-methylpropanonitrile:
This product, on reaction with concentrated sulfuric acid at about 430 K, is dehydrated and the nitrile goup (CN) hydrolyzed to the amide. This is a step-wise process involving both dehydration and hydrolysis. The reactions can be summarised as:
The temperature is decreased to 370 K and methanol is added. The amide group is hydrolyzed and esterified. The reactions can be summarised as:
The product is continuously removed by steam distillation.
(ii) From ethene, carbon monoxide and methanol
Much work has been done to find alternative sources of the monomer and a promising route, which is now in use, uses a mixture of ethene, carbon monoxide and methanol in the liquid phase under pressure of about 10 atm at 350 K:
The resulting ester, methyl propionate, is reacted with methanal to form methyl 2-methylpropenoate. A fixed bed reactor is used and the reactor and catalyst (for example, caesium hydroxide on silica) are heated to 600 K:
Polymerization of methyl 2-methylpropenoate is achieved by a free radical process using an initiator, such as an azo compound or a peroxide:
The amount of initiator employed affects both polymerization rate and resulting molecular mass of the polymer.
The process is an example of addition polymerization.
Co-monomers are often used together with the methyl 2-methylpropenoate. For example, most commercial grades of poly(methyl 2-methylpropenoate) used in injection moulding or extrusion applications contain a small amount (ca. 4%) of co-monomer, such as methyl propenoate (methyl acrylate) (when casting sheets of the polymer) and ethyl propenoate (ethyl acrylate) (when extruding sheets of the polymer).
In these co-polymers, the monomers are randomly arranged. The resulting polymers have increased thermal stability compared to the homopolymer.
With butyl propenoate (butyl acrylate), a co-polymer is produced which is used as a base for emulsion paints.
It is also co-polymerized with ABS to produce a very tough polymer which is both rigid and has excellent clarity. It is used, for example, in medical applications and in cosmetic packaging.
Date last amended: 3rd October 2013