ABSTRACT
Acrylic materials have been studied for over 160 years and constitute (meth)acrylic acid and their ester derivatives, (meth)acrylates (see Figure 5.1). Today’s acrylics industry can be divided in two distinct multibillion-dollar markets: on one hand, the polyacrylic acid (PAA) and its ester derivative polyacrylate (PAc) market and, on the other hand, the poly(methyl methacrylate) (PMMA) market. For many decades, PMMA was the predominant (meth)acrylic ester produced worldwide. A recent US market report predicts that the global PMMA market is expected to be worth US$9.7 billion by 2017, growing at a compound annual growth rate (CAGR) of 6.5% from 2012 till 2017.1 However, due to growing demand for superabsorbent polymers and water treatment polymers in emerging countries, the acrylic acid (AA) market is even expected to grow to US$14 billion by 2018,2 thereby overtaking the PMMA market. The superabsorbent polymer market (PAA) is expected to grow at a
5.1 Introduction .......................................................................................................................... 169 5.1.1 Acrylics Industries .................................................................................................... 169 5.1.2 Historical Milestones ................................................................................................ 170
5.2 Chemistry ............................................................................................................................. 170 5.2.1 Monomers ................................................................................................................. 170
5.2.1.1 Synthesis .................................................................................................... 170 5.2.1.2 Storage ....................................................................................................... 172
5.2.2 Polymerizations ........................................................................................................ 173 5.2.2.1 Free-Radical Polymerization ..................................................................... 173 5.2.2.2 Living Polymerizations .............................................................................. 176 5.2.2.3 Stereospecific Polymerization .................................................................... 177
5.3 Properties of Polyacrylates ................................................................................................... 178 5.3.1 Thermal Degradation of Polymethacrylates ............................................................. 178 5.3.2 Flame Retardancy of Acrylics .................................................................................. 180 5.3.3 Optical Properties ..................................................................................................... 181
5.3.3.1 Scattering Studies ...................................................................................... 181 5.3.4 Mechanical Properties .............................................................................................. 182
5.4 Commercial Formulations and Processing ........................................................................... 182 5.4.1 PMMA and Other Polymethacrylates ...................................................................... 182
5.4.1.1 Types and Production of PMMA ............................................................... 182 5.4.1.2 Applications of PMMA.............................................................................. 184 5.4.1.3 PMMA Blends ........................................................................................... 185 5.4.1.4 Other Types of Polymethacrylates ............................................................. 187
5.4.2 PAA and Its Polyacrylate Esters ............................................................................... 187 References ...................................................................................................................................... 188
CAGR of 5.2% from 2013 till 2018, while the acrylate markets, especially 2-ethylhexyl esters, are expected to grow at a CAGR of 4.6% from 2013 till 2018. Major players in the (P)MMA market are Mitsubishi Rayon (Japan), Arkema SA (France), LG MMA (South Korea), Chi Mei Corp. (Taiwan), Sumimoto Chemical Company Ltd. (Japan), Evonik Industries (Germany), BASF (Germany), Dow Chemical Company (USA), AkzoNobel (Netherlands), Quinn Plastics (UK), and Cytec Industries (USA). Regarding the PAA and Pac market, key manufacturers are Nippon Shokubai Company Ltd. (Japan), Arkema SA, Evonik Industries, BASF, and Dow Chemical Company.
