Formation of poly(methyl methacrylate) with novel solubility characters in the photopolymerization with bis(cyclopentadienyl)titanium dichloride in a water–methanol mixture

✍ Scribed by Tsuneyuki Sato; Tatsuo Umenoki; Makiko Seno

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 186 KB
• Volume: 69
• Category: Article
• ISSN: 0021-8995
• DOI: 10.1002/(sici)1097-4628(19980718)69:3<525::aid-app12>3.0.co;2-s

✦ Synopsis

Methyl methacrylate (MMA) was observed to be easily polymerized in the photopolymerization with bis(cyclopentadienyl)titanium dichloride (Cp 2 TiCl 2 ) in a water-methanol mixture under irradiation of a 15-W fluorescent room lamp. The polymerization proceeded heterogeneously. The rate ( R p ) of heterogeneous photopolymerization in a 1 : 1 (v/v) water-methanol mixture at 40ЊC was apparently given by R p Å k[Cp 2 TiCl 2 ] 0.2 [MMA] 2.4 . The resulting poly(MMA) was found to contain a tetrahydrofuran (THF)-insoluble part. The separated THF-insoluble part differed significantly from the usual radical poly(MMA) in solubility characters. It is of great interest that the THF-insoluble poly(MMA) was soluble in benzene and toluene, but insoluble in polar solvents, such as ethyl acetate, acetone, methyl ethyl ketone, dimethylformamide, and dimethylsulfoxide. The copolymerization results of MMA and acrylonitrile revealed that the present photopolymerization initiated with Cp 2 TiCl 2 proceeds via a radical mechanism.