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Continuous atom transfer radical block copolymerization of methacrylates
Author(s) -
Shen Youqing,
Zhu Shiping
Publication year - 2002
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.690481119
Subject(s) - methyl methacrylate , copolymer , polymer chemistry , monomer , atom transfer radical polymerization , polymerization , materials science , living polymerization , radical polymerization , methacrylate , chemistry , polymer , organic chemistry
A column reactor packed with silica‐gel‐supported copper bromide (CuBr)–hexamethyltriethylenetetramine (HMTETA) was developed for the continuous‐transition–metal‐mediated living/controlled radical polymerization [atom transfer radical polymerization (ATRP)] for homo‐ and block copolymerization of methyl methacrylate (MMA). The reactor showed good stability (>100 h) in both catalyst activity and molecular weight of the poly(methyl methacrylate) (PMMA) produced. The MMA conversion decreased as the flow rate increased. The polymerization in the reactor was in first order with respect to monomer concentration. The molecular weight of the resulting PMMA increased linearly with MMA conversion, exhibiting the characteristic feature of living polymerization. Thus, simply changing the flow rate of MMA, which in turn determined the MMA conversion, readily controlled the molecular weight of PMMA. The block copolymerization of MMA with n‐butyl methacrylate (nBMA) was carried out using two reactors connected in series. The block copolymers were slightly contaminated by PMMA prepolymer from the first column. The molecular weight of the nBMA block could be changed by the flow rate of the nBMA in the second reactor. This packed column reactor technology is feasible for continuously synthesizing polymers or block copolymers with controlled molecular weights that are readily adjustable by changing the monomer flow rates.