Atom transfer radical polymerization (ATRP) of dimethyl(1-ethoxycarbonyl)vinyl phosphate
(DECVP) was investigated in the presence of different catalyst systems and initiators. Polymers with
controlled molecular weight and relatively low polydispersity (PDI < 1.5) were obtained through ATRP
initiated with ethyl 2-bromoisobutyrate (EBriBu) in the presence of Cu(I)Cl/2,2‘-bipyridine (bpy). Faster
polymerization and higher monomer conversion were obtained in the polymerization using Cu(I)Cl/
N,N,N‘,N‘ ‘,N‘ ‘-pentamethyldiethylenetriamine (PMDETA) or Cu(I)Cl/1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) as the catalyst system. PDECVP dissolves in water below 70 °C, but its lower
critical solution temperature (LCST) depends on the polymer concentration. The conversion of PDECVP
to poly((1-ethoxycarbonyl)vinylphosphonic diacid) (PECVPD) was accomplished by reaction with bromotrimethylsilane followed by methanolysis. Block copolymers, PDECVP-b-poly(styrene) (PS), PDECVP-b-PS-b-PDECVP, and PDECVP-b-poly(methyl methacrylate) (PMMA), were synthesized by extending
from PS−Br, Br−PS−Br, and PMMA−Br macroinitiators. The controlled block copolymers were obtained,
PDECVP-b-PS with M
n = 40 500 g/mol and PDI = 1.4, PDECVP-b-PS-b-PDECVP with M
n = 41 500
g/mol and PDI = 1.23, and PDECVP-b-PMMA with M
n = 29 700 g/mol and PDI = 1.08. Initiation efficiency
exceeded 94% using PMMA−Br as the macroinitiator.