Anionic living polymerization of macromonomers: Preparation of a particle-like purging reagent and characterization of poly(macromonomer)s

Abstract

A cross-linked polystyrene particle (Merrifield resin, R-C 6 H 5 ) was reacted with benzoyl chloride in nitrobenzene to produce R-C 6 H 4 -COC 6 H 5 having a benzophenone group, and the R-C 6 H 5 -COC 6 H 5 was reacted with a sodium mirror in THF under 10 K5 mmHg to produce R-C 6 H 5 -CO K C 6 H 5 Na C containing a benzophenone sodium as a particle-like purging reagent (PPBNa). (4-vinylbenzyl)Polystyrene macromonomers (PSM4: M n Z4.6 2 !10 3 , M w /M n Z1.0 3 and PSM7: M n Z7.1 0 !10 3 , M w /M n Z1.0 2 ) were dried under 10 K6 mmHg for more than 72 h, purified by a special procedure using the PPBNa, and then were living anionically polymerized by sec-BuLi in benzene or n-BuLi in tetrahydrofuran to produce the corresponding poly(PSM) n star polymers. The resultant star polymers were characterized by gel permeation chromatography equipped with low-angle laser light-scattering (GPC-LALLS), membrane osmometry (OSM), and light-scattering (LS). Anionic living polymerization of the PSM macromonomers was confirmed by the fact that the molecular weight of the poly(PSM) n increased and by the fact that the initiation efficiency was constant despite an increase in the polymer yields. Some solution properties and specific dimensions characteristic to the poly(PSM) n star polymers are discussed by comparing the GPC-LALLS, OSM, and LS results for those polymers with the results for linear polystyrenes. q

Reverse ATRP of acrylonitrile with diethyl 2,3-dicyano-2,3-diphenyl succinate/FeCl3/iminodiacetic acid

“…PAN is usually prepared by radical polymerization without control over molecular dimension and structure [2,3], while other methods exist for more controlled polymerization of acrylonitrile (AN), such as anionic polymerization, which often involves complex catalysis or side reactions with the nitrile groups [4][5][6]. Living/controlled free radical polymerization can be used as an alternative [7].…”

Selective complete decomposition of poly(n‐hexylisocyanate) and its use in a new molecular design method

“…The a-end-styryl-terminated PHIC macromonomer (St-PHIC-NH) was radically polymerized by AIBN in Bz to produce a polymacromonomer, (PHIC-NH) f , where f is the number of side chains. 31,32 As shown in Table 3, the M w LALLS value of the (PHIC-NH) 3.43 seems to be smaller than those of common polymacromonomers such as (PSt) f and (PHIC) f reported by other groups. The major reason for this difference is that although the common polymerizations were carried out in concentrated solutions, the present polymerization was carried out in nonconcentrated solution to prepare the sample with a molecular weight distribution as narrow as possible, even if the radical polymerization was carried out.…”

“…The α‐end‐styryl‐terminated PHIC macromonomer (St‐PHIC‐NH) was radically polymerized by AIBN in Bz to produce a polymacromonomer, (PHIC‐NH) f , where f is the number of side chains 31, 32. As shown in Table 3, the M w LALLS value of the (PHIC‐NH) 3.43 seems to be smaller than those of common polymacromonomers such as (PSt) f and (PHIC) f reported by other groups.…”

Thermal and Mechanical Analysis of Urethane Acrylate Graft Copolymer Part A: Urethane Macromonomer Base on TDI and EG

“…Macromonomers are usually linear polymeric species having one or more reactive end groups that can participate in polymerization reactions (Milkovich & Chiang, 1975). Such end groups include acrylic, vinylic, allylic, propenylic, or isopropenylic functionality (Henschke et al, 1997;Shiho & Desimone, 2000), so the macromonomers can either homopolymerize to give regular comb-shaped polymers or copolymerize with conventional monomers to give graft copolymers (Se et al, 2005).…”