Synthesis of Norbornene and Methyl Methacrylate Graft Copolymers with High Norbornene Content by Using Mixed Catalytic System

Abstract

A vinyl-type polymer of norbornene containing a few pendant styrene groups obtained by copolymerization of norbornene and 1,4-divinylbenzene (1,4-DVB) was used as a macroinitiator in the reverse atom transfer radical polymerization (RATRP) of methyl methacrylate in conjunction with CuCl 2 /2,2 -bipyridine/2,2 -azobisisobutyronitrile (AIBN) as a catalyst. In the first step of the reaction, the structural characterization of the copolymers showed that norbornene and 1,4-divinylbenzene copolymerizations occur as a coordination mechanism and that true copolymers are formed by random copolymerization. With the initiation of copper dichloride and AIBN in the second step, the pendant styrene groups in the copolymers were quantitatively polymerized with methyl methacrylates, which allowed the successful synthesis of polynorbornene-based graft copolymers by RATRP mechanism. The analyses of the product by 1 H-and 13 C-NMR and GPC gel permeation chromatography (GPC) gave the verification of 'true' copolymer. Varying the monomer feed ratio controlled the thermal property of the graft copolymer.

FI Catalysts for Olefin Polymerization—A Comprehensive Treatment

“…Furthermore, block copolymers, PE- b -poly(ethylene- co -DCPD), prepared by the complex 426 were also functionalized using similar methods . Bao and co-workers prepared poly(NBE- co -1,4-divinylbenzene) with complex 428 and tried to synthesize graft copolymers of MA and MMA via atom transfer radical polymerization using pendant −C 6 H 4 CHCH 2 groups as a hold of the grafting reaction. Coates and co-workers polymerized 1,5-hexadiene (HD) using complex 152 /MAO in a living manner, resulting in polymers that had 1,3-methylenecyclopentane (MCP) and 3-vinyltetramethylene (VTM) units in the main chains with narrow molecular weight distributions .…”

Synthesis of highly thermostable norbornene-isoprene-1-octene terpolymer with titanium catalyst

“…The obtained polymer had very low molecular weight and bimodal molecular weight distribution (350 mg yield, M n = 9,000, PDI = 3.1). The C NMR spectrum of the polymer showed strong broad signals of aliphatic carbons assignable to NB units and sharp signals at 135 and 124 ppm assignable to trans ‐1,4 sequence of polyisoprene. These results imply that the obtained polymer was a mixture of homopolymer (Figure S2 in Supporting Information).…”

“…Titanium complex 1 was synthesized according to the literature . 1 H and C NMR spectra of the polymers were measured by a JEOL‐LA500 spectrometer using 1,1,2,2‐tetrachoroethane‐ d 2 or chloroform‐ d as a solvent. The obtained spectra were calibrated by the peaks originated from the solvent [chloroform‐ d : 7.26 ppm ( 1 H); 77.16 ppm ( 13 C), 1,1,2,2‐tetrachoroethane‐ d 2 : 5.91 ppm ( 1 H)].…”

“…Such copolymers are called as cyclic olefin copolymers (COCs). The development of single‐site catalysts has realized the copolymerization not only with ethylene but also with α‐olefins, styrene, and olefins with functional groups …”