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Chemistry

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes

Published: February 27th, 2017

DOI:

10.3791/54552

1Department of Chemistry, Université de Sherbrooke

We describe the catalytic insertion polymerization of 5-norbornene-2-carboxylic acid and 5-vinyl-2-norbornene to form functional polymers with a very high glass transition temperature.

Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic nature of the monomer is conserved. The resulting polymer, polynorbornene, has a very high glass transition temperature, Tg, and interesting optical and electrical properties. However, the polymerization of functional norbornenes by this mechanism is complicated by the fact that the endo substituted norbornene monomer has, in general, a very low reactivity. Furthermore, the separation of the endo substituted monomer from the exo monomer is a tedious task. Here, we present a simple protocol for the polymerization of substituted norbornenes (endo:exo ca. 80:20) bearing either a carboxylic acid or a pendant double bond. The process does not require that both isomers be separated, and proceeds with low catalyst loadings (0.01 to 0.02 mol%). The polymer bearing pendant double bonds can be further transformed in high yield, to afford a polymer bearing pendant epoxy groups. These simple procedures can be applied to prepare polynorbornenes with a variety of functional groups, such as esters, alcohols, imides, double bonds, carboxylic acids, bromo-alkyls, aldehydes and anhydrides.

Norbornene, NBE, the Diels-Alder adduct of ethylene and cyclopentadiene (obtained by "cracking" of dicyclopentadiene (DCPD)), is readily polymerized using either free-radical polymerization,1 cationic polymerization,2 ring-opening metathesis polymerization3 and catalytic insertion polymerization.4,5,6,7 Unlike the other mechanisms, the catalytic insertion polymerization leads to the formation of a very high glass-transition temperature (Tg) polymer whe....

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1. Preparation of Poly(5-norbornene-2-carboxylic acid), PNBE(CO2H)

  1. Preparation of the monomer NBE(CO2H)
    1. Weigh out acrylic acid (AA) (327 g, 4.5 mol, 2 eq.) and hydroquinone (4.9 g, 4.5 x 10-2 mol, 0.02 eq.) and add them to a 2 L round-bottom flask equipped with a condenser and a magnetic stir bar. Heat the flask at 150 °C using a silicone oil bath.
    2. Once reflux is settled, add DCPD (300 g, 2.3 mol, 1 eq.) in a single portion, and the.......

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The NBE monomers are prepared by simple Diels-Alder reaction of DCPD and a suitable dienophile, for example acrylic acid (AA). Normally, DCPD is cracked to yield cyclopentadiene (CPD) before reaction.17 Freshly cracked CPD is then engaged in the Diels-Alder reaction. However, in this protocol, both cracking and Diels-Alder steps are performed concomitantly, in a one-pot reaction. Thus, as soon as CPD is formed, it reacts with AA to yield 5-norbornene-2-carboxylic a.......

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The method proposed here is simple, and readily amenable to scale-up. All chemicals could be used as received without any purification. Note that performing the reaction at a lower scale (e.g. scales ≤1 g) usually yields lower yields due to an unavoidable loss of material during the handling and the collection.

The catalysts are formed in situ upon the reaction of commercial Pd compounds with cationizing agents. In our hands, the yield of the reaction as well as the cha.......

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The authors acknowledge funding from Fonds de Recherche du Québec - Nature et Technologies, from Conseil Recherches en Sciences Naturelles et Génie (program INNOV) and PrimaQuébec.

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Name Company Catalog Number Comments
acrylic acid Sigma-Aldrich 147230
hydroquinone Sigma-Aldrich H9003
dicyclopendadiene Sigma-Aldrich 454338
palladium allyl dichloride dimer Sigma-Aldrich 222380
silver hexfluoro antimonate Sigma-Aldrich 227730
liquid nitrogen Local Facility NA
ethyl acetate Fischer Scientific E14520
5-vinyl-2-norbornene Sigma-Aldrich 148679
toluene Fischer Scientific T290-4
palladium dba Sigma-Aldrich 227994
triphenyl phosphine Sigma-Aldrich 93090
silica gel 40-63 microns Silicycle Siliaflash
methanol Fischer Scientific BPA412-20
dichloromethane EMD Millipore DX08311
formic acid Sigma-Aldrich F0507
acetic acid Sigma-Aldrich 320099
hydrogen peroxide solution Sigma-Aldrich 216763
acetone Fischer Scientific A18-200

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