Synthesis and utility of ethylene (meth)acrylate copolymers prepared by a tandem ring‐opening polymerization hydrogenation strategy

Abstract

One new and one established functional cyclooctene were prepared and (co)polymerized using ring-opening metathesis polymerization. The resulting polymers were hydrogenated to yield the corresponding functional polyolefins that were structurally equivalent to copolymers of ethylene and either methyl methacrylate, t-butyl acrylate, or acrylic acid after deprotection. The copolymers that incorporate methyl methacrylate into the backbone were used as compatibilizers for poly(methyl methacrylate)/polyethylene blends. The copolymers that incorporate t-butyl acrylate into the backbone yielded elastomers that could be thermally crosslinked. V C 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3117-3126 KEYWORDS: compatibilization; copolymer; methyl methacrylate; ROMP; thermoset polyolefins INTRODUCTION The ring-opening metathesis polymerization (ROMP) of functionalized cyclooctenes (COEs) followed by hydrogenation of the olefinic groups in the polymer backbone is a powerful method for the preparation of functionalized polyolefins. Many 3-substituted COEs provide regiospecific polymers 1 while 4-and 5-substituted COEs typically give regioirregular polymers. The broad utility of this approach to materials useful for a wide variety of interesting applications has been clearly demonstrated in the literature. [2][3][4] The success of these approaches can be in large part attributed to the robust nature of ruthenium-based metathesis catalysts developed by Robert H. Grubbs and coworkers. [5][6][7] Indeed, these catalysts have been referred to by some as empyrean. 8

Investigation of Micromechanical Behavior and Voiding of Polyethylene Terephthalate/Polyethylene-stat-methyl Acrylate Blends during Tensile Deformation

“…The olefinic protons of the monomer between 5.7 and 5.6 ppm are shifted upfield and merged into a broader peak with a shoulder at 5.3 ppm, indicating that the ring was opened and both E and Z double bonds were present in the polymer backbone. 25 ROMP of the 5-substituted cyclooctene monomers gave regio-and stereoirregular polymers consistent with the literature. 27,28 Unsaturated polymers were then hydrogenated using diimide generated in situ by the thermolysis of p-toluenesulfonylhydrazide.…”

“…The methyl ( Z )-cyclooct-4-ene-1-carboxylate (MEC) monomer was prepared by Pd-catalyzed carboxymethylation of 1,5-cyclooctadiene (1,5-COD) following previously reported procedures. , The homopolymerization of MEC was performed in anhydrous chloroform using 0.02 mol % G2 at 50 °C (Scheme ). cis -4-Octene was used as a chain transfer agent (CTA) to control the M n of the resulting polymers.…”

“…The chain transfer agent (CTA) cis -4-octene was purchased from GFS chemicals and purified by vacuum distillation over CaH 2 . The methyl ( Z )-cyclooct-4-ene-1-carboxylate (MEC) monomer was synthesized according to literature procedures. , …”

“…The methyl (Z)cyclooct-4-ene-1-carboxylate (MEC) monomer was synthesized according to literature procedures. 24,25 1 H nuclear magnetic resonance (NMR) spectra were recorded on Bruker AX-400 and Bruker HD-500 spectrometers using residual solvent peaks as internal standards; CDCl 3 and toluene-d 8 were used as the solvents. Number-average molar mass (M n ) values for the polymers were determined on a Hewlett-Packard 1100 series liquid chromatograph fitted with a Hewlett-Packard 1047A refractive index detector and three PLgel columns (Polymer Laboratories columns with 500, 10 3 , and 10 4 Å pore sizes) calibrated using polystyrene standards with chloroform as the eluent at a flow rate of 1 mL/min at 35 °C.…”