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No abstract

It is well-known that short-chain branching (SCB) reactions (intramolecular H-abstraction) play an important role in determining the properties of ethylene homopolymers produced under high pressure by free-radical polymerization. There is little information, however, regarding SCB mechanisms that occur during the synthesis of ethylene copolymers under similar reaction conditions. This work describes SCB structures for a wide range of ethylene copolymers of varying composition (ethylene with n-butyl acrylate (nBA), methyl acrylate (MA), vinyl acetate (VAc), n-butyl methacrylate (nBMA), acrylic acid (AA), and methacrylic acid (MAA)), as determined by proton, 13 C, and 2D NMR techniques. Close examination of the resonances reveals that for many (if not all) of these copolymers, a significant fraction of the SCBs contain comonomer as a result of CH2-radical to CH2 backbiting around a comonomer unit. In addition, SCBs are formed not only by hydrogen abstraction from CH2 polyethylene units but also by abstraction of hydrogen from the comonomer methine units. This latter mechanism does not occur during production of E/VAc, E/nBMA, or E/MAA but is important for E/AA and acrylate (E/MA and E/nBA) copolymers; for these systems 10-20% of the comonomer groups in the polymer are alkylated. Implications of these findings to the polymerization kinetics are discussed.

Summary 1. We used a corer and a Downing box sampler to sample macroinvertebrates living on and beneath the introduced Trapa natans and the native Vallisneria americana in the freshwater tidal Hudson River, New York. 2. Densities of macroinvertebrates were higher in Trapa than in Vallisneria, and higher in the interior of plant beds than at their edges. These effects were largely a result of high plant biomass in Trapa beds and in bed interiors (the plants have similar surface area per unit mass). 3. The composition of both epiphytic and benthic macroinvertebrates differed distinctly between Trapa and Vallisneria, and also seasonally. 4. These compositional differences were not easily interpretable as rising from possible differences in oxygen concentrations, fish predation, or water circulation in the two macrophytes. 5. Sida crystallina (Cladocera) collected from Trapa contained more haemoglobin than those collected from Vallisneria. 6. The replacement of Vallisneria by Trapa in the Hudson probably increased system‐wide biodiversity and food for fish, although macroinvertebrates in Trapa beds may not be readily available to fish because of low oxygen concentration there.