The mutual diffusion coefficient for (meth)acrylate monomers as determined with a nuclear microprobe

摘要

The value of the mutual diffusion coefficient D~V of two acrylic monomers is determined with nuclear microprobe measurements on a set of polymer films. These films have been prepared by allowing the monomers to diffuse into each other for a certain time and subsequently applying fast ultraviolet photo-polymerization, which freezes the concentration profile. The monomer diffusion profiles are studied with a scanning 2.1 MeV proton microprobe. Each monomer contains a marker element, e.g., Cl and Si, which are easily detected with proton induced x-ray emission. From the diffusion profiles, it is possible to determine the mutual diffusion coefficient. The mutual diffusion coefficient is dependent of concentration, which is concluded from the asymmetry in the Cl- and Si-profiles. A linear dependence of the mutual diffusion coefficient on the composition is used as a first order approximation. The best fits are obtained for a value of b = (0.38±0.15), which is the ratio of the diffusion coefficient of l,3-bis(3-methacryloxypropyl)-l,1,3,3-tetramethyldisiloxane in pure 2-chloroethyl acrylate and the diffusion coefficient of 2-chloroethyl acrylate in pure l,3-bis(3-methacryloxypropyl)-l,l,3,3-tetramethyldisiloxane. Under the assumption of a linear dependence of the mutual diffusion coefficient D~V on monomer composition, it follows that D~V = (2.9±0.6) o 10~(-10) m~2/s at a 1:1 monomer ratio. With Flory-Huggins expressions for the monomer chemical potentials, one can derive approximate values for the individual monomer diffusion coefficients.