Photoinitiierte Polymerisation mit Dialkoxythiocarbonyldisulfiden – eine Polymerisationsreaktion mit Primärradikalabbruch

Photoinitiated Polymerization with Dialkoxy Thiocarbonyl Disulfides – a Polymerization Reaction with Primary Radical Termination The photoinduced free radical polymerization of methyl methacrylate (MMA) and some other vinyl monomers using dialkoxy thiocarbonyl disulfides ( 1 – 4 ) as photoinitiators was studied. The photolysis of these initiators leads to cleavage of the S S bond, which was determined by spin trapping experiments with phenyl tert-butyl nitrone. No evidence was found for a further thermal decomposition of the primary alkoxy thiocarbonyl sulfide radicals (R·) at room temperature. In the absence of scavengers the primary radicals react back exclusively to the initial compounds, due to a strong cage effect. By means of UV spectroscopic measurements and in the presence of MMA the quantum yields of the initiator decomposition were detected to be 0.8. The polymerization of acrylic and methacrylic derivatives can be initiated by the R·, contrary to the situation with fumarates and maleates. The mechanism of MMA polymerization depends on the light intensity absorbed by the initiators. At high intensities the combination of primary and polymer radicals terminates the chain reaction. This follows from the measured monomer exponent of α = 2, the light intensity exponent of β = 0,2 and the number of thiocarbonyl end groups of 2 in the polymers isolated. Contrary to this, in the low intensity region the experimental data obey the ideal kinetic equation. Kinetic modelling gives evidence for an interaction of the monomer with the cage radicals.     

Influence of different wood flour fractions on the mechanical properties of injection molded WPC with cellulose propionate

This research investigated the effect of different fractions of commercial wood flour (Type c100 from JRS, Germany) on mechanical and physical properties of wood-polymer composites (WPC). The fractions were named regarding the mean lengths of their particles in µm; 80, 130, 255, 405 and 485. The composite samples were manufactured with 30 wt% of wood flour fractions of all five groups as well as the not fractionated flour, and 70 wt% of cellulose propionate (CP). The melt mass-flow rate (MFR) of the different granules, tensile strength, and modulus of elasticity, flexural strength, flexural modulus and the impact strength of the injection molded specimens as well as the water uptake were determined in this study. WPCs with the specific size range used in this investigation exhibited improved strength and modulus of elasticity in tensile and flexural tests, compared to pure CP. Using fraction 255, the mechanical properties increased the most. Tensile strength rose by 28 and 13% compared to CP and to WPC with the not fractioned wood powder, respectively. Fraction 255 increased flexural strength by 33 and 5% compared to CP and WPC with the not fractioned flour. The MFR (tested at 190 °C with 7.16 kg) of WPC_255 is the lowest with 2.3 g/10 min. Composites with the smallest particles showed the least water uptake.