Molecular Simulation of Chain Initiation Mechanism in Oxidation of Lubricant Base Stock

Chain initiation reactions in the oxidation process of lubricant base stock molecules were studied by molecular simulations.Two ways to initiate lubricant oxidation were investigated.They included the dissociation of chemical bonds in base stock molecules and the reaction between base stock molecules and oxygen(O_(2)),respectively.Reaction activation energy of above methods was calculated.The results show that C‒C bonds are more likely to break than C‒H bonds to generate free radicals by the pyrolysis of chemical bonds.The C‒C bonds with tertiary carbon atoms are preferential positions to crack.However,their bond dissociation energy is above 360 kJ/mol,which is difficult to occur under lubricant working conditions.The chain initiation is more likely to occur by the way that O_(2) attacks the two atoms in C‒H bonds at the same time,and is then embedded into the C‒H bond to produce hydrocarbon peroxides.And then,the O‒O bond is cracked to form hydroxyl radicals and alkoxy radicals.The C‒H bonds with tertiary carbon atoms are preferential reaction sites,the reaction activation energy of which is about 190.11 kJ/mol.

Synthesis and MALDI-TOF Characterization of β-CD Core ATRP Initiators and RAFT Chain Transfers with Different Degrees of Substitution

In this paper, three different kinds of β-CD derivatives were synthesized as atom transfer radical polymerization（ATRP） initiator or reversible addition-fragmentation chain transfer polymerization（RAFT） chain transfers. The degree of substitution for each derivative was carefully characterized through 1H-NMR, 13C-NMR spectroscopy and matrix-assisted laser desorption/ionization time of flight mass spectrometry（MALDI-TOF-MS）. The factors influencing the degree of substitution were discussed. Moreover, the comparison between ATRP and RAFT was shown in the polymerization of Nisopropyl acrylamide（NIPAM）.