The synthesis of high molecular mass (Mr＞5×105) polymers with a narrow molecular mass distribution (Mr,max/Mr,min＜1.05) is a challenging theme in modem polymer chemistry. 相似文献
Summary: A new generation of anionic initiators (butyllithium free), based on trialkylaluminum and a readily available alkali metal hydride, has been developed for the control of styrene polymerization at high temperature. Triisobutylaluminum and sodium hydride form heterocomplexes that are efficient for the initiation of styrene polymerization at 100 °C in toluene or in bulk. To be active under such conditions, these systems require the presence of an excess of metal hydride with respect to AlR3 ([Al]/[Na] < 1). PS chains are specifically initiated by the hydrides coming from NaH, and molar masses are controlled in the range 0.8 < [Al]/[Na] < 1. Fast exchange between dormant 1:1 and active 1:2 complexes (Al:Na), and ligand rearrangements within the 1:2 complex, can explain the observed results.
Initiation of styrene with i‐Bu3Al/NaH systems. 相似文献
It still remains a concern to break through the bottlenecks of anionic polymerization of polar monomers, such as side reactions, low conversion and low temperature (–78°C). In this work, potassium tert‐butoxide (t‐BuOK) was chosen to initiate the anionic polymerization of 2‐ethylhexyl methacrylate (EHMA) in tetrahydrofuran. The conversions were above 99% at 0 or 30°C, and above 95% at 60°C without side reaction inhibitors. The high conversions implied t‐BuOK could suppress the side reactions. A series of block copolymers of EHMA, n‐hexyl methacrylate (HMA) and methyl methacrylate (MMA) were further synthesized at 0°C, and the conversions were all above 99%. The GPC and 1H NMR results confirmed the successful synthesis of the block copolymers. The molecular size of monomer and the state of t‐BuOK (free ion pairs or aggregates) remarkably affected the polymerization rates and the molecular structures of the products. The DMA results indicated that the glass transition temperatures of PEHMA or PHMA block and PMMA block were 20°C and 60°C, respectively, which deviated from –2°C and 105°C of homopolymer, respectively, due to the partial compatibility of the blocks. This work explored a route of the anionic polymerization of polar monomers at room temperature. 相似文献
Benzyl-substituted cyclopentadienyl lanthanide complexes were synthesized and characterized by elemental analysis, MS and IR spectroscopy. The analytical data point out the formation of monomeric, unsolvated complexes.In conjunction with AI(Et)3 as co-catalyst, the title complexes are efficient catalysts for the syndiotactic polymerization of methyl methacrylate. For the complex (C6HsCH2C5H4)2YCl, under the optimum polymerization conditions(60℃,n(MMA):n(catalyst):n(co-catalyst)=1000:1:10),a predominantly syndiotactic (rr=66%) polymerof high molecular weight (Mη=105000) was obtained. 相似文献
In an attempt to reduce the emission of hazardous VOCs, SCFs have been intensively investigated as alternative solvents during the last two decades. In this study, the application of reaction calorimetry, an efficient tool to obtain kinetic and safety data, is presented on the free radical dispersion polymerization of MMA in scCO2. The effect of three major parameters with respect to the reaction evolution are studied, namely of stirrer type and stirring speed, the monomer and CO2 concentration and the stabilizer concentration. The effective formation of the dispersion as well as the balance between the polymer formed in the continuous phase or inside the particles are key features of this analysis.
