Simultaneous Chain Growth Research Articles

Simultaneous Chain-Growth and Step-Growth Polymerization of Methoxystyrenes by Rare-Earth Catalysts.

The simultaneous chain-growth and step-growth polymerization of a monomer is of great interest and importance because it can produce unique macromolecules which are difficult to prepare by other means. However, such a transformation is usually difficult to achieve in one polymerization system because chain-growth polymerization and step-growth polymerization proceed by different reaction mechanisms. Reported here is the simultaneous chain-growth and step-growth polymerization of para- and meta-methoxystyrenes catalyzed by half-sandwich rare-earth alkyl complexes, and the step-growth polymerization proceeds by the C-H polyaddition of anisyl units to vinyl groups. This unprecedented transformation affords a new family of macromolecules containing unique alternating anisole-ethylene sequences. In contrast to para- and meta-methoxystyrenes, ortho-methoxystyrene exclusively undergo syndiospecific, living chain-growth polymerization by continuous C=C bond insertion to give perfect syndiotactic poly(ortho-methoxystyrene) with high molecular weight and narrow polydispersity (rrrr >99 %, Mn up to 280 kg mol-1 , Mw /Mn <1.10).

The role of living/controlled radical polymerization in the formation of improved imprinted polymers

In this work, living/controlled radical polymerization (LRP) is compared with conventional free radical polymerization in the creation of highly and weakly cross-linked imprinted poly(methacrylic acid-co-ethylene glycol dimethacrylate) networks. It elucidates, for the first time, the effect of LRP on the chain level and begins to explain why the efficiency of the imprinting process is improved using LRP. Imprinted polymers produced via LRP exhibited significantly higher template affinity and capacity compared with polymers prepared using conventional methods. The use of LRP in the creation of highly cross-linked imprinted polymers resulted in a fourfold increase in binding capacity without a decrease in affinity; whereas weakly cross-linked gels demonstrated a nearly threefold increase in binding capacity at equivalent affinity when LRP was used. In addition, by adjusting the double bond conversion, we can choose to increase either the capacity or the affinity in highly cross-linked imprinted polymers, thus allowing the creation of imprinted polymers with tailorable binding parameters. Using free radical polymerization in the creation of polymer chains, as the template-monomer ratio increased, the average molecular weight of the polymer chains decreased despite a slight increase in the double bond conversion. Thus, the polymer chains formed were shorter but greater in number. Using LRP neutralized the effect of the template. The addition of chain transfer agent resulted in slow, uniform, simultaneous chain growth, resulting in the formation of longer more monodisperse chains. Reaction analysis revealed that propagation time was extended threefold in the formation of highly cross-linked polymers when LRP techniques were used. This delayed the transition to the diffusion-controlled stage of the reaction, which in turn led to the observed enhanced binding properties, decreased polydispersity in the chains, and a more homogeneous macromolecular architecture.

Nitroxide-mediated copolymerization of methacrylic acid with sodium 4-styrene sulfonate: towards new water-soluble macroalkoxyamines for the synthesis of amphiphilic block copolymers and nanoparticles

The SG1-mediated copolymerization of methacrylic acid (MAA) and 4-styrene sulfonate (SS) was studied in dimethylsulfoxide solution at 76 °C, first, to determine the reactivity ratios in such conditions and second, to check the living character of the reaction at low molar fraction of SS. The reactivity ratios in the terminal model were rMAA = 0.44 and rSS = 1.34 indicating a favored incorporation of SS at the beginning of the copolymerization. All characteristics of a controlled/living system were observed, in good agreement with an efficient deactivation of the propagating radicals by the nitroxide SG1, via probable formation of an SS terminal subunit-based alkoxyamine. The method was shown to be particularly well-suited for the design of living polymers intended to be used as hydrophilic macroinitiators for the synthesis of amphiphilic block copolymers. This was demonstrated in both solution polymerization and ab initio, batch emulsion polymerization. The latter process allowed well-defined block copolymer nanoparticles to be formed at low temperature, in a single step, by simultaneous chain growth and self-assembling.

Formation of polymer vesicles by simultaneous chain growth and self-assembly of amphiphilic block copolymers

Polymerization-induced formation of amphiphilic diblock copolymer vesicles is performed in water at high concentrations by a single-step nitroxide-mediated controlled free-radical emulsion polymerization of 4-vinylpyridine, initiated by a water-soluble poly(sodium acrylate) macroalkoxyamine at alkaline pH.

Poly(l-lactic acid)/SiO2 nanocomposites via in situ melt polycondensation of l-lactic acid in the presence of acidic silica sol: Preparation and characterization

In situ melt polycondensation of l-lactic acid (LLA) in the presence of acidic silica sol (aSS) is proposed for the first time to prepare PLLA/SiO2 nanocomposites. The SiO2 nanoparticles were readily dispersed in LLA monomer, which has similar polarity and hydrophilicity to the silica sol medium. During the polycondensation process, both the matrix and the surface of SiO2 nanoparticles changed from high polarity/hydrophilicity to weak polarity/hydrophobicity due to simultaneous chain growth in the organic phase and chemical grafting on the particle surface. The chemical grafting provided steric stabilization and ensured satisfactory nano-scale dispersion in the final nanocomposites. The introduction of SiO2 nanoparticles resulted in unchanged yield and better color. The molecular weight kept almost constant at low SiO2 content (<8wt%) but decreased at higher SiO2 content. The method is also characterized by commercially available and cheap starting material and environmentally benign process. It appears to be a promising approach for the preparation of PLLA/SiO2 nanocomposites.

Cyclic Poly(thioglycolide) and Poly(d,l-thiolactide) by Zwitterionic Polymerization of Dithiolane-2,4-diones

Dithiolane-2,4-dione was polymerized either by heating in bulk to 140 °C or by reacting at 20 °C using pyridine and triethylamine as catalysts. Whereas the thermal polymerization almost exclusively yielded cyclic poly(thioglycolide), the samples prepared at 20 °C by means of tertiary amines contained cyclic and linear chains. The end groups of the linear chains varied with the nonsolvent used for the workup procedure, because chains having reactive end groups were immobilized by rapid crystallization and reacted at the electrophilic CO-chain end with the nonsolvent. d,l-5-Methyldithiolane-2,4-dione proved so stable that tertiary amines did not catalyze its polymerization even at 100 °C. Thermal polymerization at 160 °C yielded oligoester mainly consisting of cyles. A zwitterionic polymerization mechanism allowing for simultaneous chain-growth and step-growth polymerization is discussed.