Synthesis, thermal behavior, and aggregation in aqueous solution of poly(methyl methacrylate)-b-poly(2-hydroxyethyl methacrylate)

Indexación: ScieloABSTRACT Amphiphilic block copolymers of poly(methyl methacrylate) PMMA and poly(2-hidroxyethyl methacrylate) PHEMA were synthesized by a two-step atom transfer radical polymerization (ATRP). Copolymers with various degrees of polymerization and different relative block sizes were obtained. The structure of the resulting polymers have been characterized and verified by FT-IR and 1H-NMR, molecular weight were determined by size exclusion chromatography analyses. The thermal properties of these polymers were investigated by differential scanning calorimetry DSC and thermogravimetric analysis TGA. The glass transition temperature of mono halogenated PMMA increases from 116 °C to 123 °C with increasing molecular weight, whereas the glass transition temperature of block copolymers depends slightly on polymer structure. The derivatives of TGA curves indicate that thermal degradation occurs in one stage. The self-assembly of PMMA-b-PHEMA in aqueous solution have been investigated by fluorescence probing methods. The critical micelle concentrations are in the range 10-6 - 10-7 M. The micropolarity sensed by pyrene is higher than in aggregates formed by block copolymers based on polystyrene. Keywords: Block copolymers, glass transition temperature, thermogravimetric analysis, critical micelle concentration, fluorescence probing methods

Star-Like Micelles with Star-Like Interactions: A quantitative Evaluation of Structure Factor and Phase Diagram

PEP-PEO block copolymer micelles offer the possibility to investigate phase behaviour and interactions of star polymers (ultra-soft colloids). A star-like architecture is achieved by an extremely asymmetric block ratio (1:20). Micellar functionality f can be smoothly varied by changing solvent composition (interfacial tension). Structure factors obtained by SANS can be quantitatively described in terms of an effective potential developed for star polymers. The experimental phase diagram reproduces to a high level of accuracy the predicted liquid/solid transition. Whereas for intermediate f a bcc phase is observed, for high f the formation of a fcc phase is preempted by glass formation.Comment: 5 pages, 4 figures, PRL in pres

Stereocomplex formation in ABA triblock copolymers of poly(lactide) (A) and poly(ethylene glycol) (B)

Two series of triblock copolymers of poly(ethylene glycol) (PEG, number-average molecular weight [bar M ]n = 6000) and poly(L-lactide) (PLLA) or poly(D-lactide) (PDLA) were prepared by ring-opening polymerization of lactide initiated by PEG end groups using stannous octoate as a catalyst, either in refluxing toluene or in the melt at 175°C. The weight percentage of PLA in the polymers varied between 15 and 75 wt.-%. Blends of polymers containing blocks of opposite chirality were prepared by co-precipitation from homogeneous solutions. The melting temperatures of the crystalline PEG and PLA phases strongly depended on the composition of the polymers. The melting temperature of the PLA phase in the blends was approximately 40°C higher than that of the single block copolymers. Stereocomplex formation between blocks of enantiomeric poly(lactides) in PEG/PLA block copolymers was established for the first time. Water uptake of polymeric films prepared by solution casting was solely determined by the PEG content of the film

Ru-Catalyzed, cis-Selective Living Ring-Opening Metathesis Polymerization of Various Monomers, Including a Dendronized Macromonomer, and Implications to Enhanced Shear Stability

An unsaturated polymer’s cis/trans-olefin content has a significant influence on its properties. For polymers obtained by ring-opening metathesis polymerization (ROMP), the cis/trans-olefin content can be tuned by using specific catalysts. However, cis-selective ROMP has suffered from narrow monomer scope and lack of control over the polymerization (giving polymers with broad molecular weight distributions and prohibiting the synthesis of block copolymers). Herein, we report the versatile cis-selective controlled living ROMP of various endo-tricyclo[4.2.2.0^(2,5)]deca-3,9-diene and various norbornene derivatives using a fast-initiating dithiolate-chelated Ru catalyst. Polymers with cis-olefin content as high as 99% could be obtained with high molecular weight (up to M_n of 105.1 kDa) and narrow dispersity (<1.4). The living nature of the polymerization was also exploited to prepare block copolymers with high cis-olefin content for the first time. Furthermore, owing to the successful control over the stereochemistry and narrow dispersity, we could compare cis- and trans-rich polynorbornene and found the former to have enhanced resistance to shear degradation

100th Anniversary of Macromolecular Science Viewpoint: Opportunities in the Physics of Sequence-Defined Polymers

Polymer science has been driven by ever-increasing molecular complexity, as polymer synthesis expands an already-vast palette of chemical and architectural parameter space. Copolymers represent a key example, where simple homopolymers have given rise to random, alternating, gradient, and block copolymers. Polymer physics has provided the insight needed to explore this monomer sequence parameter space. The future of polymer science, however, must contend with further increases in monomer precision, as this class of macromolecules moves ever closer to the sequence-monodisperse polymers that are the workhorses of biology. The advent of sequence-defined polymers gives rise to opportunities for material design, with increasing levels of chemical information being incorporated into long-chain molecules; however, this also raises questions that polymer physics must address. What properties uniquely emerge from sequence-definition? Is this circumstance-dependent? How do we define and think about sequence dispersity? How do we think about a hierarchy of sequence effects? Are more sophisticated characterization methods, as well as theoretical and computational tools, needed to understand this class of macromolecules? The answers to these questions touch on many difficult scientific challenges, setting the stage for a rich future for sequence-defined polymers in polymer physics

Polymer Segmental Cross-Correlations from Dielectric Relaxation Spectra of Block Copolymers

Dielectric relaxation spectra of block polymers containing sequential type-A dipoles are considered. Spectra of a specific set of block copolymers can be combined to isolate the dynamic cross-correlation between the motions of two distinct parts of the same polymer chain. Unlike past treatments of this problem, no model is assumed for the underlying polymer dynamics.Comment: 7 pages, zero figure

Melt block copolymerization of ε-caprolactone and L-lactide

AB block copolymers of ε-caprolactone and (L)-lactide could be prepared by ring-opening polymerization in the melt at 110°C using stannous octoate as a catalyst and ethanol as an initiator provided ε-caprolactone was polymerized first. Ethanol initiated the polymerization of ε-caprolactone producing a polymer with ε-caprolactone derived hydroxyl end groups which after addition of L-lactide in the second step of the polymerization initiated the ring-opening copolymerization of L-lactide. The number-average molecular weights of the poly(ε-caprolactone) blocks varied from 1.5 to 5.2 × 103, while those of the poly(L-lactide) blocks ranged from 17.4 to 49.7 × 103. The polydispersities of the block copolymers varied from 1.16 to 1.27. The number-average molecular weights of the polymers were controlled by the monomer/hydroxyl group ratio, and were independent on the monomer/stannous octoate ratio within the range of experimental conditions studied. When L-lactide was polymerized first, followed by copolymerization of ε-caprolactone, random copolymers were obtained. The formation of random copolymers was attributed to the occurrence of transesterification reactions. These side reactions were caused by the ε-caprolactone derived hydroxyl end groups generated during the copolymerization of ε-caprolactone with pre-polymers of L-lactide. The polymerization proceeds through an ester alcoholysis reaction mechanism, in which the stannous octoate activated ester groups of the monomers react with hydroxyl groups