Photocrosslinked poly(vinylbenzophenone)‐core micelles via mild Friedel–Crafts benzoylation of polystyrene amphiphiles

Photocrosslinkable poly(vinylbenzophenone)‐containing polymers were synthesized via a one‐step, Friedel–Crafts benzoylation of polystyrene‐containing starting materials [including polystyrene, polystyrene‐block‐poly(tert‐butyl acrylate), polystyrene‐block‐poly(ethylene oxide), polystyrene‐block‐poly(methyl methacrylate), and polystyrene‐block‐poly(n‐butyl acrylate)] with benzoyl trifluoromethanesulfonate as a benzoylation reagent. The use of this mild reagent (which required no added Lewis acid) permitted polymers with well‐defined compositions and narrow molecular weight distributions to be synthesized. Micelles formed from one of these benzoylated polymers, [polystyrene_0.25‐co‐poly(vinylbenzophenone)_0.75]₁₁₅‐block‐poly(acrylic acid)₁₄, were then fixed by the irradiation of the micelle cores with UV light. As the irradiation time was increased, the pendent benzophenone groups crosslinked with other chains in the glassy micelle cores. Dynamic light scattering, spectrofluorimetry, and Fourier transform infrared spectroscopy were all used to verify the progress of the crosslinking reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2604–2614, 2006     

Synthesis of silicon nitride based ceramic nanoparticles by the pyrolysis of silazane block copolymer micelles

Diblock copolymer poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane)‐block‐polystyrene (polyVSA‐b‐polySt) and triblock copolymer poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane)‐block‐polystyrene‐block‐poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane) (polyVSA‐b‐polySt‐b‐polyVSA), consisting of silazane and nonsilazane segments, were prepared by the living anionic polymerization of 1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane and styrene. PolyVSA‐b‐polySt formed micelles having a poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane) (polyVSA) core in N,N‐dimethylformamide, whereas polyVSA‐b‐polySt and polyVSA‐b‐polySt‐b‐polyVSA formed micelles having a polyVSA shell in n‐heptane. The micelles with a polyVSA core were core‐crosslinked by UV irradiation in the presence of diethoxyacetophenone as a photosensitizer, and the micelles with a polyVSA shell were shell‐crosslinked by UV irradiation in the presence of diethoxyacetophenone and 1,6‐hexanedithiol. These crosslinked micelles were pyrolyzed at 600 °C in N₂ to give spherical ceramic particles. The pyrolysis process was examined by thermogravimetry and thermogravimetry/mass spectrometry. The morphologies of the particles were analyzed by atomic force microscopy and transmission electron microscopy. The chemical composition of the pyrolysis products was analyzed by X‐ray fluorescence spectroscopy and Raman scattering spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4696–4707, 2006     

Effects of the architecture and environment on polymeric molecular assemblies of novel amphiphilic diblock copolynorbornenes with narrow polydispersity via living ring‐opening metathesis polymerization

Diblock copolymers of 5‐(methylphthalimide)bicyclo[2.2.1]hept‐2‐ene (NBMPI) and 1,5‐cyclooctadiene were synthesized by living ring‐opening metathesis polymerization with a well‐defined catalyst {RuCl₂(CHPh)[P(C₆H₁₁)₃]₂}. Unhydrogenated diblock copolymers showed two glass transitions due to poly(NBMPI) and polybutadiene segments, such as two glass‐transition temperatures at ?86.5 and 115.3 °C for poly 1a and ?87.2 and 115.3 °C for poly 1b . However, only one melting temperature could be observed for hydrogenated copolymers, such as 119.8 °C for poly 2a and 121.7 °C for poly 2b . The unhydrogenated diblock copolymer with the longer poly(NBMPI) chain (poly 1a ; temperature at 10% mass loss = 400 °C) exhibited better thermal stability than the one with the shorter poly(NBMPI) chain (poly 1b ; temperature at 10% mass loss = 385 °C). Two kinds of hydrogenated diblock copolymers, poly 2a and poly 2b , exhibited relatively poor solubility but better thermal stability than unhydrogenated diblock copolymers because of the polyethylene segments. Poly[(hydrochloride quaternized 2‐norbornene‐5‐methyleneamine)‐b‐butadiene]‐1 (poly 3a ) was obtained after the hydrolysis and quaternization of poly 1a . Dynamic light scattering measurements indicated that the hydrodynamic diameters of the cationic copolymer (poly 3a ) in water (hydrodynamic diameter = 1580 nm without salt), methanol/water (4/96 v/v; hydrodynamic diameter = 1500 nm without salt), and tetrahydrofuran/water (4/96 v/v; hydrodynamic diameter = 1200 nm without salt) decreased with increasing salt (NaCl) concentration. The effect of temperature on the hydrodynamic diameter of hydrophobically modified poly 3a was also studied. The inflection point of the hydrodynamic diameter of poly 3a was observed at various polymer concentrations around 30 °C. The critical micelle concentration of hydrophobically modified poly 3a was observed at 0.018 g dL^?1. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2901–2911, 2006     

Synthesis of poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) by the competitive single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization in water

The synthesis of a block copolymer poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) is reported. This new material was synthesized by single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization (SET‐DTLRP) in two steps. First, a bifunctional macroinitiator of α,ω‐di(iodo)poly (butyl acrylate) [α,ω‐di(iodo)PBA] was synthesized by SET‐DTLRP in water at 25 °C. The macroinitiator was further reinitiated by SET‐DTLRP, leading to the formation of the desired product. This ABA block copolymer was synthesized with high initiator efficiency. The kinetics of the copolymerization reaction was studied for two PBA macroinitiators with number–average molecular weight of 10 k and 20 k. The relationship between the conversion and the number–average molecular weight was found to be linear. The dynamic mechanical thermal analysis suggests just one phase, indicating that copolymer behaves as a single material with no phase separation. This methodology provides the access to several block copolymers and other complex architectures that result from combinations of thermoplastics (PVC) and elastomers (PBA). From industrial standpoint, this process is attractive, because of easy experimental setup and the environmental friendly reaction medium. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3001–3008, 2006     

Encapsulation of ZnS:Mn2+ nanocrystals with diblock copolymers

The encapsulation of the nanocrystalline manganese‐doped zinc sulfide (ZnS:Mn) in poly(styrene‐b‐2vinylpyridine) (PS‐PVP) diblock copolymers is reported. Below the critical micelle concentration in the absence of nanocrystals (NCs), inverse micelles of PS‐PVP were induced by adding ZnS:Mn NCs, the presence of which was confirmed by scanning force microscope and dynamic light scattering. In toluene, a PS‐selective solvent, the less‐soluble PVP blocks preferentially surround the ligand‐coated ZnS:Mn NCs. For PS‐PVP encapsulated ZnS:Mn NCs, the ratio of blue emission to orange emission of ZnS:Mn NCs is dependent on both the concentration of PS‐PVP and the solvent quality. The pyridine of PVP blocks form complexes with the Zn atoms via the nitrogen lone pair and thus the sulfur vacancies are passivated. As a result, the defect‐related blue emission is selectively quenched even when the micelles are not formed. As the concentration of PS‐PVP encapsulating the ZnS:Mn NCs increases, the intensity of blue emission decreases. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3227–3233, 2006     

Metallocene copolymers of propene and 1‐hexene: The influence of the comonomer content and thermal history on the structure and mechanical properties

The relationships between the structure and properties have been established for copolymers of propylene and 1‐hexene synthesized with an isotactic metallocene catalyst system. The most important factor affecting the structure and properties of these copolymers is the comonomer content. The thermal treatment, that is, the rate of cooling from the melt, is also important. These factors affect the thermal properties, the degree of crystallinity, and therefore the structural parameters and the viscoelastic behavior. A slow cooling from the melt favors the formation of the γ phase instead of the α modification. Regarding the viscoelastic behavior, the β relaxation, associated with the glass‐transition temperature, is shifted to lower temperatures and its intensity is increased as the 1‐hexene content raises. The microhardness values are correlated with those of the storage modulus deduced from dynamic mechanical thermal analysis curves, and good linear relations have been obtained between these parameters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1253–1267, 2006     

Slow crack growth in blends of HDPE and model copolymers

The resistance to slow crack growth (SCG) was measured in binary blends of high density polyethylene (HDPE) and 5–10% concentrations of model ethylene-butene random copolymers by measuring the time to failure (t_f) under a constant stress intensity. An increase of t_f with the addition of the copolymer if the copolymer could crystallize and the increase was greater the higher branch density. The copolymer with 117 branches/1000C could not crystallize and therefore its blend had a t_f that was less than that of the HDPE. The fracture energies of the blends as determined by their resistance to SCG were compared with the energy by rapid fracture, J_c, as previously measured by Rhee and Crist. It is concluded that SCG is more sensitive to variations in the microstructure than is rapid fracture and that the differences in SCG behavior can be qualitatively explained in terms of the differences in microstructure of the blends. ©1995 John Wiley & Sons, Inc.     

Structural properties of charged diblock copolymer solutions

Aqueous micellar solutions of ionic/neutral block copolymers have been studied by light scattering, small angle neutron scattering and small angle X-ray scattering. We made use of a polymer comprised of a short hydrophobic block (polyethylene-propylene) PEP and of a long polyelectrolytic block (polystyrene-sulfonate) PSSNa which has been shown previously to micellize in water. The apparent polydispersity of these micelles is studied in detail, showing the existence of a few large aggregates coexisting with the population of micelles. Solutions of micelles are found to order above some threshold in polymer concentration. The order is liquid-like, as demonstrated by the evolution with concentration of the peak observed in the structure factor (), and the degree of order is found to be identical over a large range of concentrations (up to 20 wt%). Consistent values of the aggregation number of the micelles are found by independent methods. The effect of salt addition on the order is found to be weak. Received: 19 June 1997 / Received in final form: 4 September 1997 / Accepted: 9 October 1997     

The response of microstructure to processing in a series of poly(siloxaneimide) copolymers

Poly(siloxaneimide) (PSI) segmented copolymers exhibit organized microdomains if the blocks are sufficiently incompatible. As with neat diblock and triblock copolymers, the processing route employed to prepare films of PSI materials is expected to influence the dimensions and/or morphology of the resultant microstructure. In this work, small-angle neutron scattering (SANS) is utilized to characterize the disordered microstructure found in films of a series of PSI copolymers which are subjected to solvent casting and various thermal treatments. Microstructural dimensions such as the periodicity and correlation length are deduced from the Teubner-Strey (TS) model for disordered microemulsions. The scattering intensity of each copolymer up to q = 5.0 nm^?1, where q is the scattering vector, is found to scale as q^?2.8+?0.1. Results indicate that processing the materials as cast films or as melt-pressed films allowed to cool slowly has a small, but discernible, effect on microstructural characteristics. SANS profiles of films quenched from elevated temperatures reveal a clear transition in microdomain periodicity, which correlates well with the glass transition temperature of the imide microphase in these and other materials of similar chemical structure. © 1993 John Wiley & Sons, Inc.     

Stochastic flows on a countable set: Convergence in distribution

Consider a sequenceF ₁,F ₂,... of i.i.d. random transformations from a countable setV toV. Such a sequence describes a discrete-time stochastic flow onV, in which the position at timen of a particle that started at sitex isM _n(x), whereM _n =F _n F _n–1 F ₁. We give conditions on the law ofF ₁ for the sequence (M _n) to be tight, and describe the possible limiting law. an example called the block charge model is introduced. The results can be formulated as a statement about the convergence in distribution of products of infinite-dimensional random stochastic matrices. In practical terms, they describe the possible equilibria for random motions of systems of particles on a countable set, without births or deaths, where each site may be occupied by any number of particles, and all particles at a particular site move together.