Summary: New rheological results with molten polypropylenes of different degrees of syndiotacticity are presented. The temperature dependence of their dynamic viscoelastic functions is correlated with the characteristic ratio. Relaxation time and Newtonian viscosity values are plotted as a function of molecular weight. The very high values of both rheological parameters found for the most syndiotactic polypropylenes are explained considering the reptation model, which links conformational parameters with the viscoelastic response in the molten state.
Disengagement or reptation time as a function of molecular weight. 相似文献
We report a new method for the synthesis of block copolymers with a pentasilane core by the polymerization of alkyl methacrylate monomers using the pentasilyl dianion as an initiator. The polymerization proceeded with living features and yielded the corresponding block copolymers with controlled molecular weights. The amphiphilic block copolymer was obtained by the polymer reaction, and it formed sphere‐like aggregates in MeOH/H2O solution.
This review covers the literature concerning the modification of polysaccharides through controlled radical polymerizations (NMP, ATRP and RAFT). The different routes to well‐defined polysaccharide‐based macromolecules (block and graft copolymers) and graft‐functionalized polysaccharide surfaces as well as the applications of these polysaccharide‐based hybrids are extensively discussed.
We describe the preparation and characterization of uniaxial magnetic gels. Fibril formation of the embedded magnetic particles generates easily detectable magnetic and optical anisotropies. A finite magnetization is frozen‐in and leads to a ferromagnetic‐like response in small homogeneous external magnetic fields. We present, for the first time, frequency dependent measurements of the shear modulus G′. Despite their optical and magnetic anisotropy, the gels are mechanically isotropic.
The time‐dependent G′ for a ferrogel in the parallel orientation in a homogeneous field of 200 mT. 相似文献
Structured hybrid nanoparticles were synthesized via surface‐initiated atom transfer radical polymerization of MMA from ordered mesoporous silica (OMS) nanoparticles with various morphologies. The design of the OMS particles was adjusted to target either spherical core‐shell or cylindrical morphologies with a mean diameter below 400 nm. The polymer growth via ATRP from the silica surface was well‐controlled as demonstrated by the macromolecular characteristics of the grafted chains. Original hybrid multilayered nanoparticles composed of either a dense silica core or hollow core; an inner OMS shell showing radial orientation of the mesopores and an outer PMMA shell with controlled thickness were successfully prepared.
Summary: Polystyrene (PS) micro‐ and nanospheres with uniform dimensions and smooth surfaces have been produced by electrospray. The effect of PS molecular weight on beads morphology and the fundamental role of concentration have been investigated. Moreover, a new apparatus was designed to collect the polymer spheres during the process and to prevent the coalescence among the spheres.
PS micro‐ and nanospheres produced by electrospray 相似文献
A series of size‐controlled, cyclic poly(tetrahydrofuran)s ( of 4 400–8 600) that consist exclusively of the monomer, i.e., oxytetramethylene, unit ( I ) have been prepared in high yield through the metathesis polymer cyclization of a telechelic precursor having allyl groups, 1 , in the presence of a Grubbs catalyst, and the subsequent hydrogenation of the linking, i.e., 2‐butenoxy, unit in the presence of an Adams' catalyst (PtO2). A remarkable topology effect has subsequently been observed upon the isothermal crystallization of these two model polymers, showing distinctive spherulite growth rates and spherulite morphologies in comparison with the relevant linear poly(tetrahydrofuran) counterpart that has ethoxy end groups ( II ).
J. Chemometrics 22 (2): 135–140. DOI: 10.1002/cem.1122 It has come to our attention that an error arose during correction of this article. In Figure 3, Step 3 should as appear as follows:
A new diamine monomer containing benzimidazole‐5‐sulfonic acid has been synthesised. It has been reacted, alone or mixed with diaminodiphenyl ether, with naphthalenic dianhydride to attain polynaphthalimides in which the sulfonic acid functionality is borne by pendant benzimidazole groups. The presence of sulfonic and benzimidazole groups greatly affected the physical properties of the polyimides as the novel polymers were found to be soluble in polar organic solvents and exhibited a lower thermal resistance than their non‐sulfonated counterparts. The polymer films exhibited good mechanical properties with tensile strength in the range 100–120 MPa and with moduli in the range 2.2–3.1 GPa. Sulfonic and benzimidazole groups significantly enhanced the hydrophilicity of the copolyimides, which showed water uptake up to 39%.
A new method for determination of contributions of species present in low concentration in kinetic Monte Carlo (MC) simulations of chemical processes is proposed. It allows, for instance, to calculate of exact concentrations when species being of interest appear in MC experiments only for short time intervals. The method is based on monitoring of the cumulative life‐time of the investigated species under consideration as a function of the reaction time and subsequent differentiation of the resulting curve. It is especially useful for determination of distributions of low‐concentration active propagation species in radical polymerizations, both free and controlled ones. The method enables to reduce significantly a simulation scale required for determination of the concentrations of investigated species.
Grafted conjugated polyelectrolytes were synthesized for the first time and characterized. The polymers demonstrated properties of a convenient and efficient protocol for creating Hg2+ sensors. The unique character of the new material comes from an anionic counterion nature with no external cofactors, and imparts high selectivity and fast detection for mercury ion in a fluorescence probe. The concept may be potentially applied to create new sensors for monitoring other ions.
The use of a photocatalyst (tris(2‐phenylpyridine)iridium [Ir(ppy)3]) being able to generate both radicals and cations to initiate free radical polymerization and ring opening polymerization is presented. Remarkably, under soft irradiations (fluorescence bulb, sunlight), excellent cationic polymerization profiles and final conversions are obtained. The involved mechanisms are investigated by ESR experiments.
Summary: Bimolecular type‐II photoinitiators for radical photopolymerization suffer from a diffusion‐controlled limitation of reactivity and from deactivation by back electron transfer. Here, a very efficient concept to increase the photoinitiator activity by the covalent binding of phenylglycine to benzophenone using a methylene spacer is presented. Photo‐DSC experiments proved that the rate of polymerization can be tripled in comparison to a physical mixture of the components or an industrially applied system with triethanolamine as coinitiator.
Structure of the new photoinitiator synthesized here. 相似文献
The IUPAC recommended factor 2 preceding rate coefficients in the radical termination kinetic equations is claimed to be incorrect and confusing. This recommendation can lead to incorrect analysis of experimental data, especially while applying kinetic Monte Carlo simulations. The statement is based on the derivation of the corresponding relationships.
