New liquid-crystalline homo-and copolymers with phenyl benzoate side groups and a chiral center in a flexible spacer

The phase behavior and structure of liquid-crystalline homo-and copolymers based on structurally isomeric units belonging to the family of phenyl benzoates that differ in orientation of an ester link situated between benzene rings have been studied with X-ray diffraction, scanning calorimetry, and polarization optical microscopy. The orientation of this link in the monomer unit affects the temperature of phase transition, the type of the smectic phase, and the packing mode of side mesogenic groups in smectic layers of homopolymers. When monomer units commensurable with the monomer units of the basic component in terms of geometry but not identical to them in terms of smectogenity are randomly incorporated into macromolecules of the LC polymer, the resulting copolymer is characterized by layered packing not typical of either of the components.     

Investigation of local density of monomer units and molecular dynamics in solutions of poly-4-vinyl-pyridine by the spin label technique

The local density of monomer units of the macromolecule (local density of the host molecule, ?_host) in poly-4-vinyl-pyridine solutions in ethanol was determined by the spin label technique. In dilute solutions, ?_host is considerably greater than the mean density of monomer units in the volume of the polymer coil; when the polymer concentration rises from 0.5 to 65 wt%, its increase does not exceed 30%. This indicates that the differences between polymer coil microstructure (mutual positions of monomer units close to a chosen unit) in dilute and concentrated solutions is small. The local density of monomer units of neighbouring macromolecules (guest macromolecules, ?_guest) is strongly dependent on the polymer concentration in solution. In dilute solutions, ?_host ? ?_guest; for polymer concentrations above 2–3 wt%, overlapping and interpenetration of macromolecular coils take place, local density of monomer units of neighbouring macromolecules rises and monotonously increases as polymer concentration grows. The concentration dependence of the local rotational and translational mobility of monomer units is determined by the local density of monomer units of the neighbouring macromolecules.     

Self-assembly of polymer brushes in the presence of a surfactant: A system of strands

This theoretical study is focused on the formation of a cylindrical microstructure in a planar polymer brush in the presence of a surfactant. It is assumed that the brush may be nonuniform in the direction along the grafting plane and that there are regions with constant concentrations of monomer units and regions occupied only by the surfactant. The surfactant molecule is simulated by a dimer whose parts interact in a different manner with the monomer units of the polymer. At the interface between these regions, dimer molecules are oriented mainly perpendicularly to this interface and the surface tension is reduced. If the surface energy becomes negative, the formation of a structured brush is more favorable in terms of energy than that of a uniform brush. As a result, there may appear a cylindrical microstructure in which grafted macromolecules are united into strands perpendicular to the grafting plane. The stretching of macromolecules and their interaction with the solvent within the strands are described by the Alexander-de Gennes model, whereas the surface energy is calculated with allowance for the surface curvature of strands at a high degree of amphiphilicity of the surfactant molecules. It is shown that the arising strands have radii of the order of the surfactant-molecule length, while the number of macromolecules per strand is proportional to the surface density of their grafting. With an increase in the grafting density, the strand length increases initially, while the volume fraction of the polymer in a strand remains constant. Furthermore, strands start to shorten and their density grows. Structural characteristics are calculated as a function of the parameter characterizing the degree of amphiphilicity of the solvent molecules, their sizes, and their average energy of interaction with monomer units.     

Optically Active Methacrylic Polymers Bearing in the Side Chain the (S)-3-Hydroxypyrrolidinyl Group Linked to trans-bisazoaromatic Chromophore: Synthesis and Characterization

The synthesis by radical homopolymerization of a novel optically active methacrylic polymer containing a side-chain chiral moiety linked to a photochromic bisazoaromatic chromophore has been carried out starting from the related monomer (S)-3-methacryloyloxy-1-[4′-phenylazo-(4-azobenzene)]-pyrrolidine [(S)- MPAAP ]. The polymeric derivate has been fully characterized and its spectroscopic properties compared to those of the monomer and of the corresponding homopolymer bearing only one azoaromatic chromophore in the side chain. The optical activity displayed by the bisazo polymer is discussed in terms of extent of chiral conformation assumed by the macromolecules as a consequence of dipole-dipole interactions between the bisazoaromatic chromophores.     

Protection‐Group‐Free Synthesis of Sequence‐Defined Macromolecules via Precision λ‐Orthogonal Photochemistry

An advanced light‐induced avenue to monodisperse sequence‐defined linear macromolecules via a unique photochemical protocol is presented that does not require any protection‐group chemistry. Starting from a symmetrical core unit, precision macromolecules with molecular weights up to 6257.10 g mol^?1 are obtained via a two‐monomer system: a monomer unit carrying a pyrene functionalized visible light responsive tetrazole and a photo‐caged UV responsive diene, enabling an iterative approach for chain growth; and a monomer unit equipped with a carboxylic acid and a fumarate. Both light‐induced chain growth reactions are carried out in a λ‐orthogonal fashion, exciting the respective photosensitive group selectively and thus avoiding protecting chemistry. Characterization of each sequence‐defined chain (size‐exclusion chromatography (SEC), high‐resolution electrospray ionization mass spectrometry (ESI‐MS), and NMR spectroscopy), confirms the precision nature of the macromolecules.     

Monte Carlo Simulation of Hyperbranched Copolymerizations in the Presence of a Multifunctional Initiator

The Monte Carlo method is applied to simulate the copolymerization of a self‐condensing vinyl monomer and a conventional vinyl monomer in the presence of a multifunctional initiator at equal rate constants. With the increase of the molar ratio of self‐condensing vinyl monomer in the monomer composition, the number average degree of polymerization decreases and the weight average degree of polymerization decreases at a lower conversion of double bonds but increases at a higher conversion of double bonds. The molecular weight distribution, PI, changes from 1.01 to 12.0 and the average degree of branching, DB, increases from 0 to 0.456. We discovered that the addition of conventional vinyl monomer can modify the ratio of multi‐arm hyperbranched macromolecules in the product, i. e., the content of macromolecules with core moiety will increase with the increase of the ratio of conventional vinyl monomer. The possibility of controlling PI and DB by changing the conversion and monomer compositions is demonstrated.     

Principles of theoretical description of microstructure of linear condensation polymers

Key ideas of general original approach to the theoretical consideration of monomer sequence distribution problem are formulated for linear condensation heteropolymers showing either isomerism due to different fashions of monomer unit alternation in macromolecules of a copolymer or constitutional isomerism resulting from different orientation of asymmetric monomer units in polymers.     

Electrostatic-interaction-induced phase separation in solutions of flexible-chain polyelectrolytes

A model of a polyelectrolyte solution has been formulated on the basis of the formalism of the thermodynamic perturbation theory. Macromolecules have been described in terms of the model of a flexible chain with an excluded volume and a variable electrical charge. During construction of the thermodynamic perturbation theory, a set of three independent subsystems—polyelectrolyte macromolecules placed in a structureless charge background of counterions, counterions placed in a structureless charge background of macromolecules, and Coulomb gas ions of a low-molecular-mass salt—has been taken as the reference system. In the framework of this model, liquid-liquid phase separation due to strong correlation-induced attraction has been predicted. The behavior of the degree of ionization over a wide monomer concentration range, including the region of phase separation either in a salt-free solution or in the presence of univalent ions of a low-molecular-mass salt in the solution, has been studied. It has been shown that macromolecules in the coexisting phases should have different degrees of ionization. The occurrence of phase separation under normal conditions in the case when dimethylformamide is taken as a solvent and the nonoccurrence of this phase separation in the case of aqueous solutions of flexible-chain polyelectrolytes are predicted.     

Sequences in dendrons and dendrimers

Sequential incorporation of a variety of functional groups forms the basis for specificity in biomacromolecules. Introduction of such diversity and sequencing ability in artificial macromolecules is fundamentally interesting. In this paper, three different synthetic approaches have been used to build dendrons and dendrimers in which all the monomer units are different from each other. The synthetic strategies described in this paper involve the use of (i) an ABB(p) monomer, (ii) an ABB' monomer, and (iii) an ABB(m) monomer. The complementarity and the versatility of these synthetic approaches should render them useful for a variety of applications.     

Reactions of ozone with double bonds in polymer and biosystem chemistry

This review surveys data on the kinetics of ozone-double bonds reactions. The ozone-based procedure is compared with other known methods employed for analyzing double bonds, and it is shown how the above procedure may be used to determine the nature of terminal groups of macromolecules, the mechanisms of chain transfer and termination in polymerization processes, and the arrangement of monomer units in macromolecules (head-to-tail, head-to-head, etc.). Some aspects of ozone participation in biochemical processes proceeding in living organisms and its application in medicine are considered.     

A study of the viscosity of phenol–formaldehyde resin modified with furfural–acetone monomer FA

The results of an evaluation of the relative and dynamic viscosities of phenol–formaldehyde resin modified with furfural–acetone monomer FA monomer are presented. That there is increasing viscosity of the modified adhesive composition is established due to the formation of polycomplexes, these being new supramolecular structures with increased dimensions of macromolecules of higher molecular mass.     

Hyperbranched polyethers by ring‐opening polymerization: Contribution of activated monomer mechanism

Propagation in the cationic ring‐opening polymerization of cyclic ethers involves nucleophilic attack of oxygen atoms from the monomer molecules on the cationic growing species (oxonium ions). Such a mechanism is known as the active chain‐end mechanism. If hydroxyl groups containing compounds are present in the system, oxygen atoms of HO? groups may compete with cyclic ether oxygen atoms of monomer molecules in reaction with oxonium ions. At the proper conditions, this reaction may dominate, and propagation may proceed by the activated monomer mechanism, that is, by subsequent addition of protonated monomer molecules to HO? terminated macromolecules. Both mechanisms may contribute to the propagation in the cationic polymerization of monomers containing both functions (i.e., cyclic ether group and hydroxyl groups) within the same molecule. In this article, the mechanism of polymerization of three‐ and four‐membered cyclic ethers containing hydroxymethyl substituents is discussed in terms of competition between two possible mechanisms of propagation that governs the structure of the products—branched polyethers containing multiple terminal hydroxymethyl groups. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 457–468, 2003     

Secondary structure of globules of copolymers consisting of amphiphilic and hydrophilic units: Effect of potential range

The relation of the coil-globule transition in macromolecules consisting of amphiphilic and hydrophilic monomer units to the radius of action of the interaction potential is investigated by the method of computer-assisted experiments. The internal structure of globules formed by such macromolecules is significantly dependent on the radius of action of the potential. In the case of the long-range potential, the globule is characterized by the blob structure, while in the case of the short-range potential, a quasi-helical structure forms. In this structure, the skeleton of a macromolecule forms a helical turn, and the direction of twisting may vary from one turn to another. The coil-globule transition in such macromolecules proceeds through formation of the necklace conformation from quasi-helical micelle beads. For sufficiently long macromolecules, the dimensions of such globules are linearly dependent on the degree of polymerization.     

Phénomène de transfert de matière au voisinage des centres actifs en polymérisation anionique coordinée en solution du butène-1, en relation avec l'effet de l'hydrogène

Although the bulk and solution polymerization of but-l ene with a very stable catalytic composition (TiCl₃ AA + AlEt₂Cl) allows avoidance of effects of monomer mass transfer, one observes nevertheless a limitation of polymerization rate attributable to a diminution of the monomer concentration in the neighbourhood of active centres because of dilution of monomer caused by the polymer formed and bonded at these active centres.The favourable effect of hydrogen can be attributed to a decrease of this polymer concentration as a result of transfer which detaches macromolecules and allows a higher concentration of the monomer. A method is proposed for determination of the real catalytic activity.     

Grafting of Vinyl Monomers onto Nylon

Polymer chemists have been successful in applying polymerization techniques to develop copolymers of natural and synthetic macromolecules [l]. The literature abounds with examples of the successful formation of copolymers from natural and synthetic macromolecules [2–5]. Copolymerization is attractive to chemists as a means of modifying macromolecules since, in general, degradation can be minimized. Despite the heterogeneity and complexity of these copolymers, much has been achieved in their characterization. The desirable properties of the polymer are retained and additional properties are acquired through the added polymer. The desired material may be formed in situ by polymerization of a monomer or monomers, by condensation of reactants, or by the decomposition of a preformed polymer.     

Methacrylic Polymers Bearing in the Side-Chain an Optically Active Moiety Linked to the trans-4-Azobenzene Chromophore: Chiroptical Properties of Poly[(S)-(+)-N-methyl-(2-methacryloyloxypropanoyl)-4-aminoazobenzene]

The synthesis by radical homopolymerization of a novel optically active methacrylic polymer containing a side-chain chiral moiety linked to a photochromic chromophore has been carried out starting from the related monomer trans-(S)-(+)-N-methyl-(2-methacryloyloxypropanoyl)-4-aminoazobenzene. The chiroptical properties in solution of the polymer have been investigated by circular dichroism and compared with those of the corresponding low molecular weight model compound, trans-(S)-(+)-N-methyl-(2-pivaloyloxypropanoyl)-4-aminoazobenzene. The optical activity displayed by the polymer is discussed in terms of extent of chiral conformations assumed by the macromolecules as a consequence of dipole-dipole interactions between the azoaromatic chromophores.     

Investigation of mechanism of initiation of polymerization of cyclic acetals by protic and aprotic acids

The kinetics of polymerization of 1,3-dioxolan and degradation of polydioxolan catalyzed by boron trifluoride etherate have been studied in methylene chloride solution. The S-shape kinetic curves is found to be due to the autocatalytic action of the macromolecules formed. Effective participation of macromolecules in the initiation process has been confirmed on the basis of the relationship of the rate constants of boron trifluoride etherate reactions with cyclic monomer and with the polymer chain as well as by the decrease of the induction period on addition of the polymer or its low molecular weight analog, methylal, to the polymerization system.     

Stereospecific polymerization and chiral initiation,chiral crystallization and chiral nucleation

Helical macromolecules which are configurationally and conformationally specific can now be synthesized. Monomer structures must be selected that demand spacial restriction for monomer addition. High specificity of monomer addition during polymerization has parallels in crystallization of some inorganic salts from aqueous solution. Initiation of highly specific polymerizations with chiral initiators give helical polymers with substantial one-handedness. Nucleation of certain inorganic salts with chiral nucleating agents, the enantiomers of the salts produce enantiomerically pure chiral salts.     

Effect of structure of copolymers on the extent of selective sorption in dilute solutions in mixed solvents

The selective sorption of 2,2,3,3-tetrafluoropropanol (TFP) on to the macromolecules of polystyrene, poly(methyl methacrylate) and mixtures of these homopolymers, and also on to the macromolecules of the corresponding random and alternating copolymers has been measured. Dilute polymer solutions in a binary mixed solvent (benzene with 20 vol.-% TFP) have been studied by equilibrium dialysis and differential refractometry. The selective sorption of TFP in this system increases (at a constant copolymer composition) with increasing number of bonds between nonidentical monomer units; it takes up its highest value for the alternating copolymer and its lowest value for the mixture of the homopolymers.