Advancing from unimechanism polymerization to multimechanism polymerization: binary polymerization

Polymerizations with multiple mechanisms performed simultaneously are promising but very challenging. As the key limitation,the complicated mutual influence between different mechanisms can be hardly defined and measured. Herein we establish a universal framework for the assessment of mutual influence between different mechanisms using binary polymerization for demonstration. The kinetics and thermodynamics of polymerization with two mechanisms are compared with the corresponding homopolymerization and the difference is expressed by a hybrid function. The hybrid function is composed of a hybrid parameter that describes the extent of mutual influence and a function that describes necessary conditions for mutual influence to occur. The extent of mutual influence can be calculated using kinetic and thermodynamic data without details of reaction mechanisms, for the first time providing a straightforward method to assess the mutual influence between different polymerization mechanisms.We envision that the method has potential in more complex systems with multiple mechanisms/monomers with mutual influence.     

Towards a consistent mechanism of emulsion polymerization—new experimental details

The application of atypical experimental methods such as conductivity measurements, optical microscopy, and nonstirred polymerizations to investigations of the ‘classical’ batch ab initio emulsion polymerization of styrene revealed astonishing facts. The most important result is the discovery of spontaneous emulsification leading to monomer droplets even in the quiescent styrene in water system. These monomer droplets with a size between a few and some hundreds of nanometers, which are formed by spontaneous emulsification as soon as styrene and water are brought into contact, have a strong influence on the particle nucleation, the particle morphology, and the swelling of the particles. Experimental results confirm that micelles of low-molecular-weight surfactants are not a major locus of particle nucleation. Brownian dynamics simulations show that the capture of matter by the particles strongly depends on the polymer volume fraction and the size of the captured species (primary free radicals, oligomers, single monomer molecules, or clusters).     

Short-time isoprene polymerization under the action of a titanium–magnesium catalyst

The short-time polymerization of isoprene under the action of a TiCl₄/MgCl2?i-Bu₃Al heterogeneous catalyst has been investigated. Pulse mixing of the catalyst and monomer in a cylindrical tubular reactor with a certain length followed by ethanol injection has made it possible to carry out polymerization for 0.1?0.7 s. In the first 0.3 s, when there is a considerable rise in the activity of the catalyst, living polymerization of isoprene takes place. In this period, polyisoprene has up to 95% trans-1,4 units. Extending the polymerization time to 0.7 s diminishes the average molar mass of polyisoprene, broadens its molar mass distribution, and decreases the concentration of trans-1,4 units to 83%. The data of this study have been analyzed on the basis of the kinetic continuity of the polymer chain initiation and growth.     

Highly controlled immortal polymerization of β-butyrolactone by a dinuclear indium catalyst

An ethoxy-bridged dinuclear indium catalyst was used for the ring opening polymerization of the cyclic ester β-butyrolactone to form the biodegradable polyester poly(hydroxybutyrate) (PHB). The catalyst shows remarkable activity and control during polymerization, allowing for formation of diblock polymers. Addition of high ratios of alcohols to the catalyst leads to fast chain transfer and immortal polymerization.     

Electrochemical polymerization of dicarboxylic acids—VI. Mechanism of polymerization

The mechanism of the electrochemical polymerization of dicarboxylic acids in various solvents, which also leads to the formation of various side products, is discussed. The formation of hydrocarbons was rationalized through the formation of α,ω-biradicals which suffer coupling or disproportionation reactions. Carboxylic acids are shown to originate from reactions of ^•(CH₂)_k COOH radicals which couple radicals which couple or disproportionate among themselves or other radicals to give saturated and unsaturated acids. Cations formed from anodic oxidation of the radicals are the precursors of lactones and some olefins. The conformations of the dicarboxylate anions at the anode surface are discussed with a view of rationalizing the formation of the various products. Polymer formation was explained as occurring through α,ω-biradicals having a definite conformation. Pyridine affected to a large extent these conformations, and higher concentrations of pyridine led to an increase in the conformations which lead to polymer formation.     

Multi-walled carbon nanotubes as a ligand in nickel α-diimine based ethylene polymerization

Two novel heterogeneous nickel ?-diimine based polymerization catalysts, containing MWCNT as the main ligand, were synthesized by novel in situ catalyst preparation technique. The in situ synthesis was performed by covalent attachment of the acenaphthenic ligand core to amine functionalized MWCNT ligand arms through diimine bonding and further nickel dibromide chelation. The prepared catalysts were fully characterized and their structures and supporting efficiencies were determined. Single or double introduction of the MWCNTs through their ends or sidewall(s) in the catalytic system, as a ligand, influenced the catalytic performance, microstructure and morphology of obtained polyethylenes. MWCNT sidewall bonding to para-aryl position of the tetramethylphenyl moiety performed as more electron-donating ligand than MWCNT ends linked to the imine bond and protected the catalytic system to retain its activity. This character resulted in the maintenance of the resulting polymer topology at elevated temperatures so that the catalytic activity and the obtained polymer melting points remained around 110 g PE?mmol?1 Ni?h?1 and 123 ℃ in all polymerization temperatures respectively. In polymerization trials, molecular weight fall against temperature was not as sharp as what had been observed in sequentially prepared catalysts insofar as the molecular weight of resultant polymer at 60 ℃ reached to 310000 g?mol?1 which was close to the highest value had been reported at 30 ℃ for sequentially prepared catalysts. TEM observations showed the presence of the stopped-growth polymer chains due to geometrical constrains or ligand debonding for both catalytic systems.     

A rhodium complex-linked β-barrel protein as a hybrid biocatalyst for phenylacetylene polymerization

Our group recently prepared a hybrid catalyst containing a rhodium complex, Rh(Cp)(cod), with a maleimide moiety at the peripheral position of the Cp ligand. This compound was then inserted into a β-barrel protein scaffold of a mutant of aponitrobindin (Q96C) via a covalent linkage. The hybrid protein is found to act as a polymerization catalyst and preferentially yields trans-poly(phenylacetylene) (PPA), although the rhodium complex without the protein scaffold normally produces cis PPA.     

β-Peptide coatings by surface-initiated polymerization

Homopolymers of β-lactams can be grown by surface-initiated polymerization. These surface-linked β-peptides are living polymers with the potential to be utilized as tunable, protease-resistant interfaces in multiphase structural composites where the characteristics of the interface influence bulk properties.     

Ring opening metathesis polymerization of an η4-benzene complex: a direct synthesis of a polyacetylene with a regular pattern of π bound metal fragments

The complex (η(5)-C(5)H(5))Ir(η(4)-C(6)H(6)) reacts with Grubbs' catalyst to give a novel polyacetylene consisting of cyclopentadienyliridium bound s-cis butadiene moieties separated by C=C linkages. A crystal structure of the pentamethylcyclopentadienyl analog establishes a strong structural analogy with norbornadiene, a classical ROMP monomer.     

Tree-gel and loop-gel conversions in nonlinear polymerization

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β-Sheet-induced chirogenesis in polymerization of oligopeptides

The origin of long homochiral biopolymers in living systems has recently been the focus of intense research. In one particular research line, scientists studied, experimentally and theoretically, chiral amplification obtained during peptide formation by polymerization of amino acid building blocks. It was suggested that processes leading to temporal or spatial separation, and thus, to the growth of homochiral polymers at the expense of their heterochiral counterparts, can explain the chirality observed in larger molecules. We introduce a simple model and stochastic simulation for the polymerization of amino acids and β-sheet formation, showing the crucial effects of the β sheets on the distributions of peptide lengths. When chiral affinities are included, racemic β sheets of alternating homochiral strands lead to the formation of chiral peptides, the isotacticity of which increases with length, consistent with previous experimental results in aqueous solutions. The tendency to form isotactic peptides is shown for both initially racemic and initially nonracemic systems, as well as for closed and open systems. We suggest that these or similar mechanisms may explain the origin of chiroselectivity in prebiotic environments.     

Study on polymerization and structure of polydiphenylamine

The electrochemical oxidation of diphenylamine in acetonitrile produces an adherent uniform polymer film which exhibits mutiple colour variation(yellow-green-blue) in a wide range of potential scan. The polymerization mechanism and the structure of the polymer were studied by cyclic voltammetry, FT-IR and in situ ESR. The results indicate that the electrochemical polymerization of diphenylamine belongs to a cationic radical polymerization process. During electrolysis, only oligomers were initialy produced, then polymer film was formed on the electrode surface. The electropolymerization performs via the 4,4' C-C phenyl-phenyl coupling mechanism.     

Vapor phase composition and radical polymerization—how the gas phase influences the kinetics of heterophase polymerization

The outcome of radical styrene heterophase polymerization depends strongly on the composition of the gas phase. Data of a comprehensive experimental study show that the effect of the gas phase is quite a complex one and strongly influenced by the nature of the gas, the homogeneity or heterogeneity of the polymerization system, and the kind of initiator. Evidence is presented that the influence of air goes beyond the simple action of oxygen which can cause deceleration or acceleration of the reaction. The experimental results show that the optimum polymerization conditions are obtained in the absence of any foreign gas.     

Organocatalytic stereoselective cationic polymerization of vinyl ethers by employing a confined BrΦnsted acid as the catalyst

The properties of poly(vinyl ether)s(PVEs)are highly dependent on their tacticity,and the appealing thermoplastics features of isotactic PVEs have drawn considerable efforts to develop stereoselective cationic polymerization methods to access this class of polymers.However,reported methods that could achieve a high degree of tacticity control are limited to process employing metal-based Lewis acids,and with various limitations on catalyst loading,monomer scope,etc.Here,we introduce a metal-free stereoselective cationic polymerization of vinyl ethers by employing a class of chiral confined Br?nsted acids,imidodiphosphorimidates(IDPis),as the catalyst.This organocatalytic approach features its metal-free conditions,high efficiency,high stereoselectivity,single catalyst system,operation simplicity,etc.     

Study of ε-caprolactone polymerization by NIR spectroscopy

Near-infrared (NIR) spectroscopy is proposed for the in-line quantitative and kinetic study of the polymerization of ε-caprolactone and eventually to facilitate real-time control of the manufacturing process. Spectra were acquired with a fibre-optic probe operating in transflectance mode immersed in the reactor. The NIR data acquired were processed using a multivariate curve resolution alternating least squares (MCR-ALS) algorithm. The proposed method allows calculation of the concentration and spectral profiles of the species involved in the reaction. The key point of this method is the lack of reference concentrations needed to perform the MCR-ALS method. The use of an extended spectral matrix using both process and pure analyte spectra solves the rank deficiency. The concentration profiles obtained were used to calculate a kinetic fitting of the reaction, but the method was improved by applying kinetic constraints (hard modelling). The rate constants of batches at different temperatures and the energy of activation for this reaction were calculated. Whenever possible, the hard modelling combined with the MCR-ALS method improves the fit of the experimental data: the results show good correlation between the NIR and reference data and allow the collection of high-quality kinetic information on the reaction (rate constants and energy of activation).     

Invited Lecture. Ferroelectric liquid crystalline polymers and related model compounds with a low–moderate degree of polymerization

Abstract

Ferroelectric liquid crystalline polymers (FLCPs) with a low-moderate degree of polymerization were synthesized. These had a comb structure; the main chain was polyacrylate and the side chain consisted of a flexible spacer, a core and an optically active chiral end group. They exhibited electro-optic switching times ranging from a few milliseconds to a few seconds in the S*_c phase. As the molecular weight M _n increased, the range of the S*_c shifted to higher temperatures. At a given temperature, the switching time increased with M _n .

Spontaneous polarizations P _s , apparent cone angles 2θ, electro-optic switching times τ and rotational viscosities η of some polyoxyethylene FLCPs and corresponding low molecular weight ferroelectric liquid crystal materials (FLCs) were also measured. This is the first report of polyoxyethylene FLCPs. There was no significant difference in P _s and 2θ, which shows that the arrangement of the side chains in the FLCP is similar to that of the molecules in ordinary FLC. On the contrary, τ and η for the FLCPs were 10²–10³ times as large as those for FLCs. The rotational viscosity of the FLCP was mainly dependent on the side chain structure rather than on the spacer. Therefore collisions between adjacent side chains cause large η values in FLCPs rather than hindrance to side chain gyration due to the spacer group. By combining FLCPs with ITO-coated plastic substrates, a large area matrix driven display has been made. Although an improvement in switching time is still needed, a flexible and lightweight display like a sheet of paper will be available in the near future.     

Preparation of poly(ε-caprolactone)@attapulgite nanocomposites via a combination of controlled ring-opening polymerization and click chemistry

In this work, by a combination of controlled ring-opening polymerization (CROP) and click chemistry, we report a facile and useful method to synthesize linear poly(ε-caprolactone)@attapulgite nanocomposites with well-defined structures. For this, first, the chlorine-terminated attapulgite was prepared by the self-assembly of 3-chloropropyltrimethoxysilane from the surfaces of attapulgite. And then, the terminal chlorines of modified attapulgite were substituted with azido groups. As the second step, linear propargyl-terminated poly(ε-caprolactone) (PCLs) with different molecular weights were synthesized by the CROP of ε-CL monomer in toluene with stannous octoate as a catalyst and propargyl alcohol as an initiator. The structural characteristics of the obtained linear PCLs have been determined by ¹H NMR and gel permeation chromatography analysis. Finally, the azido-terminated attapulgite was reacted with propargyl-terminated PCLs via the click reaction.     

Cationic polymerization of dienes VIII: Is the elimination of cross-linking by a bulky electron donor a general behavior in the presence of aluminium trichloride?

Previous works on the polymerization of 1,3-pentadiene initiated by aluminium trichloride in non polar solvent at room temperature in the presence of bulky electron donor (ED) as tri-p-tolylamine have highlighted a stabilization of the polymerizing actives centres by ED, which allowed a reduction of some side reactions and the formation of more precisely defined polypentadienes than ever by cationic polymerization in non polar medium. The aim of this research was to investigate the role of bulky EDs such as tri-p-tolylamine and similar compounds in polar medium in order to obtain if possible a complete control of the polymerization of isoprene and 1,3-pentadiene. The beneficial effect of tri-p-tolylamine was shown in the case of isoprene polymerization at room temperature, with an important reduction of the cross-linked fraction for long reaction times and strong reduction of termination reactions. At −30 °C in the presence of tri-p-tolylamine, polypentadienes more controlled than in non polar solvent could be obtained, with a nearly complete elimination of the cross-linked fraction, while keeping the microstructure approximately constant.     

Host-enhanced π-π interaction for water-soluble supramolecular polymerization

Host-enhanced π-π interaction based on anthracene derivatives and cucurbit[8]uril can be used as the driving force for constructing water-soluble supramolecular polymers. For this purpose, two anthracene moieties were encapsulated into one cucurbit[8]uril cavity, forming a ternary complex. After encapsulation in the host, the distance between the two anthracene moieties was shortened, and the π-π interaction between them was enhanced significantly. To realize supramolecular polymerization, a bifunctional monomer consisting of two anthracene moieties and a short linker in between was carefully designed. Cyclization was avoided in this way. Thus, host-enhanced π-π interaction can function as a new driving force for supramolecular polymerization.