An Arbitrarily Regulated Monomer Sequence in Multi-Block Copolymer Synthesis by Frustrated Lewis Pairs

Rapid access to sequence-controlled multi-block copolymers (multi-BCPs) remains as a challenging task in the polymer synthesis. Here we employ a Lewis pair (LP) composed of organophosphorus superbase and bulky organoaluminum to effectively copolymerize the mixture of methacrylate, cyclic acrylate, and two acrylates, into well-defined di-, tri-, tetra- and even a hepta-BCP in one-pot one-step manner. The combined livingness, dual-initiation and CSC feature of Lewis pair polymerization enable us to achieve not only a trihexaconta-BCP with the highest record in 8 steps by using four-component monomer mixture as building blocks, but also the arbitrarily-regulated monomer sequence in multi-BCP, simply by changing the composition and adding order of the monomer mixtures, thus demonstrating the powerful capability of our strategy in improving the efficiency and enriching the composition of multi-BCP synthesis.     

LIQUID CRYSTALLINE POLYMERS. IV. THERMOTROPIC LIQUID CRYSTALLINE POLY(ARYLIDENE-ETHER)S AND COPOLYMERS CONTAINING N-METHYLPIPERIDONE LINKED TO THE MAIN CHAIN THROUGH SPACERS OF VARIOUS LENGTHS

Two novel series of poly(arylidene-ether)s and copoly(arylidene-ether)s were synthesized from N-methylpiperidone and/or cyclohexanone respectively. The first series (homopolymers) was derived from 4,4′-diformyl-α,ω-diphenoxyalkane or 4,4′-diformyl-2,2′ dimethoxy-α,ω-diphenoxyalkane with N-methylpiperidone. The second series (copolymers) was derived from the diphenoxyalkanes (I–VIII) with N-methylpiperidone and cyclohexanone. The inherent viscosities of the polymers thus prepared were in the range of 0.37–0.98 dI/g. The majority of the polymers and copolymers are soluble in chlorinated hydrocarbons. DSC measurements and microscope observation under polarized light demonstrate that this type of poly(arylidene-ether)s form nematic mesophase over a wide temperature range in contrast to the corresponding copoly(arylidene-ether)s. All of the polymers and copolymers exhibited thermotropic liquid crystalline properties. In most cases, the mesophase extends up to 315°C, where thermal decomposition prevents further observation. The morphology of polymer IXb and copolymer XIb as a selected example was examined by scanning electronic microscope.     

Improved Flexural Strength of N-Vinyl-Pyrrolidone Modified Acrylic Acid Copolymers for Glass-Ionomers

Abstract

The flexural strengths of N-vinylpyrrolidone modified glass-ionomer cements were investigated. The optimal molar ratio of the monomers in copolymers, composed of the three components acrylic acid, itaconic acid and N-vinylpyrrolidone, was determined using a SAS statistical program. The copolymers were prepared using a free-radical polymerization process. The viscosities of aqueous solutions of these polymers were determined. Cements were formed by the reaction of these solutions with glass particles. Flexural strength (FS) was used as the basic screening property to find the optimum molar ratio. Statistical models were applied to predict the optimum molar ratios. All strength values were recorded on the specimens conditioned in distilled water at 37°C for 7 days. The optimal molar ratio for these copolymers was 7:1:3 for poly(acrylic acid-co-itaconic acid-co-N-vinylpyrrolidone), based on flexural strength and viscosity. The effect of molecular weight (MW) on FS was also evaluated. Copolymer with a MW of 10, 800 (M_n) showed 85% higher FS than the Ketac-Molar (KM) system, along with a reasonable working viscosity.     

Dibenzylmagnesium-Initiated Anionic Oligomerizations of trans-Stilbene, 1,1-Diphenylethylene,and α-Methylstyrene in Hexamethylphosphortriamide

trans-Stilbene, 1, 1-diphenylethylene, and α-methylstyrene were allowed to react with dibenzylmagnesium to form their oligomers in hexamethylphosphortriamide (HMPA). One and two molecules of stilbene and 1, 1-diphenylethylene were incorporated into the magnesium carbon bond, and the carbanions obtained in HMPA were stable in analogy with the anionic living polymer having alkali cation as the gegenion in eithers. Intense coloration was observed during the reaction between α-methylstyrene and dibenzylmagnesium as well as in the case of stilbene and 1, 1-diphenylethylene. The low molecular weight products which were formed after a long time in the reaction between α-methylstyrene and dibenzylmagnesium were found to have no magnesium-carbon bond. It was considered that the cleavage of the propagating chain occurred gradually after the rapid propagation had proceeded to consume the monomer.     

Polymer chain conformation of copolymers with different monomer size: C NMR spectroscopy and MALS study

Copolymer composition, distribution and molecular size of the comonomer influence the final properties of polymer materials. Such influence can be followed from the effect on the chain conformation in solution determined from the scaling law between radius of gyration and molecular weight.     

Preservation of beech and spruce wood by allyl alcohol-based copolymers

Allyl alcohol (AA), acrylonitrile (AN), methyl methacrylate (MMA), monomers and monomer mixtures AA+AN, AA+MMA were used to conserve and consolidate Beech and Spruce. After impregnation, copolymerisation and polymerisation were accomplished by gamma irradiation. The fine structure of wood+polymer(copolymer) composites was investigated by Scanning Electron Microscopy (SEM). It was observed that copolymer obtained from AA+MMA monomer mixture showed the optimum compatibility. The compressional strength and Brinell Hardness Numbers determined for untreated and treated wood samples indicated that the mechanical strength of wood+copolymer composites was increased. It was found that the mechanical strength of the wood samples containing the AA+MMA copolymer was higher than the others. In the presence of P(AA/MMA), at highest conversion, the compressive strength perpendicular to the fibres in Beech and Spruce increased approximately 100 times. The water uptake capacity of wood+copolymer composites was observed to decrease by more than 50% relative to the original samples, and biodegradation did not take place.     

Photostability of novel copolymers functionalized with laser dyes based on modified rhodamine 6G and 1,8-naphthalimide

Modified rhodamine 6G molecules (Rh-Al or Rh-Aln) with polymerizable double bonds had been copolymerized with 1,8-naphthalimide derivatives. In copolymers PRNAM, naphthalimide moieties are connected to rhodamine moieties at nitrogen atom of rhodamine moiety, and in copolymers PRNM naphthalimide moieties are connected to rhodamine moieties at ester group of rhodamine moiety. We report on their photostability in liquid solution and in solid film. The photodegradation kinetics of novel copolymers functionalized with laser dyes based on modified rhodamine 6G and 1,8-naphthalimide has been studied by UV-VIS absorption spectroscopy. The results show that the rates of the photofading reactions of these novel copolymers follow quasi-first-order. The photostability of the copolymers functionalized with laser dyes in solid films is better than that in solutions. The different type of the copolymer shows the different photostability.     

Synthesis of styrene–butadiene rubber latex via miniemulsion copolymerization

High-butadiene-level styrene–butadiene rubber latexes up to high solid-contents are synthesized using the miniemulsion process. It is shown that the miniemulsion polymerization approach offers an efficient heterophase route synthesizing styrene–butadiene copolymer latexes with flexible copolymer composition and narrow size distribution of the resulting latex particles. Secondary nucleation was successfully prevented by using a hydrophobic initiator. Due to the nanoreactor situation, even at high conversions, a low crosslinking degree and, therefore, low gel contents are obtained. The microstructure of the polymers obtained in miniemulsion is independent of the synthesis parameters, especially the temperature. The molecular weight can be easily adjusted by the application of transfer agents while the insoluble gel content is substantially reduced. An up-scaling of the procedure is easily possible.     

ANTIMICROBIAL ACTIVITY OF COPOLYMERS OF 2,4-DICHLOROPHENYL ACRYLATE WITH STYRENE:SYNTHESIS,CHARACTERIZATION AND REACTIVITY RATIOS

Some copolymers of 2,4-dichlorophenyl acrylate (2,4-DCPA) with styrene (St) of different teed compositions were prepared by tree radical polymerization technique using 2,2′-azobisisobutyronitrile (AIBN) as an initiator,and the copolymers were characterized by IR spectroscopy.The copolymer composition obtained by UV-spectra led to determination of reactivity ratio by employing Fineman-Ross (F-R) and Kelen-Tudos (K-T) methods.Average molecular weight,as well as intrinsic viscosity,was obtained by vapor pre...     

Bicontinuous geometries and molecular self-assembly: comparison of local curvature and global packing variations in genus-three cubic, tetragonal and rhombohedral surfaces

Balanced infinite periodic minimal surface families that contain the cubic Gyroid (G), Diamond (D) and Primitive (P) surfaces are studied in terms of their global packing and local curvature properties. These properties are central to understanding the formation of mesophases in amphiphile and copolymer molecular systems. The surfaces investigated are the tetragonal, rhombohedral and hexagonal tD, tP, tG, rG, rPD and H surfaces. These non-cubic minimal surfaces furnish topology-preserving transformation pathways between the three cubic surfaces. We introduce `packing (or global) homogeneity', defined as the standard deviation Δd of the distribution of the channel diameter throughout the labyrinth, where the channel diameter d is determined from the medial surface skeleton centered within the labyrinthine domains. Curvature homogeneity is defined similarly as the standard deviation ΔK of the distribution of Gaussian curvature. All data are presented for distinct length normalisations: constant surface-to-volume ratio, constant average Gaussian curvature and constant average channel diameter. We provide first and second moments of the distribution of channel diameter for all members of these surfaces complementing curvature data from [A. Fogden, S. Hyde, Eur. Phys. J. B 7, 91 (1999)]. The cubic G and D surfaces are deep local minima of Δd along the surface families (with G more homogeneous than D), whereas the cubic P surface is an inflection point of Δd with adjacent, more homogeneous surface members. Both curvature and packing homogeneity favour the tetragonal route between G and D (via tG and tD surfaces) in preference to the rhombohedral route (via rG and rPD).