Synthesis of poly(trioctylammonium p-styrenesulfonate) homopolymers and block copolymers by RAFT polymerization

A method to prepare sulfonated polystyrene-containing block copolymers has been investigated by neutralizing styrene sulfonic acid with trioctylamine to produce the hydrophobic monomer trioctylammonium p-styrenesulfonate (SS-TOA). This monomer was polymerized by reversible addition fragmentation chain transfer (RAFT) polymerization to produce PSS-TOA homopolymers. A PSS-TOA homopolymer was then used as a macro-RAFT agent for the polymerization of styrene to prepare poly(trioctylammonium p-styrenesulfonate)-block-poly(styrene) (PSS-TOA-b-PS). These block copolymers could be ion-exchanged to produce either the hydrophilic sodium salt form of PSS or a hydrophobic quaternary ammonium salt. This approach will be useful for preparing PSS-containing block copolymers with a range of hydrophobic blocks for applications such as ion-exchange membranes.     

Synthesis and characterization of homopolymers and copolymers of various acrylates and acrylonitrile

Various homopolymers and copolymers of methyl acrylate, ethyl acrylate, butyl acrylate, and acrylonitrile in different feed ratios were synthesized. These were characterized by IR, ¹³C-NMR, DSC, DTA, and TGA. Spectroscopic characterization helped in differentiating copolymers of different mol ratios. Thermal analysis revealed different degradation patterns for homopolymers and copolymers. The temperature and energy changes associated with various phase transitions were dependent on the chemical composition of homo- and copolymers, as expected. © 1993 John Wiley & Sons, Inc.     

Copper(I)-catalyzed homocoupling reaction of terminal alkynes in supercritical CO2

An efficient method for CuCl-catalyzed homocoupling reaction of terminal alkynes in the synthesis of symmetric 1,3-diynes has been developed in supercritical CO₂ (ScCO₂) without organic solvent. Homocoupling of various terminal alkynes (solid or liquid) could afford the corresponding products in moderate to excellent yields. In addition, ScCO₂ play the role of reactive solvent, and DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) acts as the key additive for homocoupling reactions of terminal alkynes, which enhanced the reaction rate and the solubility of copper(I) catalyst in ScCO₂.     

Optical properties of the thin films of poly(methylpentoxysilane) homopolymers and copolymers

The optical properties of the thin films of asymmetrically substituted polysilane homopolymers and copolymers were studied. A conformational change in the organopolysilanes having (pentoxy,methyl) or (hexyl,methyl) groups was observed by polarized UV spectrometry and a wide angle X-ray diffraction. The polysilanes and polysilane copolymers having hexyl and pentoxy side chains were crystallized to form oriented films along the direction of the mechanically oriented polytetrafluoroethylene (PTFE) films. The bathochromic shifts were observed for polysilane and the polysilane copolymer having pentoxy side chains when the film thickness was small (ca. <50 nm). The influence of the thickness of the films on the spectral change was significant when the substituent was a pentoxy group, however, not when it was a hexyl group.     

Synthesis and characterisation of N-toluyl methacrylatoethyl carbamates,homopolymers and copolymers with methyl methacrylate

The paper describes the synthesis of N-2/4-toluyl methacrylatoethyl carbamates using 2/4-toluyl isocyanate and 2-hydroxyethyl methacrylate. Homopolymerisation and copolymerisation of these novel monomers with methyl methacrylate was carried out using benzoyl peroxide as an initiator and tetrahydrofuran as solvent. Photopolymerisation of N-4-toluyl methacrylatoethyl carbamate could be carried out without the use of photosensitiser. Structural characterisation of copolymers was done using ¹H-NMR. Thermal stability of copolymers was evaluated in a nitrogen atmosphere by dynamic thermogravimetry.     

Pd(OAc)2-catalyzed room temperature homocoupling reaction of arylboronic acids under air without ligand

Moderate to good yields of symmetrical biaryls were achieved under very mild conditions via homocoupling of arylboronic acids catalyzed by Pd(OAc)₂ under air without using ligand. And the reactions were performed in acetone/water (v/v = 1:1) at room temperature without giving side products. In addition, when the reaction was carried out under an oxygen atmosphere, enhancement of yield was observed which indicated the essential of oxygen.     

Block copolymers derived from azobiscyanopentanoic acid. XI. Properties of silicone–PMMA block copolymers prepared via polysiloxane(azobiscyanopentanamide)s

Mechanical, thermal, and surface properties of poly(dimethylsiloxane)–poly(methyl methacrylate) block copolymers (PDMS-b-PMMA) prepared by the use of polysiloxane(azobiscyanopentanamide)s were intensively investigated. The mechanical strength of block copolymers was found to decrease with an increase of siloxane contents. Dynamic mechanical analysis (DMA) of block copolymers having long siloxane chain length (SCL) and high siloxane content revealed the existence of two glass transitions attributable to microphase separation of two segments. Differential scanning calorimetry (DSC) also gave some evidence of microphase separation supporting the DMA results. It was observed that the incorporation of PDMS segments in block copolymers improved thermal stability of PMMA, as confirmed by thermogravimetric analysis. Surface analysis of the block copolymers films cast from several solutions indicated surface accumulation of PDMS segments, as revealed by water contact angle and ESCA measurements.     

Synthesis,physical and thermal characterization of phosphorus-containing homopolymers and copolymers based on 2,4-bis(4-aminophenoxy)-6-diethoxyphosphinyl-s-triazine

Novel phosphorus-containing homopolyimides, homopolyamides, and homopolyureas were prepared by reacting 2,4-bis(4-aminophenoxy)-6-diethoxyphosphinyl-s-triazine (BADT) with pyromellitic or benzophenone tetracarboxylic dianhydride, terephthaloyl chloride, and tolylene diisocyanate, respectively. In addition, the corresponding copolymers that contained approximately 3% phosphorus were prepared by reacting BADT and 4,4′-diaminodiphenyl sulfone with the aforementioned reagents. These polymers were characterized by inherent viscosity measurements, infrared (IR) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy as well as by differential thermal analysis (DTA) and dynamic thermogravimetric analysis (TGA). Their thermal properties were compared with those of the corresponding nonphosphorylated polymers. The copolymers were stable up to 233–272°C in nitrogen or air atmosphere. The homopolymers showed a relatively lower thermal stability. Furthermore, a model diimide, diamide, and diurea were synthesized from the reactions of BADT with phthalic anhydride, benzoyl chloride, and phenyl isocyanate, respectively. The physical and thermal characteristics of these model compounds were correlated with those of the corresponding homopolymers.     

Synthesis and characterization studies of homopolymers of N-vinylpyrrolidone,vinyl acetate,and their copolymers

Homopolymers of N-vinylpyrrolidone (VP) and vinyl acetate (VAc) were synthesized by a free-radical solution polymerization technique. Copolymers of VP and VAc in various monomer feed ratios were also synthesized by the same procedure. They were characterized by elemental analysis, FTIR, PNMR, TGA, swelling, and viscosity measurements. The reactivity ratios of the monomers were computed by both Fineman–Ross and Kelen–Tudos methods using data from both PNMR and elemental analysis studies. The activation energy values for various stages of decomposition were calculated from TGA analysis using Broido's method. The viscosity measurements were carried out at four different temperatures: 30, 35, 40, and 45°C. The activation parameters of the viscous flow, voluminosity (V_E), and shape factor (ν) were also computed for all systems. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:91–102, 1998     

Polyarylates (polyesters from aromatic dicarboxylic acids and bisphenols)

After a short review on the literature of aromatic polyarylates synthesis the following aspects are described: preparation of some monomers; preparation of the polymers by different chemical processing routes; physical properties; moulding behaviour. Amorphous polymers are especially considered. Figures on continuous melt condensation via the diphenylester route are given. Some polyarylates have attractive mechanical and electrical properties. Injection moulding is only possible if the glass temperature is not too high (≤200°C), and even with these polymers thermal decomposition during injection moulding is a limiting factor for their technical use. The weak point is the ester group. Extrusion, pressing, and solution casting are technically feasable.     

Development and characterization of homopolymers and copolymers from the family of polyphenylene oxides

Poly(2,6‐dimethyl‐1,4‐phenylene oxide), PDMPO, poly(2,6‐diphenyl‐1,4‐phenylene oxide), PDPPO, as well as their copolymers of different compositions, having both random and block structures, have been synthesized and characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, and gel permeation chromatography. Solution‐cast films were prepared from all synthesized polymers using chloroform as a solvent. The thermal properties of the resulting films were characterized by differential thermal analysis and differential scanning calorimetry, whereas their morphology was investigated using X‐ray diffraction. Ultimately, the potential of the synthesized polymers for gas separation was studied by examining gas permeation properties of the respective thin films in single gas permeation tests involving N₂, O₂, CH₄, and CO₂. In general, the O₂ and CO₂ permeability coefficients decrease with the PDPPO content. However, the largest drop in the permeability coefficients occurs between PDMPO and a copolymer having the lowest PDPPO content, and the permeability coefficients PDPPO are comparable or even lower than the permeability coefficients of the copolymers having the largest PDDPO content. On the basis of combination of the permeability coefficients and their ratios for CO₂/CH₄ and O₂/N₂, random copolymers appear to be a better candidate for gas separation membranes than their block counterparts. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Graft copolymers from commercial chlorinated polypropylene via Cu(0)‐mediated atom transfer radical polymerization

Commercially available chlorinated polypropylene has been used as a macroinitiator for the Cu(0)‐mediated atom transfer radical polymerization of methyl methacrylate and tert‐butyl acrylate to obtain well‐defined graft copolymers. The relatively narrow molecular weight distribution in the graft copolymers and linear kinetic plots indicated the controlled nature of the copolymerization reactions. Both Fourier transform infrared and ¹H NMR studies confirmed that the graft reactions had taken place successfully. After graft copolymer formation, tert‐butyl groups of poly(tert‐butyl acrylate) side chains were completely converted into poly(acrylic acid) chains to afford corresponding amphiphilic graft copolymers. © 2016 Society of Chemical Industry     

Hansen solubility parameter: from polyethylene and poly(vinyl acetate) homopolymers to ethylene–vinyl acetate copolymers

The Hansen solubility parameters (HSPs ) of two ethylene–vinyl acetate (EVA ) copolymers (with 18 and 33 wt% of vinyl acetate) and their corresponding homopolymers (polyethylene, PE , and poly(vinyl acetate), PVAc ) have been studied at various temperatures, employing the previously obtained Flory–Huggins parameters. From these latter values, a procedure based on the Hansen solubility spheres theory was employed to determine the HSPs , as well as the radius of interaction. The procedure was validated with literature data, with deviations of around 3%. The HSP values (dispersion, polar and association terms, respectively, all in MPa^{1 /2}) at 333.15 K are 14.84, ?3.88 and 1.78 for PE , 17.65, ?1.24 and 2.76 for EVA410 (with 18 wt% of vinyl acetate), 17.52, 0.15 and 3.61 for EVA460 (with 33 wt% of vinyl acetate) and 19.45, 10.59 and 5.76 for PVAc . The main characteristic of the obtained HSP values is that the high polar term of PVAc tends to increase the solubility character of the pure PE , and thus the EVA copolymers, allowing them to solubilize dispersion and polar compounds. Finally, it was also demonstrated that it is possible to predict the HSPs of EVA copolymers using the vinyl acetate content and the HSPs of pure PE and PVAc as input data. © 2017 Society of Chemical Industry     

Synthesis,crystal structures and cytotoxic activity of mononuclear nickel(II) and dinuclear zinc(II) complexes with ligand derived from S-benzyldithiocarbazate

Ni(L)₂ (1) and Zn₂(μ-OL)₂(L)₂ (2), (HL = S-benzyl-β-N-(2-bromobenzylidene) dithiocarbazate), were synthesized and characterized by elemental analysis and X-ray single-crystal diffraction analysis. 1 is a mononuclear neutral nickel(II) complex and the center nickel atom is chelated by donors of N₂S₂ possessing a distorted tetrahedral configuration, while in 2, the adjacent two complex molecules are linked through two O atoms to form a dimer and the center zinc atom is five-coordinate in a distorted trigonal–bipyramidal geometry. The cytotoxic activity study indicated that 2 showed potent cytotoxic activity against the human liver hepatocellular carcinoma (HepG2) cancer cell lines, with IC₅₀ 2.4 ± 0.2 μg·mL^− 1, which is slightly weaker than 5-fluoroacil (5-FU) (0.89 ± 0.21 μg·mL^− 1) as reference. A gel electrophoresis assay demonstrated the ability of the complex to cleave the pBR322 plasmid DNA.     

NMR and FT-IR studies of sulfonated styrene-based homopolymers and copolymers

A series of sodium poly(styrene sulfonate)-block-poly(4-tert-butylstyrene) (NaPSS-b-PtBS) copolymers and related homopolymers were characterized by Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy. The homopolymers included polystyrene (PS), poly(4-tert-butylstyrene) (PtBS), sodium poly(4-styrene sulfonate) (NaP4SS), sodium poly(styrene sulfonate) (NaPSS) with various sulfonation levels, and partially sulfonated PtBS (PtBSS). The structures of NaPSS and PtBSS were elucidated, and the effect of sulfonation level on the NaPSS FT-IR spectrum was studied. The characteristic peaks for NaPSS and PtBSS in FT-IR and NMR spectra were identified.     

Synthesis of poly(methyl methacrylate)-g-poly(dimethyl siloxane) graft copolymers via a miniemulsion process

Summary In this article, we describe the synthesis of a PMMA-g-PDMS graft copolymer via a miniemulsion process. A highly hydrophobic PDMS macromonomer was copolymerized in the presence of MMA. Latex particles were obtained with a high yield and a complete incorporation of the macromonomer by using AIBN as initiator, SDS as a surfactant and a PMMA-b-PEO block copolymer as a cosurfactant, with a given amount of methanol in order to reduce the interfacial tension. The characterization of the resulting latex by ¹H NMR and QELS evidenced the interest of such a process in order to copolymerize monomers with very different solubilities and to obtain directly a graft copolymer in aqueous dispersion. Received: 12 March 2001/ Revised version: 15 September 2001/ Accepted: 15 September 2001     

Synthesis and adhesive property study of polyoxetanes grafted with catechols via Cu(I)-catalyzed click chemistry

Mussel-inspired catechol-containing polymers have drawn great attention due to their outstanding adhesive properties. Catechol-containing polyethylene glycol (cPEG) is a well-studied catechol-containing polymer used for tissue repair. Nevertheless, catechols can only be attached to the chain ends of polyethylene glycols thus the bonding strength of the resulting polymers is limited. Aiming at solving the problem, a series of clickable polyoxetane copolymers with grafted catechol moieties were synthesized in an efficient manner. Upon addition of FeCl₃ as the cross-linker, strong bonding strength of the adhesive was achieved. Polymer containing 15.5 molar percent of catechol showed the strongest bonding strength up to 5.59 MPa on sanded stainless steel. It was found that the triazole groups also contributed to the overall adhesive performance. This polyoxetane-based adhesive also displayed strong bonding ability to a variety of other substrates including porcine skin.     

Block copolymers derived from 2,2′-azobis(2-cyanopropanol). I. Synthesis of poly(urethane-block-methyl methacrylate) and poly(urethane-block-styrene)

Block copolymers with polyester-urethane and polymethyl methacrylate (PMMA) or polystyrene (PS) sequences were obtained by the use of polyester- or polyether-urethane macroazo initiators (PUMAI). PUMAI with a well-defined number of azo groups per chain were prepared via a two-stage reaction procedure using 2,2′-azobis(2-cyanopropanol) (ACP), 4,4′-methylene diphenyl diisocyanate (MDI) and α, ω-hydroxy polycaprolactone (PCL). The characteristics of the obtained block copolymers depend on the reaction conditions, and a yield of 98% was obtained for a P(U-b-MMA) synthesized with a ratio of macroazo initiator to monomer equal to 1/400. In similar conditions, copolymerization of styrene was more difficult, and the maximum block copolymer yield obtained in this work was only of 37% for a ratio of macroazo initiator to monomer equal to 1/150. Combination of different analyses Fourier transform infrared (FTIR) spectroscopy, proton nuclear magnetic resonance (¹H-NMR), and size exclusion chromatography (SEC) carried out on both crude and fractionated copolymers showed this kind of synthesis yielding di- and triblock copolymers and only a little amount of PU homopolymer. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 613–627, 1998     

Synthesis and characterization of H-bonded side-chain and crosslinking LC polymers containing donor/acceptor homopolymers and copolymers

Side-chain copolymers consisting of proton acceptors (stilbazoles) and proton donors (benzoic acids) connected to polyacrylate backbones with different methylene spacer lengths are prepared by tuning their donor/acceptor molar ratios. The H-bonded copolymer networks are formed once they were synthesized, and showed more homogenous phase behavior than the physical blending supramolecular networks composed of donor and acceptor homopolymers. Analogous monomer–monomer and polymer–monomer (H-bonded side-chain polymer) complexes of similar structures are also investigated. According to DSC, POM, and XRD studies, it reveals that the copolymers with various spacer lengths and donor/acceptor molar ratios show the smectic A (S_A) phase. The d spacing values of XRD results suggest that the H-bonded copolymers may be constructed by either a monolayer or an interdigitated bilayer structure. Generally, the d spacing values of copolymers (in the S_A phase) increase with higher H-bonded crosslinking density between benzoic acids and stilbazoles, i.e. decrease with higher molar ratios of benzoic acids, which may be owing to the formation of hydrogen bonds between benzoic acids from different backbones. The isotropization temperatures of the H-bonded blends and copolymers increase as the molar ratios of benzoic acids increase, while the higher H-bonded crosslinking density between benzoic acids and stilbazoles stabilizes the liquid crystalline phase.     

Synthesis of block copolymers via redox polymerization

Polymerization and copolymerization of vinyl monomers such as acrylamide, acrylonitrile, vinyl acetate, and acrylic acid with a redox system of Ce(IV) and organic reducing agents containing hydroxy groups were studied. The reducing compounds were poly(ethylene glycol)s, halogen‐containing polyols, and depolymerization products of poly(ethylene terephthalate). Copolymers of poly(ethylene glycol)s‐b‐polyacrylonitrile, poly(ethylene glycol)s‐b‐poly(acrylonitrile‐co‐vinyl acetate), poly(ethylene glycol)s‐b‐polyacrylamide, poly(ethylene glycol)s‐b‐poly(acrylamide‐co‐vinyl acetate), poly(1‐chloromethyl ethylene glycol)‐bpoly(acrylonitrile‐co‐vinyl acetate), and bis[poly(ethylene glycol terephthalate)]‐b‐poly(acrylonitrile‐co‐vinyl acetate) were produced. The yield of acrylamide polymerization and the molecular weight of the copolymer increased considerably if about 4% vinyl acetate was added into the acrylamide monomer. However, the molecular weight of the copolymer was decreased when 4% vinyl acetate was added into the acrylonitrile monomer. Physical properties such as solubility, water absorption, resistance to UV light, and viscosities of the copolymers were studied and their possible uses are discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1385–1395, 1999