Synthesis and thermal,optical, and mechanical properties of sequence‐controlled poly(1‐adamantyl acrylate)‐block‐poly(n‐butyl acrylate) containing polar side group

We prepared the sequence‐controlled block copolymers including poly(1‐adamantyl acrylate) (PAdA) and poly(n‐butyl acrylate) sequences as the hard and soft segments, respectively, by the organotellurium‐mediated living radical polymerization. The thermal, optical, and mechanical properties of the adamantane‐containing block copolymers with polar 2‐hydroxyethyl acrylate (HEA) and acrylic acid (AA) repeating units were investigated. The microphase‐separated structures of the block copolymers were confirmed by the differential scanning calorimetry and atomic force microscopy observations as well as dynamic mechanical measurements. The α‐ and β‐dispersions due to the main‐chain and side group molecular motions, respectively, of the hard and soft segments were observed. Their transition temperatures and activation energies increased due to the formation of intermolecular hydrogen bonding by the introduction of the HEA and AA repeating units. The effects of the hydrogen bonding on their tensile elasticity, strength, and strain were also evaluated. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2899–2910     

Poly(9‐undecyl‐9‐methyl‐fluorene) and poly(9‐pentadecyl‐9‐methyl‐fluorene): Synthesis,solution structure,and effect of side chain asymmetry on aggregation behavior

We report on solution aggregates and backbone conformation of poly(9‐undecyl‐9‐methyl‐fluorene) (PF1‐11) and poly(9‐pentadecyl‐9‐methyl‐fluorene) (PF1‐15), having two different side chains compared with poly(9,9‐dihexylfluorene) (PF6) and poly(9,9‐dioctylfluorene) (PF8) with two identical side chains. In the poor solvent methylcyclohexane (MCH), X‐ray scattering indicates that PF1‐11 and PF1‐15 appear as three‐dimensional aggregates (5–10 nm wide and thick), forming ribbon‐like agglomerates (correlation lengths of 100 nm). PF6 and PF8 appear as two‐dimensional aggregates (>10 nm wide and 2–3 nm thick) involving ribbon‐like agglomerates (correlation lengths much greater than 100 nm). Upon heating, all aggregates undergo a gel–sol transition which occurs at lower temperatures for PF1‐11 and PF1‐15 (<60°C) than for PF6 and PF8 (>80°C). In the good solvent toluene, PF1‐11 and PF1‐15 form networks of cylindrical particles. The mesh size and the cylinder radius are smaller in 24°C toluene (60 nm, 0.5 nm) than in 60°C MCH (300 nm, 1–2 nm). Nuclear magnetic resonance spectra in toluene‐d₈ together with density functional theory calculations suggest higher torsion angles between polymer repeat units for PF6, PF8, and PF1‐11 (less planar conformation) and a gauche arrangement of the dihedral angles between the bridge carbon atom and the side chain methylene groups in PF1‐15. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 826–837     

Synthesis and polymerization reactions of cyclic imino ethers. 5: naphthalene unit‐containing poly(ether amide)s

Poly(ether amide)s containing naphthalene unit were prepared either by the polyaddition reaction of aromatic bis(2‐oxazoline)s with the different dihydroxynaphthalenes or by the homopolyaddition of a monomer containing an oxazoline, a hydroxy, and naphthalene moieties. First, polymerization method represents AA + BB mode where 1,4‐phenylene‐2,2′‐bis(2‐oxazoline) (A) and 1,3‐phenylene‐2,2′‐bis(2‐oxazoline) (B) were used as AA monomers and four different dihydroxynaphthalenes 1–4 were used as BB monomers. In the second case, 2‐(6‐hydroxynaphthalene‐2‐yl)‐2‐oxazoline (5) was used as AB‐type monomer in thermally induced polymerizations. The time dependences of polyadditions in bulk as well as in the solution were examined. The reduction of molar mass was observed after the initial fast increase of molar mass. This can be explained by the presence of side and degradation reactions. In both cases, polyadditions resulted in the linear poly(ether amide)s, which were characterized by ¹H and ¹³C NMR spectroscopy. Thermal properties of the prepared polymers were studied by differential scanning calorimetry (DSC) measurements. Comparison of the temperatures of glass transition for polymers prepared in AA + BB mode shows the strong dependence of thermal properties on the structure of the polymers. The values were in the range of 136–171°C. The glass‐transition temperature (T_g) of poly[2‐(6‐hydroxynaphthalene‐2‐yl)‐2‐oxazoline] prepared by AB‐type polyaddition is 183°C, which corresponds to the higher contents of hard aromatic segments in the latter type of polymers compared to the polymers prepared in the AA + BB‐type polyadditions. The described polymers represent novel naphthalene unit‐containing poly(ether amide)s for different applications in material science. Copyright © 2011 John Wiley & Sons, Ltd.     

Improvement of thermal and mechanical properties of poly(L‐lactic acid) with 4,4‐methylene diphenyl diisocyanate

In this study, the thermal and mechanical properties of biodegradable poly(L ‐lactic acid) (PLA) were improved by reacting with 4,4‐methylene diphenyl diisocyanate (MDI). The resulting PLA samples were characterized with Fourier transformation infrared spectrometer (FT‐IR). The glass transition (T_g) and decomposing (T_d) temperature of the resulting products were measured using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. The tensile properties were also measured with a tensile tester. The results show that when the molar ratio of ? NCO to ? OH was 2:1, the T_g value can be increased to 64°C from the original 55°C, and the tensile strength increased from 4.9 to 5.8 MPa. This demonstrated that by reacting PLA with MDI at an appropriate portion, both the thermal and mechanical performance of PLA can be increased. Copyright © 2006 John Wiley & Sons, Ltd.     

Comparative study of poly(L‐lactide) nanocomposites with organic montmorillonite and carbon nanotubes

Organic montmorillonite (OMMT) and the one‐dimensional functionalized multiwalled carbon nanotubes (FMWCNTs) were introduced into poly(L ‐lactide) (PLLA) to prepare PLLA/OMMT and PLLA/FMWCNT nanocomposites, respectively. The effects of nanofillers on melt crystallization and cold crystallization of PLLA were comparatively investigated by using polarized optical microcopy, differential scanning calorimetry and wide angle X‐ray diffraction. The results show that FMWCNTs exhibit higher nucleation efficiency for the melt crystallization of PLLA, whereas OMMT is the better one for the cold crystallization of PLLA. Rheological properties show that both OMMT and FMWCNTs at relatively higher concentrations can form the percolated network structure in the PLLA matrix, however, the latter nanocomposites exhibit relatively denser or more compact percolated networks. The difference of the networks between OMMT and FMWCNTs is suggested to be the main reason for the different cold crystallization behaviors observed in the PLLA/OMMT and PLLA/FMWCNT nanocomposites. The dynamic mechanical analysis measurements show that OMMT is the better one to improve the stiffness of the nanocomposites in the present work. The thermogravimetric analysis measurements show that FMWCNTs have higher efficiency in improving the thermal stability of PLLA compared with OMMT. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Organic–inorganic poly(N‐vinylpyrrolidone) copolymers with double‐decker silsesquioxane in the main chains: Synthesis,glass transition,and self‐assembly behavior

An organic–inorganic copolymer with polyhedral oligomeric silsesquioxane (POSS) and xanthate moieties in the main chain was synthesized via the polycondensation between 3,13‐di(2‐bromopropionate)propyl double‐decker silsesquioxane (DDSQ) and 1,4‐di(xanthate potassium)butane. This hybrid copolymer was used as the macromolecular chain transfer agent to obtain the organic–inorganic poly(N‐vinylpyrrolidone) (PVPy) copolymers via a reversible addition fragmentation chain transfer/macromolecular design via the interchange of xanthates (RAFT/MADIX) polymerization approach; the polymerization behavior of N‐vinyl pyrrolidone was investigated by means of gel permeation chromatography. It was found that the polymerization was in a living and controlled manner. Transmission electron microscopy (TEM) showed that the organic–inorganic PVPy copolymers with DDSQ in the main chains were microphase‐separated in bulks. Compared to plain PVPy, the organic–inorganic PVPy copolymers displayed the decreased glass transition temperatures (T_gs); the decreased T_gs are attributable to the effect of the introduced DDSQ cages on the packing of PVPy chains as evidenced by means of Fourier transform infrared spectroscopy (FTIR). In water, the organic–inorganic PVPy copolymers can self‐assemble into the spherical nano‐objects with the size of 20–50 nm in diameter. In the self‐assembled nano‐objects, the aggregates of the hydrophobic DDSQ constituted the cores of the polymeric micelles whereas the PVPy chains between the DDSQ behaved as the coronas of the polymeric micelles. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2949–2961     

Pulsed‐laser–deposited and plasma‐polymerized polytetrafluoroethylene (PTFE)‐like thin films: A comparative study on PTFE‐specific properties

Glass‐like and structural first‐order phase transitions are investigated in polytetrafluoroethylene (PTFE) foils and PTFE‐like films prepared by pulsed‐laser deposition (PLD) and plasma polymerization (PP). A structural comparison of the investigated polymers is performed by infrared spectroscopy and dielectric dilatometry. It is shown that dielectric dilatometry (the measurement of the susceptance vs. temperature) provides a simple and elegant means for detecting volumetric transitions in thin nonpolar polymer films. In conventional PTFE foils, the known glass‐like and structural first‐order phase transitions are identified. The structure of pulsed‐laser deposited PTFE strongly depends on the target material, ranging from highly crystalline films showing only structural phase transitions to films strongly deviating from PTFE foils, with structural characteristics comparable to plasma‐polymerized fluorocarbons. The dielectric loss of the highly crystalline PLD films compares favorably with conventional PTFE foils, making the films attractive for new applications in miniature electret devices. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2115–2125, 1999     

Organic–inorganic hybrid diblock copolymer composed of poly (ε‐caprolactone) and poly(MA POSS): Synthesis and its nanocomposites with epoxy resin

Organic–inorganic hybrid diblock copolymers composed of poly(ε‐caprolactone) and poly(MA POSS) [PCL‐b‐P(MA POSS)] were synthesized via reversible addition‐fragmentation chain transfer polymerization of 3‐methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane (MA POSS) with dithiobenzoate‐terminated poly(ε‐caprolactone) as the macromolecular chain transfer agent. The dithiobenzoate‐terminated poly(ε‐caprolactone) (PCL‐CTA) was synthesized via the atom transfer radical reaction of 2‐bromopropionyl‐terminated PCL with bis(thiobenzoyl)disulfide in the presence of the complex of copper (I) bromide with N,N,N′,N″,N″‐pentamethyldiethylenetriamine. The results of molecular weights and polydispersity indicate that the polymerizations were in a controlled fashion. The organic–inorganic diblock copolymer was incorporated into epoxy to afford the organic–inorganic nanocomposites. The nanostructures of the organic–inorganic composites were investigated by means of transmission electron microscopy and dynamic mechanical thermal analysis. Thermogravimetric analysis shows that the organic–inorganic nanocomposites displayed the increased yields of degradation residues compared to the control epoxy. In the organic–inorganic nanocomposites, the inorganic block [viz., P(MA POSS)] had a tendency to enrich at the surface of the materials and the dewettability of surface for the organic–inorganic nanocomposites were improved in terms of the measurement of surface contact angles. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

The synthesis and characterization of new thermoplastic poly(thiourethane‐urethane)s

New thermoplastic segmented poly(thiourethane‐urethane)s (SPTUUs) were prepared by a one‐step melt polymerization from 20 to 80 mol % poly(tetramethylene oxide) of = 1000 or poly(hexamethylene carbonate) diol (PHCD) of = 860 as soft segments, hexamethylene diisocyanate (HDI) and bis[4‐(mercaptomethyl)phenyl]methanone (BMMPM) as a new dithiol chain extender at the NCO/(OH + SH) molar ratio of 1 in the presence of dibutyltin dilaurate as a catalyst. The structures of the SPTUUs were examined by FTIR, X‐ray diffraction analysis, and scanning electron microscopy. The SPTUUs were also characterized by physicochemical, thermal, and tensile properties as well as Shore A/D hardness. The SPTUUs with the PHCD soft segments showed better tensile properties than those with the PTMO soft segments. A nonsegmented polythiourethane based on BMMPM and HDI is also described. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1770–1782, 2008     

Thermotropic liquid‐crystalline poly(oxadiazole)s with poly(methylene) spacers: Preparation and extraordinary odd–even effect

A novel synthetic procedure for the preparation of poly(oxadiazole)s was developed with nucleophilic substitution of α,ω-alkanediols with oxadiazole-activated bisfluoride. Seven poly(oxadiazole)s were successfully prepared by the solution polymerization of 2,5-bis(4-fluorophenyl)-1,3,4-oxadiazole and various α,ω-alkanediols [HO (CH₂)_n OH, n = 5–10 or 12] in diphenyl sulfone at temperature greater than 230 °C with K₂CO₃ as a catalyst. The reduced viscosities of the poly(oxadiazole)s were 0.14–0.51 dL/g, and the decomposition temperatures were greater than 350 °C and decreased from 436 to 379 °C with increasing spacer length (n). Corresponding model compounds, consisting of two terminal mesogenic 2,5-bisphenyl-1,3,4-oxadiazole units and central poly(methylene) spacers, were also prepared for comparison. Both the polymers and model compounds exhibited an extraordinary odd–even effect: odd ones showed higher transition temperatures (melting and clearing temperatures). With differential scanning calorimetry, polarized optical microscopy (POM), and X-ray diffraction, we found that the nematic mesophase was the only texture in the melts except for the polymers with longer methylene units (n = 9), in which smectic mesophases were observed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 293–301, 2002     

High‐Pressure Synthesis and Structural Investigation of H3P8O8N9: A New Phosphorus(V) Oxonitride Imide with an Interrupted Framework Structure

The first crystalline phosphorus oxonitride imide H₃P₈O₈N₉ (=P₈O₈N₆(NH)₃) has been synthesized under high‐pressure and high‐temperature conditions. To this end, a new, highly reactive phosphorus oxonitride imide precursor compound was prepared and treated at 12 GPa and 750 °C by using a multianvil assembly. H₃P₈O₈N₉ was obtained as a colorless, microcrystalline solid. The crystal structure of H₃P₈O₈N₉ was solved ab initio by powder X‐ray diffraction analysis, applying the charge‐flipping algorithm, and refined by the Rietveld method (C2/c (no. 15), a=1352.11(7), b=479.83(3), c=1820.42(9) pm, β=96.955(4)°, Z=4). H₃P₈O₈N₉ exhibits a highly condensed (κ=0.47), 3D, but interrupted network that is composed of all‐side vertex‐sharing (Q⁴) and only threefold‐linking (Q³) P(O,N)₄ tetrahedra in a Q⁴/Q³ ratio of 3:1. The structure, which includes 4‐ring assemblies as the smallest ring size, can be subdivided into alternating open‐branched zweier double layers {oB,${2{{2\hfill \atop \infty \hfill}}}$ }[²P₃(O,N)₇] and layers containing pairwise‐linked Q³ tetrahedra parallel (001). Information on the hydrogen atoms in H₃P₈O₈N₉ was obtained by 1D ¹H MAS, 2D homo‐ and heteronuclear (together with ³¹P) correlation NMR spectroscopy, and a ¹H spin‐diffusion experiment with a hard‐pulse sequence designed for selective excitation of a single peak. Two hydrogen sites with a multiplicity ratio of 2:1 were identified and thus the formula of H₃P₈O₈N₉ was unambiguously determined. The protons were assigned to Wyckoff positions 8f and 4e, the latter located within the Q³ tetrahedra layers.     

Synthesis and characterization of poly(higher‐α‐olefin)s with a nickel(α‐diimine)/methylaluminoxane catalyst system: Effect of chain running on the polymer properties

Homopolymerization of octadecene‐1 at different reaction conditions has been studied. Significant chain running can be seen at higher polymerization temperatures. Interestingly, insertion of octadecene‐1 into a sterically hindered nickel‐cation/carbon (secondary) bond is observed. The microstructure of the polymer was established using NMR spectroscopy. The effects of chain running on polymer melting, crystallization behavior, and dynamic mechanical thermal properties were studied using DSC and DMTA. The extent of chain running (i.e., 2,ω‐, 1,ω‐enchainments) decreases with an increase in the carbon number of α‐olefins. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 191–210, 2007     

Structure and properties of segmented poly(urethaneurea)s with relatively short hard‐segment chains

We report the structure and properties of segmented poly(urethaneurea) (SPUU) with relatively short hard‐segment chains. The SPUU samples comprised poly(tetramethylene glycol) prepolymer as a soft segment and 4,4′‐diphenylmethane diisocyanate (MDI) units as a hard segment that were extended with ethylenediamine. To discuss quantitatively the conformation of the soft‐segment chain in the microphase‐separated domain space, we used SPUU samples for which the molecular weights of the hard‐ and soft‐segment chains are well characterized. The effects of the cohesive force in the hard‐segment chains on the structure and properties of SPUU were also studied with samples of different chain lengths of the hard segment, although the window of x_H, the average number of MDI units in a hard‐segment chain, was narrow (2.38 ≤ x_H ≤ 2.77). There were urethane groups in the soft segments and urea groups in the hard segments. Because of a strong cohesive force between the urea groups, we could control the overall cohesive force in the hard‐segment chains by controlling the chain lengths of the hard segment. First of all, microphase separation was found to be better developed in the samples with longer hard‐segment chains because of an increase of the cohesive force. It was also found that the interfacial thickness became thinner. The long spacing for the one‐dimensionally repeating hard‐ and soft‐segment domains could be well correlated with the molecular characteristics when the assumption of Gaussian conformation was employed for the soft‐segment chains. This is unusual for strongly segregated block copolymers and might be characteristic of multiblock copolymers containing rod–coil chains. The tensile moduli and thermal stability temperature, T_H, increased with an increase of the cohesive force, whereas the glass‐transition temperature, the melting temperature, and the degree of crystallinity of the soft‐segment chains decreased. The increase in T_H especially was appreciable, although the variation in the chain length of the hard segment was not profound. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1716–1728, 2000     

Side‐chain conformational changes during the thermoshrinking process: γ‐Ray polymerization and spectroscopic study of uncrosslinked poly(methacryloyl‐Ala‐OMe)

Poly(methacryloyl‐L ‐alanine‐methyl ester) (1) has an optically active side chain and consists of thermoshrinking hydrogels upon crosslinking. We synthesized an uncrosslinked polymer of 1 by the γ‐ray polymerization method. For the prepared polymer, variable‐temperature circular dichroism (CD) and ¹H NMR spectra were studied, and we found conformational changes in the optically active side chains during the thermally induced phase transition. Intense CD spectra reveal ordered conformation in the side chain of 1 below the phase transition temperature (∼28 °C). A well‐resolved ¹H NMR spectrum of 1 at 0 °C shows that the conformational angles in the polymer side chain are fixed at low‐energy minima. With increasing temperature, the frozen side chain starts rotating vigorously and takes an unordered orientation. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2671–2677, 2000     

Design and preparation of poly(lactic acid) hydroxyapatite nanocomposites reinforced with phosphorus‐based organic additive: Thermal,combustion, and mechanical properties studies

A new phosphorus‐based organic additive (PDA) was designed and successfully synthesized using a three‐component reaction for improvement of the thermal and combustion resistance of polylactic acid (PLA). For compensate for mechanical properties of PLA, hydroxyapatite nanoparticles was modified via in situ surface modification with PDA and was used for preparation of PLA nanocomposites. The structure and morphology as well as thermal, combustion, and mechanical properties of the all PLA systems were investigated. The X‐ray diffraction (XRD) and field‐emission scanning electron microscopy (FE‐SEM) results indicated that the presence of PDA as surface modifier has been necessary for a desirable dispersion of hydroxyapatite (HA) nanoparticles in the PLA matrix. The thermal, combustion, and mechanical properties of the PLA system films were investigated using thermogravimetric analysis (TGA), microscale combustion calorimeter (MCC), and tensile test, respectively. The initial decomposition temperature and char residue of PLA containing 6 mass% of PDA along with 2 mass% HA nanoparticles were increased 20°C and 12% respectively, compared with that of the neat PLA. The peak of heat release rate was decreased from 566 W/g for the neat PLA to 412 W/g for PLA containing 2 mass% of PDA along with 6 mass% HA nanoparticles. By incorporation of only 2 mass% HA nanoparticles and 6 mass% of PDA, the tensile strength was obtained 51 MPa higher than that of the neat PLA.     

Synthesis,structural characterization and computational studies of catena‐poly[chlorido[μ3‐(pyridin‐1‐ium‐3‐yl)phosphonato‐κ3O:O′:O′′]zinc(II)]

Coordination polymers are constructed from two basic components, namely metal ions, or metal‐ion clusters, and bridging organic ligands. Their structures may also contain other auxiliary components, such as blocking ligands, counter‐ions and nonbonding guest or template molecules. The choice or design of a suitable linker is essential. The new title zinc(II) coordination polymer, [Zn(C₅H₅NO₃P)Cl]_n , has been hydrothermally synthesized and structurally characterized by single‐crystal X‐ray diffraction and vibrational spectroscopy (FT–IR and FT–Raman). Additionally, computational methods have been applied to derive quantitative information about interactions present in the solid state. The compound crystallizes in the monoclinic space group C 2/c . The four‐coordinated Zn^II cation is in a distorted tetrahedral environment, formed by three phosphonate O atoms from three different (pyridin‐1‐ium‐3‐yl)phosphonate ligands and one chloride anion. The Zn^II ions are extended by phosphonate ligands to generate a ladder chain along the [001] direction. Adjacent ladders are held together via N—H…O hydrogen bonds and offset face‐to‐face π–π stacking interactions, forming a three‐dimensional supramolecular network with channels. As calculated, the interaction energy between the neighbouring ladders is −115.2 kJ mol⁻¹. In turn, the cohesive energy evaluated per asymmetric unit‐equivalent fragment of a polymeric chain in the crystal structure is −205.4 kJ mol⁻¹. This latter value reflects the numerous hydrogen bonds stabilizing the three‐dimensional packing of the coordination chains.     

Synthesis,structure and properties of a new three‐dimensional interpenetrated metal–organic framework with 3,3′‐azodibenzoic acid (H2azdc) and 1,4‐bis(1H‐imidazol‐1‐yl)butane (bimb): {[Cd(azdc)(bimb)2]·H2O}n

A new three‐dimensional interpenetrated Cd^II–organic framework based on 3,3′‐azodibenzoic acid [3,3′‐(diazenediyl)dibenzoic acid, H₂azdc] and the auxiliary flexible ligand 1,4‐bis(1H‐imidazol‐1‐yl)butane (bimb), namely poly[[bis[μ₂‐1,4‐bis(1H‐imidazol‐1‐yl)butane‐κ²N³:N^3′][μ₂‐3,3′‐(diazenediyl)dibenzoato‐κ²O:O′]cadmium(II)] monohydrate], {[Cd(C₁₄H₈N₂O₄)(C₁₀H₁₄N₂)₂]·H₂O}_n, (1), was obtained by a typical solution reaction in mixed solvents (water and N,N′‐dimethylformamide). Each Cd^II centre is six‐coordinated by two O atoms of bis‐monodentate bridging carboxylate groups from two azdc²⁻ ligands and by four N atoms from four bimb ligands, forming an octahedral coordination environment. The Cd^II ions are connected by the bimb ligands, resulting in two‐dimensional (4,4) layers, which are further pillared by the azdc²⁻ ligands, affording a threefold interpenetrated three‐dimensional α‐Po topological framework with the Schläfli symbol 4¹²6³. The thermal stability and solid‐state fluorescence properties of (1) have been investigated.