Preparation and thermal studies of self-crosslinked terpolymer derived from 4-acetylpyridine oxime, formaldehyde and acetophenone

Terpolymer (4-APOFA) has been synthesized using the monomer 4-acetylpyridine oxime, formaldehyde and acetophenone in 1:5:1 molar proportion. The structure of 4-APOFA terpolymer has been elucidated based on various physicochemical techniques, i.e., FT-IR, ¹H NMR, Pyrolyis GC/MS and viscosity average molecular weight. The glass transition temperature (T_g) and thermal stability of terpolymer have been determined by DSC. The activation energy of the thermal reaction has been determined with differential scanning calorimetry using Kissinger method. The apparent activation energies (E_a) of each step during thermodegradation have been determined using Flynn-Wall-Ozawa method. The type of solid-state mechanism has been established by Craido method. From the calculation, the solid-state thermal mechanism is proposed to be D₃ (three-dimensional diffusion) at initial decomposition state and F₁ (random nucleation with one nucleus on the individual particle) at second decomposition state for 4-APOFA. It has also been shown to possess excellent antimicrobial activities as compared to other cationic resins.     

Synthesis, characterization and thermal degradation of 8-hydroxyquinoline-guanidine-formaldehyde terpolymer

Terpolymer (8-HQGF) has been synthesized using the monomers 8-hydroxyquinoline, guanidine, formaldehyde in 1:1:2 molar proportions. The structure of 8-HQGF terpolymer has been elucidated on the basis of elemental analysis and various physicochemical techniques, i.e. UV-Visible, FTIR-ATR and ¹H NMR spectroscopy. Detailed thermal degradation study of the new terpolymer has been carried out to ascertain its thermal stability. Thermal degradation curve is discussed which shows two decomposition steps (265-475 °C and 540-715 °C). Sharp-Wentworth and Freeman-Carroll methods have been used to calculate activation energies and thermal stability. The activation energy (E_a) calculated by using the Sharp-Wentworth (21.98 kJ/mol) has been found to be in good agreement with that calculated by Freeman-Carroll (23.57 kJ/mol) method. Thermodynamic parameters such as free energy change (ΔF), entropy change (ΔS), apparent entropy change (S^∗) and frequency factor (Z) have also been evaluated on the basis of the data of Freeman-Carroll method. The order of reaction (n) is found out to be 0.9979.     

Oxidative copolymerization of indene with p‐tert‐butylstyrene: Synthesis,characterization, thermal analysis,and reactivity ratios

Copolyperoxides of indene and p‐tert‐butylstyrene of different compositions were synthesized by free‐radical‐initiated oxidative copolymerization. The compositions of the copolyperoxides, obtained from ¹H and ¹³C NMR spectra, were used to calculate the reactivity ratios of the monomers. The reactivity ratios indicated a larger proportion of indene units in random placement in the copolyperoxides. Thermal‐degradation studies by differential scanning calorimetry and electron‐impact mass spectrometry supported alternating peroxide units in the copolymer backbone. The activation energy for thermal degradation suggested that the degradation was dependent on the dissociation of the peroxide (? O? O? ) bonds in the backbone of the copolyperoxide chain. The flexibility of the copolyperoxides was examined in terms of the glass‐transition temperature. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 9–18, 2002     

Synthesis and swelling behavior of amphiphilic comb‐like branched polymer (AA‐co‐CMS)‐g‐PMMA

Copolymerization of acrylic acid and p‐chloromethylstyrene (p‐CMS) in dioxane initiated with α,α′‐azobisisobutyronitrile was carried out to produce macroinitiator P(AA‐co‐CMS) containing PhCH₂Cl group at 65°C. Then methyl methacrylate was grafted onto P(AA‐co‐CMS) backbone using PhCH₂Cl group as an initiation site and FeCl₂/triphenyl phosphine complex as a catalyst. The resulted copolymer (AA‐co‐CMS)‐g‐PMMA with a comb‐like branched structure has a hydrophilic backbone (PAA) and hydrophobic side chains (PMMA). Compositions and structures of macroinitiator and the grafted product of P(AA‐co‐CMS)‐g‐PMMA were determined by ¹H‐NMR, infrared (IR), and gel permeation chromatography (GPC). The average graft number, the average length of branch chains, the graft ratio, and the graft efficiency were investigated. The swelling behavior of the comb‐like branched polymer was also investigated. The gradual increase of swelling ratios was accompanied by an increase of pH and temperature. The kinetic exponents indicated that the swelling transport mechanisms transformed from Fickian diffusion to non‐Fickian transport as the decreasing pH. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis, crystal structures and properties of four manganese coordination polymers with 4,4-bipyridine-derived ligands

Four new coordination polymers, namely Mn₂(4,4-bpy)₂(o-tol)₄ 1, Mn₂(4,4-bpy)₂(m-tol)₄ 2, Mn₂(bpp)₂(m-tol)₄ 3 and {[Mn₂(4,4-bpy)₂(p-tol)₄][Mn(4,4-bpy)₂(H₂O)₂(p-tol)₂]}·6H₂O 4 have been synthesized from 4,4′-bipyridine (4,4-bpy), 1,3-bis(4-pyridyl)-propane (bpp), o-toluic acid (o-Htol), m-toluic acid (m-Htol) and p-toluic acid (p-Htol). All four complexes feature dinuclear Mn₂(tol)₄ moieties, which are bridged by 4,4-bpy or bpp ligands to form 1D double-chain structures. The resulted 1D double-chains are assembled via hydrogen bonding or π···π stacking into 2D supramolecular layers. The complexes were characterized by physico-chemical (thermal behavior) and infrared spectroscopy. Variable temperature magnetic characterization suggest weak antiferromagnetic coupling exchange between dimeric Mn(II) centers (J = ?0.46 cm^?1 for 1, ?0.56 cm^?1 for 2, ?1.28 cm^?1 for 3 and ?0.59 cm^?1 for 4).     

Thermogravimetric study of 8-hydroxyquinoline 5-sulfonic acid–melamine–formaldehyde terpolymer resins-II

The title terpolymer (8-HQ5-SAMF-II) is synthesized by the condensation of 8-hydroxyquinoline 5-sulfonic acid (8-HQ5-SA) and melamine (M) with formaldehyde (F) in the presence of acid catalyst and using 2:1:3 M proportions of the reacting monomers. The synthesized terpolymer resin is then characterized by different physicochemical techniques viz. number average molecular mass determination, intrinsic viscosity determination, and spectral studies like UV–Visible, IR, ¹H NMR, and ¹³C NMR spectra. The morphology of synthesized terpolymer was studied by scanning electron microscopy (SEM). The thermogravimetry of the terpolymer resin prepared in this study has been carried out by non-isothermal thermogravimetry technique in which sample is subjected to condition of continuous increase in temperature at linear rate. Thermal study of the resin was carried out to determine their mode of decomposition and relative thermal stabilities. Thermal decomposition curves were studied carefully with minute details. The Freeman-Carroll and Sharp-Wentworth methods have been used in the present investigation to calculate thermal activation energy and different kinetic parameter of the terpolymer resins. Thermal activation energy E _a calculated with the two above-mentioned methods are in close agreement. The advantage of Freeman-Carroll method is to calculate both the order of reaction n and energy of activation in one single stage by keeping heating rate constant. By using data of thermogravimetry, various thermodynamic parameters like frequency factor Z, entropy change ΔS, free energy change ΔF, and apparent entropy S* have been determined using Freeman-Carroll method.     

Thermal properties of polyimide system containing silicone segments

The influence of the structure properties relationships of silicone incorporated polyimide (PI) on thermal stability was investigated by using single scan thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) in nitrogen. Four systems have been synthesized based on monomer 4-(4-(1-(4-(4-aminophenoxy) phenyl)-1-methylethyl) phenoxy) aniline (BAPP)/3,3??,4,4??-Biphenyltetracarboxylic dianhydride including parent PI (S-1), PI siloxane copolymer (S-2 and S-3), and PI siloxane hybrid (S-4). The derivative thermogravimetric analysis (DTG) and DSC curves indicate a double and single stage decomposition process and glass transition temperature (T _g), respectively. While the PI, PIS, and PSH showed distinctive features towards thermal analysis, it was found that the rate of degradation (???/??t) was influenced by the flexibility of Si?CO?CSi in the backbone and in Si?CO?CSi itself. These results revealed that the presence of Si?CO?CSi in either the backbone or matrix indicates its stability with regard to high thermal service applications.     

Preparation of telechelic oligomers by controlled thermal degradation of isotactic poly(1-butene) and poly(propylene-ran-1-butene)

It was found that telechelic isotactic oligo(1-butene) and telechelic oligo(propylene-ran-1-butene) could be isolated as nonvolatile oligomers from polymer residues resulting from the thermal degradation of isotactic poly(1-butene) and poly(propylene-ran-1-butene), respectively. Their structures were determined by ¹H and ¹³C NMR with attention being paid to their reactive end groups. The maximum average number of terminal vinylidene groups per molecule (f_TVD) was 1.8, indicating that about 80 mol% were α,ω-diene oligomers having two terminal vinylidene groups. This useful new telechelic oligomer had a lower polydispersity than the original polymer, in spite of its lower molecular weight and T_m. The composition of end groups of nonvolatile oligomers obtained by thermal degradation of poly(propylene-ran-1-butene) could be explained by the differences in bond dissociation energy and activation energy of elementary reactions during thermal degradation, based on the monomer composition of the original polymer.     

Formation of Zinc(II) and Cadmium(II) Complexes with Pyridine Oxime Ligands in Aqueous Solution

Complex formation equilibria involving pyridine-2-carboxaldehyde oxime (1), 1-(2-pyridinyl)ethanone oxime (2) and 6-methylpyridine-2-carboxaldehyde oxime (3), HL, with zinc(II) and cadmium(II) ions were studied in aqueous 0.1 M NaCl solution at 25° C by potentiometric titrations with a glass electrode. Experimental data were analysed with the least-squares computer program SUPERQUAD to determine the complexes formed and their stability constants. With Ligands 1 and 2 the sets of complexes for Zn(II) and Cd(II) are essentially the same, mono- and dinuclear oxime complexes and their deprotonated/hydrolysed products H_pM_q(HL)^2q+p _r. Owing to the steric requirements of the 6-methyl group, sets of complexes formed with 3 are distinctly different. For zinc(II), only dinuclear oximato species H_pZn₂(HL)^4q+p ₂ ( p = ? 2, ? 3, ? 4) are found, while for the larger cadmium(II) ion mononuclear oximato species CdL⁺ and CdL₂ are detected in addition to the dinuclear complex H_pCd₂(HL)^4q+p ₂ ( p = ? 3).     

Synthesis, physical and electrochemical characterization of mono- and heterobinuclear m-functionalized iron(III) Schiff base complexes

Mo(NO)T _p ^* Cl₂ (T _p ^* ?=?3,5-dimethyl pyrazole) when reacted with m-functionalized Fe(III) Schiff base complexes; the Schiff base ligands being derived from condensation of 2,4-dihydroxybenzaldehyde or salicylaldehyde with a variety of ??,??-diamines [1,2-C₆H₄(NH₂)₂, NH₂(CH₂) _n NH₂; n?=?2?C4] affords bimetallic complexes containing two potential reduction centers. The compounds were characterized by physicochemical and spectroscopic methods. It is shown that as the polymethylene carbon chain of the Schiff base backbone increases, the physicochemical and spectroscopic properties also change gradually. Electrochemical data show that the m-functionalized complexes reduce at potentials less cathodic than their p-substituted analogues. It is also shown that the redox potentials are solvent dependent.     

Thermal properties and flame retardancy of novel epoxy based on phosphorus‐modified Schiff‐base

Through addition reaction of Schiff‐base terephthalylidene‐bis‐(p‐aminophenol) ( DP‐1 ) and diethyl phosphite (DEP), a novel phosphorus‐modified epoxy, 4,4'‐diglycidyl‐(terephthalylidene‐bis‐(p‐aminophenol))diphosphonate ether ( EP‐2 ), was obtained. An modification reaction between EP‐2 and DP‐1 resulted in an epoxy compound, EP‐3 , possessing both phosphonate groups and C?N imine groups. The structure of EP‐2 was characterized by Fourier transform infrared (FTIR), elemental analysis (EA), ¹H, ¹³C, and ³¹P NMR analyses. The thermal properties of phosphorus‐modified epoxies cured with 4,4'‐diaminodiphenylmethane (MDA) and 4,4'‐diaminodiphenyl ether (DDE) were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The activation energies of dynamic thermal degradation (E_d) were calculated using Kissinger and Ozawa's methods. The thermal degradation mechanism was characterized using thermogravimetric analysis/infrared spectrometry (TG‐IR). In addition, the flame retardancy of phosphorus‐modified epoxy thermosets was evaluated using limiting oxygen index (LOI) and UL‐94 vertical test methods. Via an ingenious design, phosphonate groups were successfully introduced into the backbone of the epoxies; the flame retardancy of phosphorus‐modified epoxy thermosets was distinctly improved. Due to incorporation of C?N imine group, the phosphorus‐modified epoxy thermosets exhibited high thermal stabilities; the values of glass‐transition temperatures (T_gs) were about 201–210°C, the values of E_d were about 220–490 kJ/mol and char yields at 700°C were 49–53% in nitrogen and 45–50% in air. These results showed an improvement in the thermal properties of phosphorus‐modified epoxy by the incorporation of C?N imine groups. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and spectral characterization of some complexes of platinum(II) containing η-methyleugenol

Several complexes of the formula trans-[Pt(Meug)(Am)Cl₂], Meug: methyleugenol (4-allyl-1,2-dimethoxybenzene), a η²-coordinated olefin, and Am: ammine, methylamine, diethylamine, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine and p-anisidine have been prepared. UV, IR, Raman, ¹H NMR, ¹³C NMR and 2D NMR spectra of the complexes were recorded and analyzed.     

Pyrolysis mechanism of trisbipyridineiron(II) chloride to iron nanoparticles

Pyrolysis of trisbipyridineiron(II) chloride under controlled thermal conditions and inert atmosphere of argon gas yields a residue of iron nanoparticles. Evolved gas analysis by GC?CMS and ¹H NMR revealed emission of bipyridine, 6-chlorobipyridine, 6,6??-dichlorbipyridine, bipyridine hydrochloride, and hydrochloric acid as decomposition products. CHN, XRPD, EDXRF, TEM, AFM, and ⁵⁷Fe M?ssbauer spectroscopy of the residue indicated formation of pure iron nanoparticles in the size range of 50?C72?nm. Based on these results a mechanism for thermal degradation of trisbipyridineiron(II) chloride has been worked out.     

Biodegradable liquid crystalline aromatic/aliphatic copolyesters. Part I: Synthesis, characterization, and hydrolytic degradation of poly(butylene succinate-co-butylene terephthaloyldioxy dibenzoates)

To increase the thermal and mechanical properties of the aliphatic polyester poly(butylene succinate) (PBS), a series of potentially biodegradable liquid crystalline aromatic/aliphatic random copolyesters were prepared by melt polycondensation of new mesogenic monomers dimethyl 4,4′-(terephthaloyldioxy) dibenzoate (MTB), dimethyl succinate, and 1,4-butanediol. The synthesized copolyesters were characterized by means of proton nuclear magnetic resonance spectroscopy (¹H NMR), gel permeation chromatography (GPC), viscosity measurements, differential scanning calorimetry (DSC), thermogravimetry (TG), X-ray diffraction (XRD), polarizing light microscopy (PLM) and mechanical property measurements. The MTB content was varied so that the effects of the mesogen content on the thermal and mechanical properties, degradable behaviours and mesophase were examined. It was found that introducing the rigid rod mesogens could increase the thermal stability and the mechanical properties, while it reduced the melting temperature (T_m), the crystallization temperature (T_c), the degree of relative crystallinity (X_c) and the hydrolytic degradation rate. Only the homopolyester poly(butylenes terephthaloyldioxy dibenzoates) was able to show the schlieren texture characteristic of nematics.     

NMR assignments and the acid–base characterization of the pomegranate ellagitannin punicalagin in the acidic pH-range

In exploring the capability of nuclear magnetic resonance (NMR) spectroscopy for pomegranate juice analysis, the eight aromatic singlet resonances of α- and β-punicalagin were clearly identified in the ¹H NMR spectra of juice samples. The four downfield resonances were found to be sensitive to small pH changes around pH 3.50 where the NMR spectra of the juice samples were recorded. To understand this unusual behavior, the ¹H and ¹³C resonance assignments of the punicalagin anomers were determined in aqueous solution and pH titrations with UV and ¹H NMR detection carried out to characterize the acid–base properties of punicalagin over the pH range 2–8. Simultaneous fitting of all of the pH-sensitive ¹H NMR signals produced similar but significantly different pK _a values for the first two deprotonation equilibria of the gallagic acid moiety of the punicalagin α- (pK _a1?=?4.57?±?0.02, pK _a2?=?5.63?±?0.03) and β- (pK _a1?=?4.36?±?0.01, pK _a2?=?5.47?±?0.02) anomers. Equivalent pK _a values, (α?:?6.64?±?0.01, β?:?6.63±?0.01) were measured for the third deprotonation step involving the ellagic acid group, in good agreement with a prior literature report. The punicalagin anomer equilibrium readjusts in parallel with the proton dissociation steps as the pH is raised such that β-punicalagin becomes the most abundant anomer at neutral pH. The unusual upfield shifts observed for the glucose H3 and H5 resonances with increasing pH along with the shift in the α/β anomer equilibrium are likely the consequence of a conformational rearrangement.

Excess molar quantities of (a halogenated n-alkane + an n-alkane) A comparative study of mixtures containing either 1-chlorobutane or 1,4-dichlorobutane

Excess molar volumes V_m^E at 298.15 K were obtained, as a function of mole fraction x, for series I: {x1-C₄H₉Cl + (1 ? x)n-C_lH_{2l + 2}}, and II: {x1,4-C₄H₈Cl₂ + (1 ? x)n-C_lH_{2l + 2}}, for l = 7, 10, and 14. 10, and 14. The instrument used was a vibrating-tube densimeter. For the same mixtures at the same temperature, a Picker flow calorimeter was used to measure excess molar heat capacities C_{p, m}^E at constant pressure. V_m^E is positive for all mixtures in series I: at x = 0.5, V_m^E/(cm³ · mol^?1) is 0.277 for l = 7, 0.388 for l = 10, and 0.411 for l = 14. For series II, V_m^E of {x1,4-C₄H₈Cl₂ + (1 ? x)n-C₇H₁₆} is small and S-shaped, the maximum being situated at x_max = 0.178 with V_m^E(x_max)/(cm³ · mvl^?1) = 0.095, and the minimum is at x_min = 0.772 with V_m^E(x_min)/(cm³ · mol^?1) = ?0.087. The excess volumes of the other mixtures are all positive and fairly large: at x = 0.5, V_m^E/(cm³ · mol^?1) is 0.458 for l = 10, and 0.771 for l = 14. The C_{p, m}^Es of series I are all negative and |C_{p, m}^E| increases with increasing l: at x = 0.5, C_{p, m}^E/(J · K^?1 · mol^?1) is ?0.56 for l = 7, ?1.39 for l = 10, and ?3.12 for l = 14. Two minima are observed for C_{p, m}^E of {x1,4-C₄H₈Cl₂ + (1 ? x)n-C₇H₁₆}. The more prominent minimum is situated at x′_min = 0.184 with C_{p, m}^E(x′_min)/(J · K^?1 · mol^?1) = ?0.62, and the less prominent at x″_min = 0.703 with C_{p, m}^E(x″_min)/(J · K^?1 · mol^?1) = ?0.29. Each of the remaining two mixtures (l = 10 and 14) has a pronounced minimum at low mole fraction (x_min = 0.222 and 0.312, respectively) and a broad shoulder around x = 0.7.     

Reactivity ratios for the terpolymerization of methyl methacrylate,vinyl acetate,and molecular oxygen

The copolymerization of methyl methacrylate (MMA) and vinyl acetate (VAc) under high oxygen pressure was investigated. Copolyperoxides of various compositions were synthesized by the free‐radical‐initiated oxidative copolymerization of MMA and VAc monomers. The copolyperoxide compositions obtained from ¹H and ¹³C NMR spectra were used for determining the reactivity ratios of the monomers. The reactivity ratios indicated a larger proportion of MMA units statistically placed in the copolyperoxides. A theoretical analysis based on semiempirical AM1 calculations was performed to support the reactivity ratios. NMR studies showed irregularities in the copolyperoxide chain due to the cleavage reactions of the propagating peroxide radical. Thermal analyses of the copolyperoxides by differential scanning calorimetry gave evidence for the presence of alternating peroxide units in the copolyperoxide chain. The activation energies of thermal degradation suggested that degradation was controlled by the dissociation of the peroxide (? O? O? ) bond in the backbone of the copolyperoxide chain. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 564–572, 2002; DOI 10.1002/pola.10115     

Stilbene‐containing polyactylenes: Molecular design,synthesis, and relationship between molecular structure and NLO properties

Polyacetylenes ( P1–P4 ) containing different stilbene groups, ? [(CH?C) ? Ph? CH?CH? Ph? R]_n? (R?OC_mH_2m+1 (m = 4 ( P1 ), 10 ( P2 ), 16 ( P3 )), or NO₂ ( P4 )) were designed and synthesized, respectively, using [Rh(nbd)Cl]₂ as a catalyst. Their structures and properties were characterized and evaluated by FTIR, ¹H‐NMR, ¹³C‐NMR, GPC, and UV, PL, respectively. The optical limiting and nonlinear optical properties were investigated by using a frequency doubled, Q‐switched, mode‐locked Continuum ns/ps Nd:YAG laser system and their optical limiting mechanism was discussed. It is surprising to see that the stilbene pendants endow the polyacetylenes with a high thermal stability (T_d ≥ 270 °C), novel optical limiting properties and large third‐order nonlinear optical susceptibilities (up to 4.61 × 10^?10 esu). The optical limiting mechanism is mainly originated from reverse saturable absorption of molecules. In addition, it is found that the polymer with electron accepted NO₂ moiety exhibits better optical properties than that with electron donated alkoxy group because of larger π electron delocalization and dipolar effect. The strong interaction between stilbene pendants and the polyene main chain significantly results in red‐shift of fluorescence emitting peak. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4529–4541, 2008     

Molecular structure and thermal behavior of N-Benzoyl-3,3-dinitroazetidine

N-Benzoyl-3,3-dinitroazetidine (BDNAZ) has been synthesized and characterized by elemental analysis, FT-IR spectroscopy, ¹H NMR and X-ray single crystal diffraction technique. BDNAZ crystallizes in the monoclinic space group P2₁/c. Its thermal behavior was studied under a non-isothermal condition by DSC and TG/DTG methods, the value of E _a and A of the exothermic decomposition reaction of BDNAZ are 143.19 kJ mol^?1 and 10^14.34 s^?1, respectively. The specific heat capacity of BDNAZ was determined with a continuous C _p mode of micro-calorimeter and theoretical calculation. The adiabatic time-to-explosion was evaluated as 109.9?C124.4 s.     

Mizoroki-Heck reaction, catalysis by nitrogen ligand Pd complexes and activation of aryl bromides

Nitrogen ligands are an excellent alternative for the traditional P-ligands in the Pd catalyzed Mizoroki-Heck reaction. Pd complexes of dimethyl glyoxime, 8-hydroxyquinoline, salen, picolinic acid, DAB ligands gave high yields of the E-cinnamates and E-stilbenes. Acetophenone oxime N,N-dimethybenzyl amine and ferrocenyl oxime palladacycle were better catalysts and comparable yields, TON (95,000) and TOF's (2500 h⁻¹) to P-ligand catalysts, were obtained. Aryl iodides, aryl bromides and in a few cases, aryl chlorides could be also be activated by these complexes by the use of Lewis acid and (C₄H₉)₄NI as additive. DAB ligands gave good yields with electron rich aryl bromides and the use of ionic liquid improved the yield. These metal complexes can be readily synthesized and the N-ligands possess the advantage of easy functional group modifications and convenient synthetic methods compared to P-ligands. The degradation reactions associated with P-ligands is not observed in the N-ligands, with comparable high thermal, moisture and air stability and insensitivity.