Solubility parameters of poly(di-n-alkyl cyclohexyl-) and poly(di-n-alkyl phenyl itaconates)

Solubility parameters of poly(dicyclohexyl-), poly(diphenyl itaconate) and of the first three members of the poly(dialkyl cyclohexyl-) and poly(dialkyl phenylitaconate) homologous series were determined from limiting viscosity numbers in various solvents and solvent mixtures, differing in structure, polarity and composition. The values obtained are within limits of 19.0 and 16.7 (J^1/2. cm^-3/2). Phenyl groups in the substituents lead to slightly higher values than cyclohexyl rings and the introduction of alkyl groups in both series results in a progressive decrease of the solubility parameter. The experimental values are slightly lower than those obtained by calculation from molar attraction constants.     

Synthesis and characterization of poly(1-vinyl-3-alkylimidazolium) iodide polymers for quasi-solid electrolytes in dye sensitized solar cells

A series of new poly(1-vinyl-3-alkylimidazolium) iodide polymers with different alkyl derivatives such as methyl, propyl and perflurodecyl have been synthesized. The alkyl substituent influenced some properties such as solubility, thermal stability, glass transition and crystallinity of the polymers. For instance, polymer having the propyl substituent was soluble in solvents of intermediate polarity such as acetonitrile, chloroform and THF, the one with the methyl substituent was only soluble in very polar solvents such as water and methanol and the fluorinated polymer was only soluble in DMF. The alkyl substituent also influenced the thermal stability in the order methyl > propyl > perflurodecyl and all the polymers thermally decomposed between 250 and 400 °C in nitrogen. The poly(1-vinyl-3-alkyl-imidazolium) iodide polymers having propyl and methyl substituents were amorphous polymers showing a glass transition temperature of 43 and 21 °C, respectively; and perflurodecyl polymers were semi-crystalline with a Tm at 153 °C and a Tg at 20 °C, as indicated by differential scanning calorimetry.Polymer electrolytes were formulated as mixtures of the ionic liquid 1-methyl-3-propylimidazolium iodide and the poly(1-vinyl-3-alkylimidazolium) iodide polymers. These polymer electrolytes showed ionic conductivities in the range of 10⁻³ to 10⁻⁷ S/cm at room temperature which strongly depended on the ionic liquid content. Finally, poly(1-vinyl-3-propyl-imidazolium) iodide was used to obtain gel electrolytes by adding it to a typical acetonitrile electrolyte used in dye sensitized solar cells (DSSCs). Solar cells with 1 cm² area prepared using the polymer gel electrolyte yielded a maximum light-to-electricity conversion efficiency of 3.73%.     

Preparation and solubility of a partial ladder copolymer from p-phenylenediamine and o-phenetidine

A series of copolymers were synthesized by chemically oxidative polymerization of p-phenylenediamine (PPD) and o-phenetidine (PHT) in acidic aqueous media. The polymerization yield, intrinsic viscosity, and solubility of the copolymers were comprehensively studied by changing the comonomer ratio, polymerization time and temperature, oxidant, monomer/oxidant ratio, and acidic medium. As-prepared fine powder of the PPD/PHT copolymers was characterized by FT-IR, UV-vis, high-resolution ¹H-NMR, and DSC techniques. A circular dichroism technique was firstly used to characterize the macromolecular structure of the copolymers. The results showed that the oxidative copolymerization from PPD and PHT is exothermic and the resulting copolymers exhibit an enhanced solubility in most of the organic solvents as compared with poly(p-phenylenediamine), sometimes also with poly(o-phenetidine). The polymer obtained is a real copolymer containing PPD and PHT units, and the actual PPD/PHT ratio calculated by ¹H-NMR spectra of the polymers is very close to the feed ratio. The DSC measurement indicates that the copolymers are amorphous and chemically instable at elevated temperature.     

Determination of the interaction parameter χ of poly(ethylene oxide) by gas-liquid chromatography below the melting temperature

The interaction parameter χ of poly(ethylene oxide) in different solvents at temperatures below the melting point (T_m) of the polymer has been determined by means of the solubility parameters of the polymer and solvents at this temperature, chromatographically obtained from their values at higher temperatures (70°–140°C). The value of the interaction parameter so obtained is not only in good agreement with those calculated by other techniques but also independent of the temperature range employed in the chromatographic measurements. Moreover, using the equation-of-state theory formulation, we have determined values of the interaction parameter χ1 for different poly(ethylene oxide)/probe systems and from it the contact interaction energy X₁₂, in the temperature range between 70° and 140°C.     

White Electroluminescence from a Single-Polymer System with Simultaneous Three-color Emission

A series of polymers were synthesized by incorporating low contents of fluorenone (FO) and 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (DBT) into the main chain of poly(9,9-dioctylfluorene). White-light emission was obtained from a single polymer by adjusting the FO and DBT contents. All polymers showed good thermal stability with 5% weight loss up to 410 °C and good solubility in common organic solvents. Electroluminescence devices with indium tin oxide/poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate)/emission layer/Ca/Al structure were found to emit white light with Commission Internationale de l’Eclairage coordinate of (0.37, 0.34). These devices exhibited a maxium brightness of 3414 cd/m² and a maximum current efficiency of 2.79 cd/A.     

Organosoluble and light‐colored fluorinated polyimides based on 1,1‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]‐1‐phenylethane and various aromatic dianhydrides

To investigate the CF₃ group affecting the coloration and solubility of polyimides (PI), a novel fluorinated diamine 1,1‐bis[4‐(4‐amino‐2‐ trifluoromethylphenoxy)phenyl]‐1‐phenylethane (2) was prepared from 1,1‐ bis(4‐hydrophenyl)‐1‐phenylethan and 2‐chloro‐5‐nitrobenzotrifluoride. A series of light‐colored and soluble PI 5 were synthesized from 2 and various aromatic dianhydrides 3a–f using a standard two‐stage process with thermal 5a– f(H) and chemical 5a–f(C) imidization of poly(amic acid). The 5 series had inherent viscosities ranging from 0.55 to 0.98 dL/g. Most of 5a–f(H) were soluble in amide‐type solvents, such as N‐methyl‐2‐pyrrolidone (NMP), N,N‐ dimethylacetamide (DMAc), and N,N‐dimethylformamide (DMF), and even soluble in less polar solvents, such as m‐Cresol, Py, Dioxane, THF, and CH₂Cl₂, and the 5(C) series was soluble in all solvents. The GPC data of the 5a–f(C) indicated that the Mn and Mw values were in the range of 5.5–8.7 × 10⁴ and 8.5–10.6 × 10⁴, respectively, and the polydispersity index (PDI) Mw /Mn values were 1.2–1.5. The PI 5 series had excellent mechanical properties. The glass transition temperatures of the 5 series were in the range of 232–276°C, and the 10% weight loss temperatures were at 505–548 °C in nitrogen and 508–532 °C in air, respectively. They left more than 56% char yield at 800°C in nitrogen. These films had cutoff wavelengths between 356.5–411.5 nm, the b* values ranged from 5.0–71.1, the dielectric constants, were 3.11–3.43 (1MHz) and the moisture absorptions were in the range of 011–0.40%. Comparing 5 containing the analogous PI 6 series based on 1,1‐bis[4‐(4‐aminophenoxy)phenyl]‐1‐ phenylethane (BAPPE), the 5 series with the CF₃ group showed lower color intensity, dielectric constants, and better solubility. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2399–2412, 2005     

Synthesis and characterization of phosphorus containing aromatic poly(amide-imide)s copolymers for high temperature applications

A series of novel thermally stable poly(amide-imide)s (PAIs) based on non-coplaner diimide-diacid (DIDA) monomer is synthesized. These polymers are characterized by elemental analysis, FT-IR, ¹H-NMR, ¹³C-NMR and ³¹P-NMR spectroscopic techniques and their physical and thermal properties are also studied. Four different dianhydrides pyromellitic anhydride (PMDA)/3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA)/1,4,5,8-naphthalene tetracarboxylic dianhydride (NTDA)/4,4′-oxydiphthalic anhydride (ODPA) and amino acid l-tryptophan are used to synthesize DIDA. The polymerization of DIDA with phosphorus containing triamines having phenyl moieties gives poly(amide-imide)s. The synthesized polymers are obtained in high yield and possessed inherent viscosity in the range 0.66–0.98 dL/g. These polymers display higher solubility in polar aprotic solvents, such as DMSO, NMP and DMF. In addition, the absorption edge values (λ _o) obtained from their UV curves are determined, and all the resulting poly(amide-imide)s films exhibited high optical transparency. The glass transition temperature (T _g) of these polymers is recorded in the range 211–265 °C, initial decomposition temperature in excess of 435 °C and char yield at 800 °C in nitrogen ranged from 52 to 70 %. Wide angle X-ray diffraction showed that all the polymers are almost amorphous.     

Synthesis,characterization and side chains crystallization of comb-like poly(<Emphasis Type="Italic">p</Emphasis>-<Emphasis Type="Italic">n</Emphasis>-alkylstyrene)s

A series of comb like poly(p-n-alkylstyrene)s with linear alkyl groups, containing even numbers of carbon atoms from 12 up to 22 were synthesized by radical polymerization and characterized by FTIR, ¹H NMR, TGA, TVA DSC, and WAXS. All polymers were obtained in good yields and were soluble in organic solvents as chloroform, dichloromethane or tetrahydrofuran and insoluble in methanol; they are stable up to temperatures near 300 °C. On the other hand, the alkylic side chains of all series are able to crystallize in a paraffinic phase in which the melting temperature and enthalpy increase with the methylene number of the n-alkyl chain.     

Comblike Complexes of Poly(itaconic acid) and Poly(mono methyl itaconate) and Alkyltrimethylamonium Cationic Surfactants

Summary A series of complexes from poly(itaconic acid) and poly(mono methyl itaconate) and alkyltrimethylammonium bromide surfactants with linear alkyl groups, containing even number of carbon atoms from 12 up to 22 were synthesized. The complexes were obtained in good yields and were soluble in organic solvents and stable up to temperatures near 150 °C. On the other hand, the paraffinic side chains are able to crystallize depending on the methylene number of the surfactant n-alkyl chain.     

Separation of aqueous phenol through polyurethane membranes by pervaporation. III. Effect of the methylene group length in poly(alkylene glycols)

Separation of phenol from dilute aqueous solution through polyurethane membranes by pervaporation was investigated. The effect of the methylene group length in poly(alkylene glycols) on permselectivity and solubility of phenol was studied. The poly(alkylene glycols) were obtained by polycondensation of 1,6‐hexanediol, 1,8‐octanediol, and 1,10‐decanediol with a sulfuric acid catalyst. Polyethyleneglycol and polytetramethyleneglycol were commercially available. Progress of the polymerization in the poly(alkylene glycols) was confirmed by FTIR, ¹H‐NMR analysis, and SEC measurement. The polyurethanes were obtained by polyaddition reaction of 1,6‐hexamethylenediisocyanate and the poly(alkylene glycol), and were confirmed by FTIR analysis and SEC measurement. The phenol concentration in a permeate liquid increased from 25.1 to 36.2 wt %, and the phenol partial flux also increased from 49.3 to 68.9 g · m⁻² · h⁻¹ with increasing the methylene group length in the poly(alkylene glycols), whereas the water partial flux slightly decreased. As a result of sorption measurements, the change in the degree of swelling was small, and the phenol concentration in the membrane increased from 42.1 to 70.8 wt %. The increase in the methylene group length of the poly(alkylene glycols) should contribute to an increase in the hydrophobicity of the polyurethane so that the solubility of phenol to the membrane should increase. The phenol concentration in the permeate liquid and the phenol partial flux increased with an increase in the methylene group length of the poly(alkylene glycols) due to the increase in the phenol solubility for the polyurethane membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 654–664, 2000     

The solubility parameters of aromatic polyamides

The degrees of swelling of rigid aromatic polyamide networks in various solvents, nonsolvents, and solvent mixtures were used to determine their solubility parameters. This was made possible because of the amorphous nature of the rigid networks and the low levels of intersegmental H-bonding. The solubility parameters are: δ = 23.0 (MPa)^1/2, δ_d = 18.0 (MPa)^1/2, δ_p = 11.9 (MPa)^1/2, and δ_H = 7.9 (MPa)^1/2. The determined values are believed to be good approximations of the solubility parameters of stiff linear aromatic polyamides, because of the essential identity of their structure and the stiff segments in the networks.     

Synthesis of novel mono-substituted polyacetylenes bearing functional urea groups in side chains

Novel mono-substituted polyacetylenes bearing urea groups in side chains, i.e. poly(N-propargylureas), were successfully synthesized for the first time. The solubility of the resulting three polymers (poly(1)–poly(3)) was examined, and it was found that the solubility of them largely depended on the pendent groups; the polymer with benzene cycle (poly(2)) showed high solubility in polar solvents including DMF and DMSO. The effects of polymerization temperature, solvents, and the ratio of monomer concentration to the catalyst concentration ((nbd)Rh⁺B⁻(C₆H₅)₄ (nbd = norbornadiene)) on the polymerization of monomer 2 were investigated. Poly(2) could be obtained with moderate molecular weights (20,100–29,200) in high yields (⩾90%), and the cis content of the polymer backbones was quite high (⩾96%).     

Solubilities and polymer-solvent-nonsolvent θ-compositions of poly (di-n-alkyl itaconates)

In order to establish the prerequisites for the examination of solution properties of poly(di-n-alkyl itaconates), the solubilities of the first 11 members of this polymer homologous series were determined in 70 solvents, and the results correlated with the lengths of the ester substituents of the polymer chain, the solvent solubility parameters and the solvent hydrogen bonding capacities. The relation between solvent strength and the lengths of ester substituents of the monomer units was established quantitatively for several solvents in terms of φ_{2 crit.,} the nonsolvent volume fraction in ternary polymer-solvent-nonsolvent θ-mixtures, and evaluated according to a turbidometric titration method proposed by ELIAS ¹. Both groups of results are a guideline for the probable existance of θ-conditions for particular polymer-solvent pairs and permit the prediction of solubilities of still higher members of the series.     

One-step synthesis of poly(triazole-ether-quinoxaline)s using click reaction: preparation and properties of magnetic nanocomposites with modified Fe3O4 for metal ions removal

A new dialkyne-terminated monomer, 2,3-bis(4-(prop-2-yn-1-yloxy)phenyl)quinoxaline, was synthesized and used in the click reaction with various alkyl dibromides by a convenient one-pot procedure to yield poly(triazole-ether-quinoxaline)s (PTAEQ). The weight average molecular weights (M_w) of PTAEQs were measured by GPC and were in the range of 1.87×10⁴–2.41×10⁴ g/mol. These polymers exhibited T_g and 10 % weight loss temperatures (T_10%) in the range of 177–262 °C and 350–420 °C, respectively. PTAEQs showed excellent solubility in various polar organic solvents and formed low-colored and tough thin films via solution casting. A series of nanocomposites was prepared from solution blending of PTAEQs with epoxide-end capped Fe₃O₄ nanoparticles. Structure and morphology of the prepared magnetic nanocomposites (MNCPTAEQ)s were investigated, and the effect of interfacial adhesion between organic and inorganic phases on thermal, solubility, mechanical and optical properties of composites was investigated. The functional sites in the polymer chains were also tested for the removal of toxic metal ions such as Cr³⁺, Pb²⁺, Cd²⁺, Sn²⁺, Cu²⁺ and Hg²⁺ from aqueous solutions either individually or in the mixture.     

Solubility parameters of polymethacrylonitrile,poly(methacrylic acid) and methacrylonitrile/methacrylic acid copolymer

The solubility behaviors of polymethyacrylonitrile (PMAN), poly(methacrylic acid) (PMAA), and its random copolymer methacrylonitrile (MAN)/methacrylic acid (MAA) in various solvents were investigated. The results were used in a computer program to obtain a 3-dimensional representation of the polymer solubility region in the Hansen space. Thus, the values of dispersion (δ_d,p), polar (δ_p,p) and hydrogen bonding (δ_h,p) components of the total solubility parameter (δ_t,p) were obtained. Comparisons between the experimental results and the estimated values are discussed. Also, prediction for solubility parameter values for MAN/MAA copolymer via their homopolymers, PMAN, and PMAA has been evaluated.     

Study of solution properties of poly(α-methyl styrene) in various solvents by dilute-solution viscometry

The values of Mark–Houwink–Sakurada constants were determined for poly(α-methyl styrene) (PαMs) of high and low molecular weights in a variety of solvents by a new approach, which requires only polydisperse samples. The results are in accord with those reported in the literature. In addition, the present work reports the values of the Flory interaction parameter for PαMs in 13 solvents of distinct solvent power at various temperatures. Three refined methods pertaining to both polar and nonpolar solvents were applied to estimate the solubility parameter (δ₂) of PαMs resulting in δ₂ = 18.75 ± 0.15 (J/mL)^1/2 at 30°C. Finally, the scatter data of the Huggins coefficient over a range of expansion factors varying from 0.7 to 2.6 seem to conform better to a newly proposed empirical equation than to the contemporary model after Imai. © 1993 John Wiley & Sons, Inc.     

Ortho alkyl substituents effect on solubility and thermal properties of fluorenyl cardo polyimides

Five fluorenyl cardo diamines containing different alkyl substituents were synthesized and characterized. A series of fluorenyl cardo polyimides were prepared by polycondensation of these cardo diamines with 4,4′-oxydiphthalic anhydride (ODPA), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3′,4,4′-biphenyl tetracarboylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA). Most of fluorenyl cardo polyimides exhibited excellent solubility in common organic solvents such as m-cresol, chloroform, tetrahydrofuran (THF), N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAC) etc. and intrinsic viscosity in N,N-dimethylacetamide (DMAC) ranged from 0.31 to 0.92 dl/g. T_g of polyimides based on ODPA decrease with the number and size of alkyl substituents on fluorenyl cardo diamine. The results show that the incorporation of noncoplanar structure led by the introducing alkyl substituents on fluorenyl cardo diamines improves the solubility of cardo polyimides in organic solvents without sacrificing thermal properties.     

Synthesis and characterization of N‐ and O‐alkylated poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline]

Poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline] was synthesized in an aqueous hydrochloric acid medium with a determined feed ratio by chemical oxidative polymerization. This polymer was used as a functional conducting polymer intermediate because of its side‐group reactivity. To synthesize the alkyl‐substituted copolymer, the initial copolymer was reacted with NaH to obtain the N‐ and O‐anionic copolymer after the reaction with octadecyl bromide to prepare the octadecyl‐substituted polymer. The microstructure of the obtained polymers was characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, and X‐ray diffraction. The thermal behavior of the polymers was investigated by thermogravimetric analysis and differential scanning calorimetry. The morphology of obtained copolymers was studied by scanning electron microscopy. The cyclic voltammetry investigation showed the electroactivity of poly [aniline‐co‐N‐(2‐hydroxyethyl) aniline] and N and O‐alkylated poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline]. The conductivities of the polymers were 5 × 10^?5 S/cm for poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline] and 5 ×10^?7 S/cm for the octadecyl‐substituted copolymer. The conductivity measurements were performed with a four‐point probe method. The solubility of the initial copolymer in common organic solvents such as N‐methyl‐2‐pyrrolidone and dimethylformamide was greater than polyaniline. The alkylated copolymer was mainly soluble in nonpolar solvents such as n‐hexane and cyclohexane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Compatibility of polyacrylates and polymethacrylates with poly(vinyl chloride): 2. Measurement of interaction parameters

Interactions of various solvents with poly(vinyl chloride) and a series of polyacrylates and polymethacrylates have been studied by inverse gas chromatography. Values of the interaction parameters χ₁₂ have been calculated and show the importance of specific interactions between the polymers and the solvents. Low values of χ₁₂ indicating a strong interaction were found for the polyacrylates and polymethacrylates with a proton donating solvent, chloroform, and for the poly(vinyl chloride) with some proton accepting solvents, especially butan-2-one. Interactions of solvents, with mixtures of poly(vinyl chloride) with some compatible polyacrylates and polymethacrylates, have also been studied. From this, and using the values of χ₁₂ found above, values of the polymer-polymer interaction parameters χ₂₃ have been calculated. Low values of χ₂₃, indicating a strong interaction were found, especially for polymethacrylates and polyacrylates with shorter ester side chains. Lower values were obtained for polymethacrylates than polyacrylates again indicating greater interactions. These results fit in well with the results of a previous paper where we found that the polymers with longer ester side chains were not compatible with PVC or phase separated on heating, and that fewer acrylates than methacrylates are compatible with PVC.     

Solubility parameters in polyoxetanes: Poly(oxetane), poly(3,3-dimethyl oxetane), and poly(3,3-diethyloxetane)

The solubility parameter of poly(oxetane), poly(3,3-dimethyloxetane) and poly(3,3-diethyl oxetane) has been estimated by measuring solution viscosities. Values of δ = 9.4, 7.9, and 7.9 cal^1/2·cm^?3/2 for each polymer were obtained and compared with those calculated from empirical methods. The 3-dimensional solubility parameter approach has been also applied in order to get additional information on the effect of structural modifications on the main chain in the solubility behavior.