Sulfur-containing polymers. Synthesis and properties of novel poly(arylene thioether)s based on 2,2-bis(4-mercaptophenyl)propane

Novel poly(arylene thioether)s were synthesised using the one pot polymerisation method from the bis(N,N-dimethyl-S-carbamate) of 2,2-bis(4-mercaptophenyl)propane and activated difluoro aromatic compounds. Each of the polymers, obtained in good yields and with fairly high molecular weights, were characterised by IR, GPC and NMR analyses. In particular, the NMR characterisation was performed using ¹H NMR, ¹³C NMR, DEPT, 2D COSY and 2D HSQC experiments. To study the effect on the thermal properties of replacing the ethereal oxygen atoms with sulfur atoms, we have synthesised the counterparts, the poly(arylene ether)s, with similar molecular weights. We observed that the substitution of the ethereal oxygen atoms with sulfur atoms results in a slightly lower thermal stability for the poly(thioether ketone)s, both under nitrogen and in air, and does not modify the T_g values. For the poly(thioether sulfone), on the other hand, the thermal stability is equal to that of the poly(ether sulfone), while the T_g is 10 °C lower. Furthermore, each sample is completely amorphous, with the exception of one of the poly(thioether ketone)s (sample 1b), which shows the capacity to crystallise, even if with a very slow crystallisation kinetics.     

POLYMERIZATION BY PHASE TRANSFER CATALYSIS. 25. SYNTHESIS OF POLYCARBONATES AND POLYTHIOCARBONATES DERIVED FROM DIPHENOLS CONTAINING GERMANIUM AND SILICON IN THE MAIN CHAIN†

Polycarbonates and polythiocarbonates derived from diphenols containing Si or Ge, bis(4-hydroxyphenyl)-dimethyl-germane (I), bis(4-hydroxyphenyl)-diphenyl-germane (II), bis(4-hydroxy-phenyl)-dimethyl-silane (III), and bis(4-hydroxyphenyl)-diphenyl-silane (IV), and phosgene (a) or thiophosgene (b), respectively, were synthesized under phase transfer conditions using several phase transfer catalysts. The results were evaluated by the yields and η_inh values, showing that this technique was effective for the synthesis of this kind of polymers. The yields were low compared with those obtained with other diphenols, due probably to the use in this work of stoichiometric amounts of NaOH to avoid the decomposition of the diphenol, which hindered a salting out effect of the diphenolate to the organic phase.

     

Poly(ether sulfone)s using a rigid dibenzothiophene dioxide heterocycle

Poly(aryl ether)s were prepared by nucleophilic aromatic substitution using conformationally restricted dichloro‐ and difluorodibenzothiophene dioxide heterocyclic monomers with bisphenol A or bisphenol AF. The heterocyclic monomers were prepared from the bis(4‐halophenyl) sulfones in two steps via lithiation followed by copper catalyzed intramolecular coupling and characterized by ¹H, ¹³C, ¹⁹F NMR spectroscopy and GC/MS. Reactivity of the fluorine containing monomer was examined using semi‐empirical methods and NMR spectroscopy measurements and found to be potentially more reactive than bis(4‐fluorophenyl) sulfone, even with a conformationally locked sulfone as the electron withdrawing group. Successful polymerizations of both the fluorine and chlorine containing monomers with bisphenol A and bisphenol AF nucleophiles were accomplished, providing polymers with number average molecular weights of approximately 45 kg/mol (difluoro monomer) and 10–20 kg/mol (dichloro monomer). The polymers exhibited high T_gs ranging from 238 to 256 °C and displayed good thermal stability with 5% degradation temperatures in air from 453–510 °C, depending on molecular weight and bisphenol composition. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3127–3131     

Synthesis and characterization of poly(thioether ether sulfone imide)s derived from isomeric bis(chlorophthalimide)s and bis(4-mercaptophenyl) sulfone

A series of isomeric bis(chlorophthalimide)s (BCPIs) were conveniently prepared from 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, and mixtures thereof. Polymerization of BCPIs with bis(4-mercaptophenyl) sulfone (BMPS) proceeded smoothly in the presence of tributylamine, from which a class of isomeric poly(thioether ether sulfone imide)s (PTESIs) with inherent viscosities of 0.45-0.82 dL/g were obtained. The solubility, thermal stability, and mechanical properties of these polymers were characterized. Compared to the PTESIs derived from single BCPIs, i.e., 3,3′-, 3,4′-, or 4,4′-BCPIs, the PTESIs derived from mixed BCPIs showed better solubility and higher storage modulus. These PTESIs also demonstrated good thermal stability, giving only 5% weight loss at temperature of 490 °C in nitrogen atmosphere. The glass transition temperatures (T_gs) of these isomeric PTESIs were between 242 and 265 °C, and were increased with increasing of the ratio of 3-chlorophthalimide unit in the polymer backbone.     

Synthesis of novel poly(thioether‐naphthalimide)s that utilize hydrazine as the diamine

A series of bis(4‐thio‐1,8‐naphthalic anhydride)s and the corresponding bis(N‐amino naphthalimide) derivatives were synthesized from readily available compounds in high yield. A series of novel poly(thioether‐naphthalimide)s, which utilized hydrazine as the diamine, were synthesized by a one‐step polymerization reaction in m‐cresol. Poly(thioether‐naphthalimide)s with inherent viscosities of 0.57–1.73 dL/g were obtained. The polymers were soluble in CHCl₃ and were determined to have high molecular weights by means of gel permeation chromatographic analysis. They were soluble in m‐cresol and could be cast into tough films from m‐cresol solution. The glass‐transition temperature (T_g) values of the polyimides ranged from 320 to 353 °C. Polyimides from the bisphenol dianhydride, derived from 9,9‐bis(4‐hydroxyphenyl)fluorene, did not show a clear transition in the DSC analysis. Degradation temperatures for 5% weight loss all occurred above 430 °C in nitrogen. The series of monomers were successfully copolymerized with each other. Monomers 6a and 7a , containing the bisphenol A moiety, could also be copolymerized with perylenetetracarboxylic dianhydride. These copolymers had high T_g's and were thermally stable. The UV–vis absorption properties of the polymers were also examined. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1040–1050, 2001     

Preparation and characterisation of novel random copoly(arylene ether-thioether ketone)s containing 2,2-bis(4-phenylene)propane units

This study investigates on the preparation and characterisation of new random copolymers containing the monomeric units of a poly(arylene ether ketone) (PEAEK) and a poly(arylene thioether ketone) (PTATK) previously synthesised by our group. The syntheses were performed using a one-pot polymerisation method starting from 4,4′-difluorobenzophenone, bis(N,N-dimethyl-S-carbamate) of 2,2-bis(4-mercaptophenyl)propane (MBTA) and bisphenol A (BPA). Different mole percentages of BPA with respect to MBTA, varying from 20% to 80%, were used. The copolymers, obtained in good yields, have molecular weights in the range from 19,000 to 32,000 as determined by GPC. The structural proof is provided by ¹H NMR spectroscopy. The TGA analysis shows that the high stability of PEAEK is only slightly affected by the introduction of the PTATK co-units in the chain. Indeed, the presence of sulphur atoms induces an initial degradation process at temperatures slightly lower than that of PEAEK, but in a second stage tends to improve the formation of crosslinkings. Moreover, the copolymers with an amount of PEAEK equal to 40 and 20 mol% show a small crystallinity, due to the presence of PTATK units. The T_g values are not affected by the composition of copolymers. Therefore, the presence of sulphur atoms in the polymer backbone does not significantly modify the PEAEK characteristics, whereas can induce important new properties, such as better flame resistance or higher refractive index.     

Allyl-containing polyaryl ethers with perfluorinated mono- and biphenylene fragments

A method for the synthesis of fluorinated allyl-containing bisphenol based on 4,4′-[(2,3,5,6-tetrafluoro-1,4-phenylene)bis(oxy)]diphenol has been elaborated. Curable aromatic polyethers have been prepared via polycondensation of the synthesized bisphenol with decafluorobiphenyl. The influence of bases, namely K₂CO₃ and NaH, on the molecular weights of polymers has been studied, and the conditions of their curing at allyl moieties have been found. Mechanical, physicochemical, and dielectric properties of allylcontaining polymers are dependent on the method of their preparation and curing.     

Fast liquid chromatography-tandem mass spectrometry for the analysis of bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether and their derivatives in canned food and beverages

In this work a fast liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS) method using a C18 Fused Core™ column, was developed for the simultaneous analysis of bisphenol A diglycidyl ether (BADGE), bisphenol A (2,3-dihydroxypropyl) glycidyl ether (BADGE·H₂O), bisphenol A bis(2,3-dihydroxypropyl) ether (BADGE·2H₂O), bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether (BADGE·HCl), bisphenol A bis(3-chloro-2-hydroxypropyl) ether (BADGE·2HCl) and bisphenol A (3-chloro-2-hydroxypropyl)(2,3-dihydroxypropyl ether) (BADGE·HCl·H₂O) and bisphenol F diglycidyl ether (BFDGE), bisphenol F bis(2,3-dihydroxypropyl) ether (BFDGE·2H₂O), bisphenol F bis(3-chloro-2-hydroxypropyl) ether (BFDGE·2HCl). The LC method was coupled with a triple quadrupole mass spectrometer, using an ESI source in positive mode and using the [M+NH₄]⁺ adduct as precursor ion for tandem mass spectrometry experiments. The method developed was applied to the determination of these compounds in canned soft drinks and canned food. OASIS HLB solid phase extraction (SPE) cartridges were used for the analysis of soft drinks, while solid canned food was extracted with ethyl acetate. Method limits of quantitation ranged from 0.13 μg L⁻¹ to 1.6 μg L⁻¹ in soft drinks and 1.0 μg kg⁻¹ to 4.0 μg kg⁻¹ in food samples. BADGE·2H₂O was detected in all the analyzed samples, while other BADGEs such as BADGE·H₂O, BADGE·HCl·H₂O, BADGE·HCl and BADGE·2HCl were also detected in canned foods.     

Synthesis of Aromatic Polythioethers Containing 1,3,5-Triazine Ring by Aromatic Nucleophilic Substitution Polymerization

Abstract

Reaction of 2,4-dichloro-6-phenyl-1,3,5-triazines with bis(4-mercaptophenyl) sulfide in the presence of a base in THF afforded the corresponding condensation polymer as a whole aromatic polythioether in moderate yield. The polymerization of several 2,4-dichloro-1,3,5-triazine derivatives with this dithiols also proceeded in the o-dichlorobenzene-water two-phase system by using phase transfer catalysts. The resulting polymers consisted of THF-soluble and -insoluble fractions. The x-ray diffraction pattern indicated that these THF-insoluble polymers have a highly crystalline nature. Further, the polymers obtained here showed high thermal stability.     

Effect of gamma radiation on fluoropolymers

A series of fluoropolymer films were synthesized by reacting several bisphenol monomers with 1,3‐bis(1,1,1,3,3,3‐hexafluoro‐2‐pentafluorophenyl methoxy‐2‐propyl)benzene via a nucleophilic aromatic substitution to form polyethers. The bisphenols used included two diphenol‐substituted spirodilactams (SDL; aliphatic and aromatic), biphenol, bisphenol A, bisphenol AF, bisphenol O, and bisphenol F to form seven different polymers. Polymers were irradiated by a Gamma beam 651‐PT at a dose rate of 10.5 kGy/h; the absorbed dose in each film was varied between 300 and 1000 kGy. The effect on the chemical structure upon radiation was studied by DSC, TGA, FTIR‐ATR, and NMR after and before irradiation. Thermal analysis showed a lessened thermal stability and a lower T_g after irradiation. Further, irradiation caused a decrease in molecular weight as a result of cleavage of sp³ bonds. These data allowed calculation of the radiochemical yield scission (G_s) for each of these polymers. The SDL aromatic system proved the most radiation‐resistant. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1617–1626, 2009     

Synthesis,crystal structures and spectral studies of square planar nickel(II) complexes containing an ONS donor Schiff base and triphenylphosphine

Five mononuclear nickel(II) complexes, viz. [Ni(L1)(PPh₃)] (1), [Ni(L2)(PPh₃)] (2), [Ni(L3)(PPh₃)] (3), [Ni(L4)(PPh₃)] (4) and [Ni(L5)(PPh₃)] (5) (where L1, L2, L3, L4 and L5 are dianions of N-(2-mercaptophenyl)salicylideneimine, 5-methyl-N-(2-mercaptophenyl)salicylideneimine, 5-chloro-N-(2-mercaptophenyl)salicylideneimine, 5-bromo-N-(2-mercaptophenyl)salicylideneimine and N-(2-mercaptophenyl)naphthylideneimine, respectively), have been synthesized and characterized by means of elemental analysis, electronic, IR, ¹H, ¹³C and ³¹P NMR spectroscopy. Single crystal X-ray analysis of two of the complexes (1 and 5) has revealed the presence of a square planar coordination geometry (ONSP) about nickel. The crystal structures of the complexes are stabilized by intermolecular π–π stacking between the ligands (L) and by various C–H···π interactions.     

Polyesters containing sulfur. VII. New aliphatic‐aromatic polyesters for synthesis of polyester‐sulfur compositions and polyurethanes

New linear polyesters containing sulfur in the main chain were obtained by melt polycondensation of diphenylmethane‐4,4′‐bis(methylthioacetic acid) (DBMTAA) or diphenylmethane‐4,4′‐bis(methythiopropionic acid) (DBMTPA) and diphenylmethane‐4,4′‐bis(methylthioethanol) (DBMTE) at equimolar ratio of reagents (polyesters E‐A and E‐P) as well as at 0.15 molar excess of diol (polyesters E‐A_OH and E‐P_OH). The kinetics of these reactions was studied at 150, 160, and 170°C. Reaction rate constants (k₂) and activation parameters (ΔG^≠, ΔH^≠, ΔS^≠) from carboxyl group loss were determined using classical kinetic methods. E‐A and E‐P (M̄_n = 4400, 4600) were used for synthesis of new rubber‐like polyester‐sulfur compositions, by heating with elemental sulfur, whereas oligoesterols E‐A_OH and E‐P_OH (M̄_n = 2500, 2900) were converted to thermoplastic polyurethane elastomers by reaction with hexamethylene diisocyanate (HDI) or methylene bis(4‐phenyl isocyanate) (MDI). The structure of the polymers was determined by elemental analysis, FT‐IR and liquid or solid‐state ¹H‐, ¹³C‐NMR spectroscopy, and X‐ray diffraction analysis. Thermal properties were measured by DTA, TGA, and DSC. Hardness and tensile properties of polyurethanes and polyester‐sulfur compositions were also determined. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 835–848, 1999     

Kinetic study of semifluorinated arylene vinylene ether polymers

Fluorinated arylene vinylene ether (FAVE) polymers were prepared from the base‐promoted addition of commercial 2,2‐bis(4‐hydroxyphenyl)hexafluoropropane (6F bisphenol A) to aryl trifluorovinyl ether (TFVE), 2,2′‐bis(4‐trifluorovinyloxybiphenyl)‐1,1,1,3,3,3‐hexafluoropropane. The step‐growth polymerization kinetics by using stoichiometric NaH and catalytic Cs₂CO₃ were investigated by monitoring the ¹⁹F NMR signals of the aryl TFVEs. The nth order kinetic model was used to determine rate constants over a series of programmed temperatures. Polymerization using stoichiometric NaH resulted in second‐order kinetics with an activation energy of 59 kJ/mol. This model kinetic study provided insight into the mechanistic pathways of the FAVE polymer system that has recently shown a lot of interest in many areas of materials science. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Effect of Cation Structure in Quinolinium-Based Ionic Liquids on the Solubility in Aromatic Sulfur Compounds or Heptane: Thermodynamic Study on Phase Diagrams

Experimental and theoretical studies on thermodynamic properties of quinolinium-based ionic liquids (ILs) based on bis(trifluoromethylsulfonyl)imide anion (namely N-butyl-quinoloinium bis(trifluoromethylsulfonyl)imide, [BQuin][NTf₂], N-hexylquinoloinium bis(trifluoromethyl-sulfonyl)imide, [HQuin][NTf₂], and N-octylquinoloinium bis(trifluoromethyl-sulfonyl)imide, [OQuin][NTf₂]) with aromatic sulfur compounds and heptane, as a model compound of fuel were examined in order to assess the applicability of the studied ionic liquids for desulfurization of fuels. With this aim, the temperature-composition phase diagrams of 13 binary mixtures composed of organic sulfur compounds (thiophene, benzothiophene, or 2-methylthiophene) or heptane and ionic liquid (IL) were investigated at ambient pressure. A dynamic method was used to determine the (solid–liquid) equilibrium phase diagrams in binary systems over a wide composition range and temperature range from T = 255.15 to 365.15 K up to the fusion temperature of ILs. The immiscibility gap with an upper critical solution temperature (UCST) was observed for each binary system under study. The influence of the alkane chain length of the substituent on the IL cation and of the sulfur compounds (the aromaticity of the solvent) was described. The experimental (solid + liquid) phase equilibrium dataset were successfully correlated using the well-known NRTL equation.     

Synthesis and characterization of poly(esters) derived from diacids and diphenols containing silicon and germanium

Poly(esters) containing two heteroatoms, Si or Ge, in the main chain, derived from diphenols bis(4-hydroxyphenyl)-dimethyl-germane, bis(4-hydroxyphenyl)-diphenyl-germane, bis(4-hydroxyphenyl)-dimethyl-silane and bis(4-hydroxyphenyl)-diphenyl-silane, and the acid dichlorides bis(4-chloroformyl-phenyl)-dimethyl-germane, bis(4-chloroformyl-phenyl)-diphenyl-germane, bis(4-chloroformyl-phenyl)-dimethyl-silane and bis(4-chloroformyl-phenyl)-diphenyl-silane, were synthesized under phase transfer conditions using two phase transfer catalysts, and characterized by spectroscopic methods. This technique showed low effectivity for the synthesis of these kinds of polymers, showing a low increase of the yields and η_inh values in comparison with the interphasial process. In these experimental conditions there were no important differences neither in the studied parameters between the monomers with Si or Ge, nor between the catalysts.     

An efficient one-pot three-step domino synthesis of substituted bis(pyrazino[2′,3′:4,5]thieno[3,2-d]pyrimidin-4(3H)-ones)

A convenient and efficient one-pot three-step domino approach to bis(pyrazinothienopyrimidinones) from ethyl 3-(triphenylphosphoranylideneamino)-thieno[2,3-b]pyrazine-6-carboxylate 1 has been developed. In this method, treatment of phosphazene 1 with a mixture of isocyanates, nitrogen, sulfur, and oxygen bis(nucleophiles) and K₂CO₃ in refluxing THF regioselectively furnishes the corresponding bis(pyrazino[2′,3′:4,5]thieno[3,2-d]pyrimidin-4(3H)-ones) in satisfactory to good yields. This methodology is highly versatile and efficient for the generation of these functionalized bis(triheterocyclic) compounds that are not readily available by other synthetic methods.     

Novel random copoly(arylene ether-thioether ketone)s based on 2,2-bis(4-mercaptophenyl)propane and 4,4′-dihydroxybiphenyl: Synthesis and properties

A series of novel poly(arylene ether-thioether ketone) random copolymers were synthesised by copolymerisation of 4,4′-difluorobenzophenone with bis(N,N-dimethyl-S-carbamate) of 2,2-bis(4-mercaptophenyl)propane (MBTA) and 4,4′-dihydroxybiphenyl (BP). The syntheses were performed using a one pot polymerisation method starting from different mole percentages of BP with respect to MBTA, varying from 20% to 80%. The copolymers were obtained in good yields and had molecular weights in the range 10,000–17,000 as determined by GPC. The structural proof was provided by ¹H-NMR spectroscopy. In order to study the effect of the copolymerisation on the thermal properties and crystal behaviour, also the poly(ether biphenyl ether ketone) homopolymer (PEBEK) has been synthesised using the same polymerisation method. The TGA analysis shows that the high stability of PEBEK is only slightly affected by the introduction of co-units in the chain. The copolymers with an amount of PEBEK variable from 80 to 50 mol% are crystalline, with percentage of crystallinity and melting temperature which decrease as the co-unit content increases. The samples with lower amount of PEBEK (40 and 20 mol%) are amorphous. The T_g values tend to decrease with the reduction of the percentage of PEBEK units.     

Copolymerization of fluorene‐based main‐chain benzoxazine and their high performance thermosets

A series of fluorene‐based benzoxazine copolymers were synthesized from the mixture of 9,9‐bis(4‐hydroxyphenyl)fluorene and bisphenol A, and 4,4′‐diaminodiphenyloxide and paraformaldehyde. And the cured polybenzoxazine films derived from these copolymers were also obtained. Fourier transform infrared spectroscopy (FTIR) and hydrogen nuclear magnetic resonances confirmed the structure of these benzoxazines. Their molecular weight was estimated by gel permeation chromatography. The curing behavior of the precursors was monitored by FTIR and differential scanning calorimetry. Dynamic mechanical analysis and thermogravimetric analysis were performed to study the thermal properties of the cured polymers. The cured polybenzoxazines exhibit excellent heat resistance with glass transition temperatures (T_g) of 286–317°C, good thermal stability along with the values of 5% weight loss temperatures (T₅) over 340°C, and high char yield over 50% at 800°C. The mechanical properties of the cured polymers were also measured by bending tests. Copyright © 2015 John Wiley & Sons, Ltd.     

Polycarbonate-poly(methyl methacrylate) block copolymers: Synthesis and characterization

The interfacial copolymerization of bisphenol A polycarbonate, bisphenol A-terminated poly-(methyl methacrylate), and bisphenol A bischloroformate is described. Monofunctional hydroxy-terminated poly(methyl methacrylates) were synthesized by the chain transfer polymerization of methyl methacrylate with 2-mercaptoethanol. Further reaction with bisphenol A bischloroformate yielded monofunctional bisphenol A-terminated poly(methyl methacrylates). The structure and functionality of these polymers were proven by proton nuclear magnetic resonance (PNMR) spectroscopy. Block copolymers prepared by the interfacial copolymerization were washed with methanol and extracted with acetone to remove unreacted bisphenol A bischloroformate and bisphenol A-terminated poly(methyl methacrylates). The series of block copolymers, which contained from 0.11 to 0.86 mole fraction polycarbonate, were characterized by infrared, PNMR, and molecular weight analysis.     

固相萃取-高效液相色谱-串联质谱测定水中8种双酚-二环氧甘油醚

建立了水中8种双酚-二环氧甘油醚（双酚A二缩水甘油醚（BADGE）及其衍生物双酚A（3-氯-2-羟丙基）甘油醚（BADGE·5HCl）、双酚A双（3-氯-2-羟丙基）醚（BADGE·52HCl）、双酚A（2,3-二羟丙基）甘油醚（BADGE·5H₂O）、双酚A双（2,3-二羟丙基）醚（BADGE·52H₂O）、双酚A（3-氯-2-羟丙基）（2,3-二羟丙基）醚（BADGE·5HCl·5H₂O）和双酚F-二环氧甘油醚（BFDGE）及其衍生物双酚F双（3-氯-2-羟丙基）醚（BFDGE·52HCl））的固相萃取-高效液相色谱-串联质谱（SPE-HPLC-MS/MS）测定方法。10个饮用水接触涂料样品在室温避光条件下,以超纯水浸泡（24±1）h,然后取200 mL经C₁₈固相萃取柱进行净化浓缩,以C₁₈色谱柱进行分离,以5 mmol/L醋酸铵、甲醇和水为流动相进行梯度洗脱,质谱多反应监测（MRM）模式检测,外标法定量。结果表明,8种双酚-二环氧甘油醚在0.007~5.00 μg/L线性关系良好,相关系数均大于0.9990,该方法对8种双酚-二环氧甘油醚的定量限为7~91 ng/L,回收率为79.1%~101%,RSD为4.0%~12%。该方法具有灵敏度高、选择性强的特点,能够满足水中双酚-二环氧甘油醚的快速检测和准确定量。