Synthesis and characterization of novel polyarylates from 2,5-bis(4-hydroxyphenyl)-3,4-diphenylfuran and aromatic diacid chlorides

New tetraphenylated heterocyclic diol, 2,5-bis(4-hydroxyphenyl)-3,4-diphenylfuran, was synthesized by the oxidative coupling of 4-methoxydeoxybenzoin as a starting material, followed by simultaneous cyclodehydration and demethylation. Tetraphenylfuran-containing polyarylates with inherent viscosities of 0.2–0.7 dL/g were prepared from various diacid chlorides by both solution polycondensation and phase transfer catalyzed two-phase polymerization methods. All the polymers were easily soluble in dichloromethane, o-chlorophenol, 1,4-dioxane, pyridine, and N-methyl-2-pyrrolidone and showed semicrystalline patterns as evidenced by the X-ray diffraction studies. These polyarylates have glass transition temperatures in the range of 222–236°C and 10% weight loss was observed above 430°C in both air and nitrogen.     

Synthesis and characterization of new aromatic polyesters and polyethers derived from 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethylene

New polyarylates and aromatic polyethers were synthesized from 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethylene, and aromatic dicarboxylic acid chlorides and aromatic dihalides, respectively. The polyarylates having inherent viscosities of 0.28–1.05 dL/g were synthesized by either the two-phase method or the high-temperature solution method. All the polymers were easily soluble in N-methyl-2-pyrrolidone, N,N-dimethylformamide, pyridine, m-cresol, 1,4-dioxane, and 1,1,2,2-tetrachloroethane. They have glass transition temperatures in the range of 217–250°C and showed no weight loss below 315°C in both air and nitrogen atmospheres. Aromatic polyethers with inherent viscosities of 0.85–1.21 dL/g were obtained by the polycondensation of 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethylene and aromatic difluorides in the presence of potassium carbonate. These polymers having glass transion temperatures of 193–220°C were also soluble in the aforementioned solvents and stable up to around 350deg;C in both atmospheres. © 1994 John Wiley & Sons, Inc.     

Synthesis and properties of a novel perfluorononenyloxy group containing polyarylates

A series of novel perfluorononenyloxy group containing polyarylates were synthesized by a high-temperature solution condensation of 5-(perfluorononenyloxy)-isophthaloyl chloride ( II ) with various aromatic diols in o-dichlorobenzene. All the polyarylates were amorphous and readily soluble in many organic solvents such as o-chlorophenol, o-dichlorobenzene, chloroform, and polar aprotic solvents at room temperature or on heating. Transparent, tough, and flexible films of these polymers could be cast from the o-chlorophenol solutions. The polymers having inherent viscosity of 0.61–1.63 dL/g were obtained in quantitative yields. These polymers were thermally quite stable. The glass transition temperatures of these polyarylates were in the range of 219–242°C by DSC and 224–251°C by DMA, and the 10% weight loss temperatures in nitrogen and air were above 415 and 397°C, respectively. Moreover, these polymers maintained good mechanical properties (G′ ∼ 10⁸ Pa) up to 220°C and had lower moisture absorption than common polyarylates. The dielectric constants of these polymers ranged from 3.23 to 3.75. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 645–653, 1998     

Preparation and properties of polyarylates both from 2,2′-bibenzoyl chloride and bisphenols and from biphenyl-2,2′-diol and aromatic dicarboxylic acid chlorides

Polyarylates having inherent viscosities up to 1.02 dL/g were synthesized both by the phase-transfer catalyzed two-phase polycondensation of 2,2′-bibenzoyl chloride with various bisphenols and by the high-temperature solution polycondensation of biphenyl-2,2′-diol with aromatic dicarboxylic acid chlorides. All the polyarylates were amorphous and soluble in a variety of organic solvents including N,N-dimethylformamide, N-methyl–2-pyrrolidone, chloroform, m-cresol, and pyridine. Transparent and flexible films of these polymers could be cast from the chloroform solutions. These polyarylates had glass transition temperatures in the range of 120–250°C and began to lose weight at around 380°C in air. © 1992 John Wiley & Sons, Inc.     

Synthesis of soluble polyarylates with a propeller-like structure via Diels-Alder reaction

Soluble propeller-like polyarylates with M¯_n ≈ 1 × 10⁴ and melting in the range 200–220°C were synthesized via one-pot simultaneous Diels-Alder (using anthracene or (E,E)-1,4-diphenylbutadiene as enophile and the fumaroyl moiety as dienophile) and polycondensation reaction. Thermal properties of all polyarylates were evaluated. Decomposition occurs in two steps between approximately 300–400°C. The first step is due to retro-Diels-Alder reaction and the second one to main-chain decomposition.     

Preparation and properties of fluorine-containing polyarylates from tetrafluoroisophthaloyl chloride and bisphenols

Fluorine-containing polyarylates having inherent viscosities of 0.2–0.8 dL/g were prepared from tetrafluoroisophthaloyl chloride and various bisphenols by low temperature solution polycondensation in chloroform with triethylamine or by two-phase polycondensation in a dichloromethane-water or nitrobenzene-water system with benzyltriethylammonium chloride as the phase transfer catalyst. These polyarylates were amorphous and were readily soluble in various solvents, including chloroform and N-methyl-2-pyrrolidone. The glass transition temperature of the polymer derived from 2,2-bis(4-hydroxyphenyl) propane was 150°C. These polyarylates started to lose weight around 350°C in an air or nitrogen atmosphere.     

Preparation and properties of polyarylates from 5-t-butylisophthaloyl chloride and various bisphenols

Polyarylates containing a t-butyl pendant group were prepared from 5-t-butylisophthaloyl chloride and various bisphenols through the phase-transfer catalyzed two-phase polycondensation. The polyarylates having inherent viscosities up to 3.1 dL/g were obtained quantitatively. They were readily soluble in various solvents such as chloroform, m-cresol, and pyridine. Coloreless, transparent, and flexible films could be cast from the chloroform solutions of the polymers. The polyarylates had glass transition temperatures between 210 and 320°C, and did not lose weight below 350°C, with 10% weight loss being recorded at 395–450°C in air.     

Synthesis and characterization of aromatic polymers containing pendant silyl groups. I. Polyarylates

Polyarylates containing pendant silyl group were prepared by the phase-transfer catalyzed, two-phase polycondensations of 2,2-bis (4-hydroxyphenyl) propane with corresponding dicarbonyl chlorides such as 2-trimethylsilylterephthaloyl chloride, 5-trimethylsilylisophthaloyl chloride, 5-dimethylphenylsilylisophthaloyl chloride, and 5-triphenylsilylisophthaloyl chloride. The resulting amorphous polyarylates with glass transition temperatures of 163–214°C had inherent viscosities in the range of 0.41–0.95 dL/g. These polyarylates were readily soluble in common chlorinated hydrocarbons and it was possible to obtain transparent, flexible, and tough films from the polymer solutions. The prepared polyarylates showed fairly good thermal stabilities as well as tensile strengths, i.e., the tensile strengths of the cast films from chloroform solution were 6.0–6.7 kg/mm². And TGA data revealed 10% weight losses and residual weights at 800°C were 437–495°C and 27–40% under nitrogen atmosphere, respectively. © 1992 John Wiley & Sons, Inc.     

Synthesis and electrochromism of novel organosoluble polyarylates bearing triphenylamine moieties

A series of novel aromatic polyarylates with triphenylamine units in the main chain and as the pendent group were prepared from the dicarboxylic acid monomer, N,N‐bis(4‐carboxyphenyl)‐N′, N′‐diphenyl‐1,4‐phenylenediamine (1), and various bisphenols. These polyarylates were amorphous and readily soluble in common organic solvents. They had excellent levels of thermal stability associated with moderately high T_g values (182–263 °C). These polymers exhibited strong UV–vis absorption bands at 357–360 nm in toluene solution and the photoluminescence spectra showed maximum bands around 493–503 nm in the green region. The hole‐transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyarylates exhibited two reversible oxidation redox couples in acetonitrile solution at E_onset 0.77–0.79 V and 1.12–1.14 V, respectively. The typical polymer 3b film revealed good stability of electrochromic characteristics, with color change from colorless to green and blue at applied potentials ranging from 0.00 to 1.24 V. These anodically polymeric electrochromic materials not only showed excellent reversible electrochromic stability with good green coloration efficiency (CE = 159 cm²/C) and blue coloration efficiency (CE = 154 cm²/C) but also exhibited high contrast of optical transmittance change (ΔT%), 54% in 895 nm for green color and up to 84% in 595 nm for blue color. After over 100 cyclic switches, the polymer films still exhibited excellent stability of electrochromic characteristics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2004–2014, 2007     

Synthesis and properties of aramids and polyarylates having perfluoro-substituents on the benzene ring

A new series of 16 aramids and 16 polyarylates having perfluoro-substituents on the benzene ring was prepared by a low temperature solution or an interfacial polycondensation. The effects of fluorine substituents on the structure and properties of polymers were examined. Fluorinated aramids exhibited higher crystallinity, while fluorinated polyarylates show lower crystallinity. The melting point (T_m) of aramids decreased with fluorine substitution, whereas T_m of polyarylates from fluorinated aromatic diols was higher than that of those from unfluorinated ones. The temperature of 10% weight loss and the residue at 900°C decreased with fluorine substitution except for the aramids from fluorinated diamines. Solubility and contact angle also increased with fluorine substitution. Some polyarylates were found to exhibit an optical anisotropy.     

Synthesis and properties of new polyarylates from 1,4‐bis(4‐carboxyphenoxy)naphthyl or 2,6‐bis(4‐carboxyphenoxy)naphthyl and various bisphenols

New 1,4‐naphthyl and 2,6‐naphthyl‐containing polyarylates having inherent viscosities up to 1.28 dL/g were synthesized by the high‐temperature solution polycondensation from the acid chloride of 1,4‐bis(4‐carboxyphenoxy)naphthyl or 2,6‐bis(4‐carboxyphenoxy)naphthyl and various bisphenols. Most of the resulting polyarylates showed amorphous characteristics and were readily soluble in common organic solvents such as N,N‐dimethylacetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), o‐chlorophenol, and chloroform. Transparent, flexible, and colorless films of these polymers could be cast from the DMAc solutions. Their cast films had tensile strengths ranging from 54.9 to 84.2 MPa, elongations at break from 5.3% to 19.0%, and initial modulus from 2.0 to 2.8 GPa. These polymers had glass transition temperatures in the range of 172–280°C and began to lose weight around 400°C, with 10% weight loss being recorded at about 450°C in air. Dynamic mechanical analysis (DMA) reveals that the polyarylates containing isopropylidene linkages have three transitions on the temperature scale between −100 and 300°C. However, only two transitions were observed in the other polyarylates without isoproylidene linkage. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 645–652, 1999     

Preparation and properties of polyarylates and copolyarylates from phenylindanedicarbonyl chloride and bisphenols

A series of polyarylates having inherent viscosities of 0.4–1.1 dL/g was prepared by the two phase polycondensation of 1,1,3-trimethyl-3-(4-chloroformylphenyl)indanecarbonyl chloride with various bisphenols in an organic solvent–aqueous alkaline solution system in the presence of a phase transfer catalyst. Similarly, copolyarylates of high molecular weights were prepared from a mixture of the phenylindanedicarbonyl chloride, terephthaloyl chloride, and 2,2-bis(4-hydroxy-phenyl)propane. All the polyarylates were characterized by their amorphous nature and high solubility in organic solvents. They gave transparent and tough films by the solution casting. The films had tensile strength of 33–46 MPa, elongation at break of 3–16%, and tensile modulus of 1.2–1.6 GPa. These polyarylates had glass transition temperatures in the range of 205–310°C, and began to decompose at ca. 350°C in air.     

A three parameter kinetic model of formation of linear polyurethane from 2,4‐toluenediisocyanate and butane‐1,4‐diol

A model of linear isothermal polymerization of two bi‐functional monomers, one of which has alike functional groups of different reactivities, is presented. The model has been applied to the polymerization of 2,4‐toluenediisocyanate (TDI)^a and butane‐1,4‐diol carried out in solution at 86 or 101°C. The rate constant K of the reaction between an isocyanate group in position 4 of TDI and a hydroxy group, the ratio κ of reactivities of groups in position 4 relative to that in position 2, and the ratio k_φ of reactivities of an isocyanate group in the monomer relative to that at the end of an oligomer chain, have been evaluated from experimental data to be 6.51·10^–4 dm³·mol^–1·s^–1, 1.47, and 1.55 at 86°C, and 17.2·10^–4 dm³·mol^–1·s^–1, 1.55, and 1.62 at 101°C, respectively.     

Synthesis and characterization of novel polyaryloxydiphenylsilane derived from 2,2′- dimethyl-biphenyl-4,4′-diol

A novel polyaryloxydiphenylsilane was synthesized successfully by solution polycondensation of 2,2′-dimethyl-biphenyl-4,4′-diol with diphenyldichlorosilane and the catalyst triethylamine in toluene at 80 °C. Polymers with a relatively high inherent viscosity and yield were obtained when the reactions were carried out in aromatic and lipophilic solvents. The novel polyaryloxydiphenylsilane was soluble in chlorinated aliphatic hydrocarbons such as methylene chloride and chloroform as well as in polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide and also in some common organic solvents such as benzene and toluene. However, it was insoluble in both aliphatic hydrocarbons as well as in alcoholic solvents. The polyaryloxydiphenylsilane began losing weight around 400 °C under a nitrogen atmosphere, and the 10% weight-loss temperature was 473 °C. The glass-transition temperature of the polyaryloxydiphenylsilane was 102 °C. The glass transition could be lowered by the copolymerization technique with 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane as an aromatic diol comonomer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4591–4595, 1999     

Preparation of CuFe2O4/SiO2 nanocomposite starting from Cu(II)–Fe(III) carboxylates embedded in hybrid silica gels

Nanocomposites of the type 30 % CuFe₂O₄/70 % SiO₂ were synthesized using the modified sol–gel method starting from tetraethylorthosilicate, metal nitrates (Fe(NO₃)₃·9H₂O, Cu(NO₃)₂·3H₂O) and the diol: 1,3-propane diol. The obtained hybrid gel, which contains within the pores, the metal nitrates and diol, was thermally treated at 140 °C, when the redox reaction between metal nitrates and 1,3-propane diol takes place forming Cu(II)–Fe(III) carboxylate compounds of malonate type. The thermal decomposition of the carboxylates within the gels pores, at ~300 °C, leads to simple or mixed metal oxides, uniformly distributed within the amorphous silica matrix. The spinel system CuFe₂O₄/SiO₂ was obtained starting with 700 °C. The evolution of the spinel phase with the annealing temperature was investigated and resulted that at 1,000 °C, the matrix crystallizes into cristobalite and quartz. The formation of bulk CuFe₂O₄, starting from the same type of Cu(II)–Fe(III) carboxylate compounds was also investigated. A comparison between the thermal evolution of bulk CuFe₂O₄ and CuFe₂O₄/SiO₂ starting from Cu(II)–Fe(III) carboxylate compounds was made. The magnetic behavior of the ferrite nanocrystallites depending on the annealing temperature was also investigated.     

Dehydrocoupling Polymerization: Poly(silylether) Synthesis by Using an Iron β-Diketiminate Catalyst

We describe the iron-catalyzed polymerizations of diol and silane monomers to obtain fourteen different poly(silylether) products with number average molecular weights (M_n) up to 36.3 kDa. The polymerization reactions developed in this study are operationally simple and applicable to 1° and 2° silane monomer substrates and a range of benzylic and aliphatic diol substrates as well as one polyol example. The polymers were characterized by IR spectroscopy, DSC and TGA and, where solubility allowed, ¹H, ¹³C{¹H}, ²⁹Si{¹H} NMR spectroscopies, GPC and MALDI-TOF were also employed. The materials obtained displayed low T_g values (−70.6 to 19.1 °C) and were stable upon heating up to T_–5%,Ar 421.6 °C. A trend in T_–5%,Ar was observed whereby use of a 2° silane leads to higher T_–5%,Ar compared to those obtained using a 1° silane. Reaction monitoring was undertaken by in situ gas evolution studies coupled with GPC analysis to follow the progression of chain-length growth which confirmed a condensation polymerization-type mechanism.     

Synthesis and properties of new aromatic poly‐(ether benzoxazole)s from 2,2′‐bis(4‐amino‐3‐hydroxyphenoxy)biphenyl and aromatic dicarboxylic acid chlorides

A new bis(o‐aminophenol) with a crank and twisted noncoplanar structure and ether linkages, 2,2′‐bis(4‐amino‐3‐hydroxyphenoxy)biphenyl, was synthesized by the reaction of 2‐benzyloxy‐4‐fluoronitrobenzene with biphenyl‐2,2′‐diol, followed by reduction. Biphenyl‐2,2′‐diyl‐containing aromatic poly(ether benzoxazole)s with inherent viscosities of 0.52–1.01 dL/g were obtained by a conventional two‐step procedure involving the polycondensation of the bis(o‐aminophenol) monomer with various aromatic dicarboxylic acid chlorides, yielding precursor poly(ether o‐hydroxyamide)s, and subsequent thermal cyclodehydration. These new aromatic poly(ether benzoxazole)s were soluble in methanesulfonic acid, and some of them dissolved in m‐cresol. The aromatic poly(ether benzoxazole)s had glass‐transition temperatures of 190–251 °C and were stable up to 380 °C in nitrogen, with 10% weight losses being recorded above 520 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2656–2662, 2002     

Polyurethane elastomers based on amphiphilic poly(caprolactone)‐b‐poly(butadiene)‐b‐poly(caprolactone) triblockcopolyols

Hydroxyl‐terminated poly(butadiene) (HTPB; M_n = 2100 g mol⁻¹) was capped with 30 and 60 wt % of ɛ‐caprolactone to reach amphiphilic triblock copolymers in form of capped poly(butadiene) CPB. The former (CPB30; M_n = 3300 g/mol) is amorphous with a glass temperature of −56 °C. CPB60 (M_n = 4000 g mol⁻¹) is semi‐crystalline with a melting point of 50 °C and a glass transition at −47 °C. The CPBs, HTPB and polycaprolactone diol (M_n = 2000 g mol⁻¹) were used as soft segment components in the preparation of polyurethane elastomers (PUE), using a 1/1 mixture of an MDI prepolymer and uretonimine modified MDI, and hard phase components in form of 1,3‐propane diol, 1,4‐butane diol, and 1,5‐pentane diol. CPB‐based elastomers with 1,4 butane diol (8 wt %) show hard domains as fringed aggregates with a better connection to the continuous phase than the HTPB‐based PUE. The soft segment glass transition temperature (T_g) is at −28 °C for HTPB‐based PUE and at −43 °C for those of CPB. The tensile strength of the CPB30&60‐based PUE is found between 20 and 30 MPa at an elongation at break of 400% and 550%, respectively. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1162–1172     

Influence of Isosorbide on Glass‐Transition Temperature and Crystallinity of Poly(butylene terephthalate)

Copolyesters of isosorbide and 1,4‐butane diol were prepared by Ti(OBu)₄‐catalyzed transesterifications with dimethyl terephthalate in bulk at temperatures up to 250°C. The content of isosorbide was considerably lower than expected from the feed ratio and the molar masses were low, so that no DSC measurements were conducted. Copolycondensations of isosorbide and 1,4‐butane diol with terephthaloyl chloride were either performed in dichloromethane at 40°C or in toluene at 100°C. The second method gave the higher molar masses. However, both series of polycondensations had the content of isosorbide roughly paralleled the feed ratios in common. The DSC measurements revealed that even 6 mol% of isosorbide is sufficient to raise the glass‐transition temperature (T_g) by 10–12°C (up to 55°C). With 50 mol% of isosorbide, the T_g reaches 100°C. Yet, incorporation of isosorbide also reduces the melting temperature T_m and the degree of crystallinity, and a mol percentage above 30% prevents crystallization completely. In summary, incorporation of isosorbide allows for fine‐tuning of T_g and T_m of poly(butylene terephthalate) over a wide range.     

Rigid triol and diol with adamantane‐like core derived from naturally occurring myo‐inositol and their polyaddition with diisocyanates

Two orthoester derivatives 1 and 2 that are easily accessible from naturally occurring myo‐inositol were exploited as new triol‐ and diol‐type monomers bearing a rigid adamantane‐like structure to polyaddition with diisocyanates that gave the corresponding networked and linear polyurethanes. DSC analysis of the networked polyurethanes revealed their high glass transition temperatures ranging from 155 to 248 °C, suggesting the contribution of the rigidity of the adamantane‐like structure introduced at the nodes of the networked polyurethanes 6. Besides, the polyaddition of 2 with diisocyanates gave the corresponding linear polyurethanes 4, of which glass transition temperatures were high, ranging from 105 to 177 °C, presumably by virtue of the rigidity of the adamantane‐like structure introduced into the main chains. T_gs of the networked polyurethanes 6 were higher than those of the linear polyurethanes 4. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3498–3505