Soluble Poly Arylene Research Articles

Soluble Polyarylates Based on Methyl-substituted Bisphenols Containing Pendent Biphenyl Moiety: Synthesis, Characterization, and Thermal Properties

Soluble Polyarylates Based on Methyl-substituted Bisphenols Containing Pendent Biphenyl Moiety: Synthesis, Characterization, and Thermal Properties

Research on the relationship between structure and properties of the soluble polyaryl ether ketone terminated with phthalonitrile

A novel soluble poly(aryl ether ketone) (PAEK) terminated with 4-nitrophthalonitrile was designed and synthesized, which was used to solve the problem of difficult solution processing. Then, a series of cross-linked PAEK films with different thermal treatment temperatures were fabricated by using 4,4-bis(3,4-dicyanophenoxy)biphenyl (BPH) as a novel cross-linking agent, improving the glass transition temperature (Tg) of the traditional PAEK. Then, the fourier transform infrared (FT-IR) spectrum, X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA), dynamic mechanical analysis (DMA), mechanical testing machine and LCR meter were used to investigate the microstructure, thermal, mechanical and dielectric properties of PAEK films, respectively. The results indicated that the increase in heat-treatment time and temperature are beneficial for the improvement of the value of Tg and T5%, and the excellent thermal stability and mechanical properties of PAEK films are demonstrated. Compared to PAEK-1 film, the Tg and T5% both increased by 63 °C for PAEK-4 film. Significantly, the tensile strength of PAEK-3 film (42 MPa) reaches the highest value in comparison with other samples. In addition, the dielectric constants (e) and loss tangent (tan δ) of PAEK-4 film is as low as 3.67 and 0.001 at 1 kHz, respectively. More importantly, the dielectric properties are found to be relatively stable to near the Tg value, which can be widely used for applications in dielectric energy storage at high temperatures.

Preparation and characterization of novel soluble polyarylates derived from 9,9-bis[4-(4-chloroformylphenoxy)phenyl]xanthene with various bisphenols

A series of new polyarylates bearing cardo xanthene groups were synthesized by phase-transfer-catalyzed interfacial polycondensation of 9,9-bis[4-(4-chloroformylphenoxy)phenyl]xanthene with various bisphenols containing the isopropylidene, hexafluoroisopropylidene, 1-phenylethylidene, diphenylmethane, cyclohexane, and xanthene structures. High-molecular-weight polyarylates with number-average molecular weight and polydispersity index in the range of 30,100–35,300 and 1.82–2.17, respectively, exhibited high glass transition temperatures ranged from 226°C to 261°C, and their 10% weight loss temperatures were in the range of 421–452°C with char yields above 45% at 700°C in nitrogen. All the polyarylates were amorphous and readily soluble in organic solvents such as dichloromethane, chloroform, tetrahydrofuran, meta-cresol, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, and 1-methyl-2-pyrrolidinone at room temperature and could be cast into tough, transparent, and flexible films with tensile strengths of 85.6–108.3 MPa, elongations at break of 2–3%, and tensile moduli of 7–9 GPa.

CTAB induced emission from water soluble polyarylene ether nitrile carboxylate and selective sensing of Fe (III) ions

Polyarylene ether nitrile (PEN) is traditionally used as high performance thermoplastics in various advanced engineering materials fields. However, the preparation of optically active PEN based materials, especially in aqueous solution, is still a great challenge. In this work, the side chain carboxylated PEN can be readily dissolved in alkaline solution but showing strongly quenched luminescence. Fortunately, the cationic surfactant of cetyltrimethylammonium bromide (CTAB) was able to recover the fluorescence emission of water soluble PEN, which can be subsequently quenched by Fe3+ ions, leading to the selective determination of Fe3+ ions in aqueous solution.

Soluble polyarylates containing phosphorus in main chains with thermal stability

ABSTRACTA series of polyarylates containing phosphorus (pho‐PARs) were synthesized from bisphenol A with different molar ratios of bis‐(4‐carboxyphenyl) phenyl phosphine oxide (BCPPO) to terephthalic acid (TPA). When the contents of BCPPO are in the range of 0.4–1.0, the pho‐PARs are readily soluble in a wide range of organic solvents and have the glass transition temperatures of 243.0–260.4°C. The initial degradation temperatures of these pho‐PARs are all above 450°C and their char yields at 800°C under nitrogen atmosphere are in the range of 28.7–33.0%, suggesting they have excellent thermal stability. The results of TG‐FTIR and FT‐IR show the introduction of BCPPO change the decomposition model of the pho‐PARs. The limiting oxygen indexes are at a range of 30.7–34.5%, which suggests that the pho‐PARs are a kind of excellent inherent flame retardant materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3521–3529, 2013

Synthesis of novel polyarylate with elecrooptical chromophores as side chain as electro-optic host polymer

Two novel soluble polyarylates with different nonlinear optical chromophores as the side chains were prepared and characterized by UV–visible spectra, nuclear magnetic resonance, and infrared spectroscopy. The titled polymers show us good thermal stability; the thermal decomposition temperature values were 201 and 253 °C, respectively, for polymer sPAR-CTCF and sPAR-CTCP. The glass transition temperatures were 139 and 122 °C for sPAR-CTCF and sPAR-CTCP, respectively. Chromophore FTC-wl was doped in these polymers as a guest chromophore to form binary chromophore electro-optic (EO) system. And super large EO coefficients (124 pm/V) were found from FTC-wl-doped sPAR-CTCP binary chromophore system at high chromophore loading density.

Synthesis and characterization of readily soluble polyarylates derived from either 1,1‐bis(4‐hydroxyphenyl)‐1‐phenylethane or tetramethylbisphenol A and aromatic diacid chlorides

AbstractA series easily soluble polyarylates were synthesized from either 1,1‐bis(4‐hydroxyphenyl)‐1‐phenylethane or tetramethylbisphenol A with various aromatic diacid chlorides by the two‐phase interfacial polycondensation. These polyarylates have the inherent viscositiesin the range of 0.36–0.97 dL/g, and their number‐average and weight‐average molecular weights determined by gel permeation chromatography are 14,200–43,200 and 31,900–102,500, respectively. All these polyarylates are readily soluble in a wide range of organic solvents, thus these polymers can be convenient to process into heat resistance films by cast, spin‐ or dip‐coating. The polyarylates have the glass transition temperatures in the range of 165.0–201.6°C. The pendent phenyl‐containing polyarylates reveal excellent thermal stability, and their initial degradation temperatures are all above 480°C and char yields at 700°C are 37.97–40.53% in nitrogen atmosphere. However, the polymers prepared from tetramethylbisphenol A have a large decrease in thermal stability, and their initial degradation temperatures in nitrogen are only about 440°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Modification of cyanate ester resin by soluble polyarylates

AbstractSoluble polyarylates were prepared from the reaction of 2,2‐bis(4‐hydroxyphenyl)propane (bisphenol‐A) and aromatic acid dichlorides (phthaloyl chloride and related diacid dichlorides), and used to improve the brittleness of a cyanate ester resin. The polyarylates include poly[2,2‐di(4‐phenylene)propane phthalate] (PPA), poly[2,2‐di(4‐phenylene)propane phthalate‐co‐2,2‐di(4‐phenylene)propane isophthalate] (IPPA) and poly[2,2‐di(4‐phenylene)propane phthalate‐co‐2,2‐di(4‐phenylene)propane terephthalate] (TPPA). Furthermore, a commercial polyarylate, U‐polymer, was also used as a modifier. The morphologies of the modified resins depended on the polyarylate structure and concentration. The most effective modification of the cyanate ester resin could be attained because of the co‐continuous phase structure of the modified resin: 25 wt% inclusion of IPPA (50 mol% isophthalate units, weight average molecular weight (Mw) 38 500 g mol−1) led to a 130% increase in the fracture toughness (KIC) for the modified resin, with retention of its flexural properties and glass transition temperature, as compared with the values for the unmodified resin. Water absorptivity of the IPPA‐modified resin was smaller than that of the unmodified resin. Copyright © 2003 Society of Chemical Industry

Thermally Stable Polyarylenes with Low Dielectric Constant: Direction towards the Lowest Limit of Dielectrics.

We successfully prepared a series of soluble, thermally stable Polyarylenes with low dielectric constant (k) by coupling polymerization of aromatic dihalides and/or bismesylates of the corresponding bisphenols using Zn and Ni-phosphine catalysts. Among the non-fluorinated polyarylenes, a soluble copolyarylene derived from bismesylates of 9, 9-bis(4-hydroxyphenyl)fluorene and 4, 4′-dihydroxyphenyl-diphenylmethane showed with k=2.7 (@1MHz), Tg:>300°C, and Td (5%, N2):549°C the lowest k value. The polyarylene with the lowest k, a fluorinated polymer prepared from the bismesylate of 2, 2-bis-(4-hydroxyphenyl)hexafluoropropane, showed k=2.2 (@1MHz), Tg:249°C and Td (5%, N2):508°C. Among organic polymers, soluble polyarylenes proved to be very promising as low k materials with high thermal stability. In addition, we show based on these new results and previous results with fluorenyliden-substituted polyimides how to estimate the dielectric constant in polyimides and polyarylenes as a function of polar linkage (imide) concentration and fluorine content.

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.

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.

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 polyarylates from 2,2′‐dihydroxy‐1,1′‐binaphthyl and aromatic dicarboxylic acid chlorides

Amorphous soluble polyarylates [O(C 10 H 6 )-(C 10 H 6 )-OCO-Ar-CO] n (Ar= Ph, C 10 H 6 , PhPh, PhOPh) were synthesized by ultrasound-assisted two-phase polycondensation. The polymers had 10% weight loss temperatures of 470-490°C under nitrogen

Synthesis and Ni(0)‐catalyzed polymerization of 2,5‐bis(4‐chloro‐1‐naphthyl)biphenyl

A novel synthetic route to bis(4-chloro-1-naphtyl)aryl derivatives which are starting monomers for the preparation of soluble polyarylenes containing 1,1-binaphtylene and 2,5-biphenylene units. The present polymers [(C 10 H 6 )-Ph(Ph)-(C 10 H 6 )] n are soluble in conventional organic solvents

Synthesis of soluble polyarylenes containing alternating 4,4?-(1,1?-binaphthyl) and 4,4?-(3,3?-diphenyl)biphenyl structural units

The synthesis and Ni(0) catalyzed homocoupling polymerization of 4,4′-bis[5-(trifluoromethanesulfonyloxy)-2-biphenylyl]-1, 1′-binaphthyl (9) are described. This polymerization reaction produces a soluble polyarylene containing alternating 4,4′-(1,1′-binaphthyl) and 4,4′-(3,3′-diphenyl)biphenyl structural units.

Soluble polyarylenes with alternating sequences of alkyl-substituted phenylene and pyrrolic or terpyrrolic units

Soluble polyarylenes with alternating sequences of alkyl-substituted phenylene and pyrrolic or terpyrrolic units

Soluble polyarylenes containing alternating binaphthylene and biphenylene structural units

AbstractThis article describes the synthesis of a novel series of soluble polyarylenes containing alternating binapthylene and biphenylene structural units. They were obtained by the cation‐radical polymerization of bis(1‐naphthyl) biphenyls. The following monomers were synthesized and polymerized : 4,4′‐bis(1‐naphthyl) biphenyl (9), 3,3′‐bis(1‐naphthyl) biphenyl (10), 2,2′‐bis(1‐naphthyl)biphenyl (11), and 2,5‐bis(1‐naphthyl)biphenyl (14). All polymerizations were performed in nitrobenzene using FeCl3 as oxidant. Polymers with number average molecular weights of up to 4000 g/mol were obtained.

Polyaeylates based on carbonyl-containing bisphenols

1. Homogeneous and mixed polyarylates of 1, 3- and 1, 4-bis-(4′-hydroxybenzoyl)benzenes and 2, 2-bis- (4′-hydroxyphenyl)acenaphthanone with aliphatic and aromatic dicarboxylic acids were synthesized and their properties were investigated. 2. The transition from cyclic structure of phenolphthalein to the “open” structure of 1, 3- and 1, 4-bis- (4′-hydroxybenzoyl) benzenes in polyarylates based thereon results in increased crystallization tendency and sharply decreased solubility; amorphous, highly soluble polyarylates of 1, 3- and 1,4-bis- (4′-hydroxybenzoyl) benzene s have relatively low softening temperatures. 3. Comparison of polyarylates of 2, 2-bis-(4′-hydroxyphenyl)acenaphthenone with polyarylates of phenolphthalein, phenolfluorene, and phenolanthrone shows that polymers of this type have similar properties.