Synthesis and characterization of novel fluorinated polyimides derived from 4,4′-[2,2,2-trifluoro-1-(3,5-ditrifluoromethylphenyl)ethylidene]diphthalic anhydride and aromatic diamines

A novel fluorinated aromatic dianhydride, 4,4′-[2,2,2-trifluoro-1-(3,5-ditrifluoromethylphenyl) ethylidene] diphthalic anhydride (9FDA), was synthesized, which was employed to polycondense with various aromatic diamines, including 4,4′-oxydianiline, 1,4-bis(4-aminophenoxy) benzene, 3,4′-oxydianiline and 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene to produce a series of fluorinated aromatic polyimides. The fluorinated polyimides obtained had inherent viscosities ranged of 0.61-1.14 dL/g and were easily dissolved both in polar aprotic solvents and in low boiling point common solvents. High quality polyimide films could be prepared by casting the polyimide solution on glass plate followed by thermal baking to remove the organic solvents and volatile completely. Experimental results indicated that the fluorinated polyimides exhibited good thermal stability with glass transition temperature ranged of 245-283 °C and temperature at 5% weight loss of 536-546 °C. Moreover, the polyimide films showed outstanding mechanical properties with the tensile strengths of 87.7-102.7 MPa and elongation at breaks of 5.0-7.8%, good dielectric properties with low dielectric constants of 2.71-2.97 and low dissipation factor in the range of 0.0013-0.0028.     

Polyamide-imides bearing furan moieties. 1. Solution polycondensation of aromatic dianhydrydes with 2-furoic acid dihydrazides

Novel polyamide-imides containing flexible segments were synthesized from aromatic dianhydrides and various furan dihydrazides by a two-steps procedure that included ring opening polyaddition to give polyhydrazide-acids, followed by thermal or chemical cyclodehydration. The polyhydrazide-acids had inherent viscosities ranging from 0.045 to 0.11 l/g. The polyamide-imides showed good solubility in aprotic polar solvents and had inherent viscosities up to 0.070 l/g, glass transition temperatures close to 250 °C and good thermal stability up to 350 °C.     

Preparation and properties of novel polyimides with side chains containing biphenyl units

Novel polyimides with side chains containing various methylene spacers and biphenyl end groups were prepared. They were characterized by the inherent viscosity, mechanical properties, and solubility and by Fourier transform infrared, ¹H‐nuclear magnetic resonance, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. All the polyimides with biphenyl side groups could be formed into tough films. WAXD showed that all the films were apparently amorphous. By incorporating side chains, the solubility was greatly enhanced and all the polyimides with side chains showed good solubility in polar aprotic solvents, while the high moduli and strength of typical polyimides were maintained and even improved. However, the heat‐resistant properties such as the thermal stability and glass transition temperature were generally decreased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3291–3298, 2003     

Organosoluble asymmetric aromatic polyamides bearing pendent phenoxy groups

This study focuses on the synthesis and characterization of new polyamides based on an aromatic asymmetric diamine‐containing phenoxy‐substituted benzophenone segment. Low‐temperature solution polycondensation reactions of this diamine with various aromatic diacid chlorides containing ether, hexafluoroisopropylidene or diphenylsilane groups resulted in polyamides with molecular weights in the range 102 900–113 200 g mol^?1. The structures of these monomers and the corresponding polymers were fully confirmed using elemental analysis and infrared and NMR spectroscopy. All polyamides were easily soluble at room temperature in polar aprotic solvents and even in less polar solvents such as tetrahydrofuran. The polymers showed excellent thermal stability, up to 385 °C, and displayed glass transition temperatures in the range 225–256 °C. All the polymers presented blue florescence upon irradiation with UV light and thus show promise for applications in electroluminescent devices. Copyright © 2011 Society of Chemical Industry     

Synthesis and characterisation of organosoluble polyimides containing the anisyl moiety

A new type of diamine monomer containing the anisyl moiety was synthesized via a straight‐forward one‐step procedure. Anisaldehyde was reacted with 2,6‐dimethylaniline in the presence of dry HCl to attain bis(4‐amino‐3,5‐dimethylphenyl)anisylmethane. A series of organo‐soluble polyimides were prepared using the anisyl diamine and various aromatic dianhydrides via a two step method involving thermal imidization. All polyimides are soluble in strong polar solvents such as N‐methyl‐2‐pyrollidone, N,N‐Dimethylformamide, and N,N‐DimethylAcetamide. The polyimides show excellent thermal stability and good mechanical properties. The glass transition temperatures of the polyimides are in the range 265–294 °C. The tensile strengths are in the range 79–99 MPa and the temperatures at which 10 % weight loss occurs are in the range 460–496 °C. Copyright © 2004 Society of Chemical Industry     

Solvent interactions with polysulfone

We have used gas chromatography to study solvent interactions with polysulfone at temperatures below the glass transition. A previously published procedure has been employed to decompose the Gibbs energy of sorption of various solvents in polysulfone into its component contributions from dispersion forces, polar forces, and forces of specific interactions such as hydrogen bonding. The gas chromatographic results and the analysis of Gibbs energy of sorption has been used to establish general criteria for solubility of nonpolar, polar, and specifically interacting solvents in polysulfone.     

Mechanical and Electrical Properties of SomeSilicon-Containing Poly(Amide-Imide)s

Aromatic silicon-containing poly(amide-imide)s have been prepared by low temperature solution polycondensation reaction of various aromatic diamines having ether bridges between phenylene rings with a diacid chloride, namely bis[N-(4-chlorocarbonylphenyl) phthalimidyl]dimethylsilane. These polymers were easily soluble in polar amidic solvents such as N-methylpyrrolidone,N,N-dimethylacetamide, and N,N-dimethylformamide and can be cast from solutions into thin, flexible films. They showed good thermal stability, with initial decomposition temperature being above 410°C and glass transition temperature in the range of 263–285°C. The polymer films exhibited good mechanical properties with tensile strengths in the range of 78–109 MPa, tensile modulus in the range of 1.44–1.76 GPa, and elongation at break values ranging from 11% to 24%. Electrical insulating properties of two polymer films were evaluated on the basis of dielectric constant and dielectric loss and their variation with frequency and temperature.     

Preparation and properties of melt‐processable polyimides based on fluorinated aromatic diamines and aromatic dianhydrides

Two series of melt‐processable polyimides were prepared from 4,4′‐bis(3‐amino‐5‐trifluoromethylphenoxy)biphenyl (m‐6FBAB) and 4,4′‐bis(4‐amino‐5‐trifluoromethylphenoxy) biphenyl (p‐6FBAB) with various aromatic dianhydrides. The effects of the chemical structures of the polyimides on their properties, especially the melt processability and organic solubility, were investigated. The experimental results demonstrate that some of the fluorinated aromatic polyimides showed good melt processability at elevated temperatures (250–360°C) with relatively low melt viscosities and could be melt‐molded to produce strong and tough polyimide sheets. Meanwhile, the polyimides showed excellent organic solubility in both polar aprotic solvents and common solvents to give stable polyimide solutions with high polymer concentrations and relatively low viscosities. Thus, we prepared high‐quality polyimide films by casting the polyimide solutions on glass plates followed by baking at relatively low temperatures. The polyimides derived from m‐6FBAB showed better melt processability and solubility than the p‐6FBAB based polymers. The melt‐processable polyimides showed a good combination of thermal stability and mechanical properties, with decomposition temperatures of 547–597°C, glass‐transition temperatures in the range 205–264°C, tensile strengths of 81.3–104.9 MPa, and elongations at break as high as 19.6%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

氯化聚丙烯溶度参数的研究

氯化聚丙烯是对聚丙烯材料有很好的粘结力 ,为了进行基础的应用研究 ,用浊度法对其溶度参数进行了测定 ,得到其溶度参数为 16 .72～ 2 1.15 (J/cm3 ) 1/ 2 。氯化聚丙烯溶解性能实验表明 :氯化聚丙烯属于弱极性物质。在溶度参数接近时 ,一般弱极性溶剂为良溶剂 ,中等极性溶剂为微溶溶剂。还用三维溶度参数对CPP的溶解性能进行了讨论。     

Poly(ether imide)s containing cyano substituents and thin films made from them

A series of poly(ether imide)s containing functional cyano groups has been prepared by polycondensation reaction of 2,6‐bis(m‐aminophenoxy)benzonitrile with different bis(ether dianhydride)s, such as 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]isopropane dianhydride, 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)‐phenyl]hexafluoroisopropane dianhydride, 1,1‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]cyclohexane dianhydride, and 3,3‐bis[4‐(3,4‐dicarboxyphenoxy) phenyl]phthalide dianhydride. The polymers were soluble in polar aprotic solvents and even in less polar solvents and were processed into thin films by casting their solutions. The properties of the polymers, particularly the crosslinking of macromolecular chains through cyano groups, were studied by using dynamic mechanical analysis (DMA), thermal stability, glass transition, and solubility measurements. Also, the molecular relaxations were evidenced by DMA and dielectric spectroscopy. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fluorinated poly(aryl thioether)s and poly(aryl sulfone)s derived from 2,3,4,5,6‐pentafluorobenzoic acid

Poly(aryl thioether)s (F‐PTEs) containing 2,3,5,6‐tetrafluoro‐1,4‐phenylene moiety and polar moiety, such as 1,3,4‐ozadiazole, ether ketone, and amide groups, were synthesized by nucleophilic aromatic substitution reaction of aryl fluorides and 4,4′‐thiobisbenzenthiol. F‐PTEs were amorphous with good thermal properties including high glass transition temperature (T_g) and thermal stability, solubility, and hydrophobicity. F‐PTEs were transformed into poly(aryl sulfone)s (F‐PSs) by the oxidation reaction with hydrogen peroxide in acetic acid. Because of the sulfone group, the T_gs of the F‐PSs were 30–40°C higher than those of the corresponding F‐PTEs. F‐PSs maintained solubility in polar aprotic solvents and exhibited hydrophobicity in spite of the content of polar sulfone groups due to the highly substituted fluorine atoms. These F‐PTEs and F‐PSs were a new class of high‐performance polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fabrication,characterization, and thermal property evaluation of silver nanofluids

Silver nanoparticles were successfully prepared in two different solvents using a microwave heating technique, with various irradiation times. The silver nanoparticles were dispersed in polar liquids (distilled water and ethylene glycol) without any other reducing agent, in the presence of the stabilizer polyvinylpyrrolidone (PVP). The optical properties, thermal properties, and morphology of the synthesized silver particles were characterized using ultraviolet-visible spectroscopy, photopyroelectric technique, and transmission electron microscopy. It was found that for the both solvents, the effect of microwave irradiation was mainly on the particles distribution, rather than the size, which enabled to make stable and homogeneous silver nanofluids. The individual spherical nanostructure of self-assembled nanoparticles has been formed during microwave irradiation. Ethylene glycol solution, due to its special properties, such as high dielectric loss, high molecular weight, and high boiling point, can serve as a good solvent for microwave heating and is found to be a more suitable medium than the distilled water. A photopyroelectric technique was carried out to measure thermal diffusivity of the samples. The precision and accuracy of this technique was established by comparing the measured thermal diffusivity of the distilled water and ethylene glycol with values reported in the literature. The thermal diffusivity ratio of the silver nanofluids increased up to 1.15 and 1.25 for distilled water and ethylene glycol, respectively.     

Synthesis and properties of novel benzocyclobutene‐functionalized siloxane thermosets

Two kinds of novel benzocyclobutene (BCB) functionalized monomers were synthesized through imidization of siloxane‐containing dianhydride with 4‐aminobenzocyclobutene. The BCB monomers obtained exhibited good solubility in various organic solvents. They were converted into crosslinked polymer via ring opening and the following Diels–Alder reaction at proper temperature. The curing kinetics were studied by non‐isothermal differential scanning calorimetry. The BCB polymers showed good thermal stability, excellent dielectric properties, low water absorption and good planarization. Moreover, the thermal and mechanical properties of the BCB resins could be adjusted by the length of the siloxane unit. The BCB resins with a shorter siloxane chain exhibited higher glass transition temperature, higher modulus and lower coefficient of thermal expansion than BCB resins with longer chains. © 2013 Society of Chemical Industry     

Synthesis and properties of novel soluble polychloro substituted aromatic polyamides

A novel monomer of tetrachloroterephthaloyl chloride (TCTPC) was prepared by the chlorination of terephthaloyl chloride catalyzed by ferric chloride at 175–180°C for 10 h, and confirmed by FTIR, MS, and elemental analysis. A series of new polychloro substituted polyamides with inherent viscosities of 1.17–1.28 dL/g have been prepared from TCTPC with various aromatic diamines. All the polyamides were amorphous and readily soluble in polar solvents such as NMP, DMAc, DMF, and DMSO at room temperature, and could afford flexible and tough films via solution casting. The cast films exhibited good mechanical properties with tensile strengths of 83.6–106.8 MPa, elongations at breakage of 3.9–7.1%, and tensile modulus of 2.28–3.98 GPa. These polyamide films also exhibited good thermal stability with the glass transition temperature of 250–284°C, the temperature at 5% weight loss of 470–504°C and high char yields of 57.8–59.7% in nitrogen. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly(phenylquinoxaline-imide-amide)s containing perfluoroisopropylidene units

Poly(phenylquinoxaline-imide-amide)s have been synthesized by solution polycondensation of aromatic diamines containing preformed phenylquinoxaline units with diacid dichlorides incorporating preformed imide rings and perfluoroisopropylidene units. These polymers show high thermal stability; they decompose above 400°C and have glass transition temperatures in the 225–290°C range. Comparison of these compounds with related heterocyclic polymers leads to the conclusion that the decomposition of the former ones begins with the destruction of amide groups. Films prepared from polymer solutions showed good electrical insulating properties, comparable to those of a standard film (Film H). The highest quality of these poly(phenylquinoxaline-imide-amide)s is their remarkable solubility in polar aprotic solvents, which is very important for practical applications.     

Synthesis and characterization of novel polyimides derived from 1,1-bis[4-(4′-aminophenoxy)phenyl]-1- [3″,5″-bis(trifluoromethyl)phenyl]-2,2,2-trifluoroethane

A novel fluorinated aromatic diamine monomer, 1,1-bis[4-(4′-aminophenoxy)phenyl]-1-[3″,5″-bis(trifluoromethyl)phenyl]-2,2,2-trifluoroethane(9FTPBA), was synthesized by coupling 3′,5′-bis(trifluoromethyl)-2,2,2-trifluoroacetophenone with 4-nitrophenyl phenyl ether under the catalysis of trifluoromethanesulfonic acid, followed reduced by reductive iron and hydrochloric acid. A series of new fluorine-containing polyimides having inherent viscosities of 0.96-1.23 dl/g was synthesized from the novel diamine with various commercially available aromatic dianhydrides using a standard two-stage process with thermal imidization and chemical imidization of poly(amic acid) films. All the fluorinated polyimides were soluble in many polar organic solvents such as NMP, DMAc, DMF, and m-cresol, as well as some of low boiling point organic solvents such as chloroform and acetone. The polymer films have good thermal stability with the glass transition temperature of 223-225 °C, the temperature at 5% weight loss of 535-568 °C in nitrogen, and have outstanding mechanical properties with the tensile strengths of 68-89 MPa, initial moduli of 2.14-2.19 GPa, and elongations at breakage of 3.2-10.5%.     

Organosoluble and light-colored fluorinated semialicyclic polyimide derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride

In this study, the alicyclic dianhydrides 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) was polymerized with seven kinds of fluorinated aromatic diamines, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (1), 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (2), 1,4-bis(4-amino-2-trifluoromethylphenoxy)diphenyl (3), 1,4-bis(4-amino-2-trifluoromethylphenoxy) diphenyl ether (4), 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane (5), 4,4′-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone (6), and 2,7-bis(4-amino-2-trifluoromethylphenoxy)naphthalene (7), via a two-step polycondensation procedure to prepare seven kinds of fluorinated semialicyclic polyimides (PI) PI-1 ∼ PI-7. The structures of these polyimides were confirmed by infrared spectroscopy (IR). Solubility of the polyimides was tested in various organic solvents and their thermal properties were investigated by dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). Ultraviolet-visible spectra (UV-vis) and near infrared absorption spectra (NIR) were obtained to evaluate the optical properties of these polyimides. The obtained polyimides PI-1 ∼ PI-7 displayed excellent solubility in a variety of organic solvents; they were readily soluble in amide-type polar solvent. These polyimide films exhibited good optical transparency in the visible light region (400–700 nm) with the transmittance higher than 80% at 450 nm, and these polyimide films showed little absorption at the optocommunication wavelengths of 1.30 and 1.55 μm. These polyimides showed good thermal stability with the 10% thermal decomposing temperatures higher than 443°C in nitrogen and the glass transition temperatures higher than 265°C. In addition, the effect of the structure of fluorinated diamines on the properties of polyimide films was also compared. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of poly(amide imide)s containing cyclohexylidene moieties with bulky substituents

Novel poly(amide imide)s (PAI) containing alkyl-substituted cyclohexylidene moieties were synthesized by conventional polycondensation of trimellitic anhydride chloride with novel aromatic diamines followed by chemical imidization using acetic anhydride and pyridine. The inherent viscosities of the resulting PAIs are relatively high and range from 71 to 112 mL g^–1. The prepared PAIs show excellent thermal stability and good solubility. The glass transition temperatures (T_g) measured by DSC are observed in the range of 312–342°C. Furthermore, all the polymers are readily soluble in less hygroscopic organic solvents like cyclohexanone, γ-butyrolactone as well as aprotic polar solvents.     

Spectroscopic and thermal characterization of the swelling behavior of nafion membranes in mixtures of water and methanol

The spectroscopic and thermal properties of swollen Nafion membranes in methanol aqueous mixtures were investigated to understand the behavior of commercial electrolytes in the presence of polar solvents. Several differences were observed in the absorption processes depending on the composition of the solvent. Deconvolution methods were applied to study specific contributions of solvents and polymer groups based on Fourier transform infrared spectroscopy and thermogravimetric analysis. The results evidence compositional effects on the interactions between solvents and Nafion. A major influence of the nonpolar domains (hydrophobic regions) in the absorption of methanol together with a reduction of the interactions with sulfonate groups was observed. Such changes are accompanied by a modification of the cluster morphology of the equilibrated membranes evaluated by differential scanning calorimetry. These findings can be useful to improve the knowledge on Nafion's microstructure in the presence of polar solvents. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Poly(ether ether sulfone amide)s as a new category of processable heat-resistant polymers

The aim of study was to prepare novel polyamides with improved solubility and processability without sacrifice of their thermal and mechanical properties. Polyamides containing ether and sulfone units were obtained via condensation of a special diamine with various diacid chlorides. Poly(ether ether sulfone amide)s were obtained in good inherent viscosities ranging from 0.72 to 0.84 dL/g. All the polyamides were amorphous and readily soluble in polar solvents and swelled in CH₂Cl₂ and tetrahydrofuran. Flexible films of polymers were obtained by solution casting. Polyamide films exhibited good mechanical and thermal stability including the temperature for 10% weight loss of 449–476 °C.