Synthesis and liquid crystalline behavior of phosphorus-containing aliphatic–aromatic copoly(ester-imide)s

A series of phosphorus-containing copoly(ester-imide)s was prepared by polycondensation reaction of 2-(6-oxido-6H-dibenz<c,e><1,2>oxaphosphorin-6-yl)-1,4-naphthalene diol, 1, or of various mixtures of 1 and 1,12-dodecanediol, 3, with an aromatic diacid chloride containing preformed imide rings, 2, namely 4-chloroformyl-N-(p-chloroformylphenyl)-phthalimide. The polymers exhibited thermotropic liquid crystalline behavior, as was observed by means of polarized light microscopy, differential scanning calorimetry, and X-ray investigations. The copoly(ester-imide)s showed good thermal stability having the temperature of 5% weight loss above 365–408 °C and char yield at 700 °C in the range 8.8–48%.     

Poly(aryl imino sulfone)s as new high-performance engineering plastics

Abstract  

Poly(aryl imino sulfone)s (PAISs) as novel high-performance polymers have been obtained by the condensation polymerization of 4,4′-dibromodiphenyl sulfone with different primary aromatic diamines via Palladium-catalyzed aryl amination reaction. The influence of the halogen-containing monomers, solvent, concentration, and temperature on the polycondensation reaction was investigated. The structure of polymers synthesized was characterized by means of FT–IR, NMR spectroscopy, and elemental analysis, the results showed an agreement with the proposed structure. Differential scanning calorimetry and thermal analysis measurements showed that polymers possessed high glass transition temperature (T _g > 145 °C) and good thermal stability with high decomposition temperatures (T _D > 450 °C). These novel polymers also exhibited good mechanical behaviors and good solubility.     

Synthesis,characterization, and properties of novel aromatic polyamides containing phthalazinone moiety

A unsymmetrical and kink non-coplanar heterocyclic dicarboxylic acid monomer, 4-[4-(4-carboxy phenoxy)-naphthyl]-2-(4-carboxyphenyl)phthalazin-1-one (3) was successfully synthesized with high purity and high yields. A series of novel polyamides containing phthalazinone were prepared from the newly synthesized dicarboxylic acid with various aromatic diamines by means of the phosphorylation polycondensation reaction. Molecular weights of the obtained polyamides were evaluated viscometrically, and the inherent viscosities (η_inh) measured were in the range 0.54–0.69 dL/g. These polyamides were amorphous and readily soluble in many organic solvents, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimetheylformamide, dimethyl sulfoxide, pyridine, and m-cresol etc., and they could easily be solution-cast into transparent, flexible films with good mechanical properties, with tensile strength ranging from 63.9 to 81.6 MPa and elongation at break from 7.2 to 11.4%. These polymers still kept good thermal stability with high-glass transition temperatures in the range of 283–338 °C, and the decomposition temperature in nitrogen for a 10% weight-loss temperatures in excess of 490 °C, and char yield at 800 °C in nitrogen ranged from 56 to 63%. Furthermore, the polyamides films were essentially colorless; their cut-off wavelengths were between 365 and 379 nm.     

Synthesis and properties of new aromatic copolyesters containing phosphorous cyclic bulky groups

A series of phosphorus‐containing copolyesters was prepared by polycondensation of 2‐(6‐oxido‐6H‐dibenz<c,e><1,2>oxaphosphorin‐6‐yl)‐1,4‐naphthalene diol, 1 , or of an equimolecular amount of 1 and different bisphenols 2 , such as 4,4′‐isopropylidenediphenol, 4,4′‐(hexafluoroisopropylidene)diphenol and 2,7‐dihydroxynaphthalene, with an aromatic diacid chloride containing two preformed ester groups 3 , namely, terephthaloyl‐bis‐(4‐oxybenzoyl‐chloride). The copolyesters exhibited good thermal stability having the temperature of 5% weight loss above 380°C and char yield at 700°C in the range of 20–31.2%. The glass transition temperature was in the range of 136–147°C. The polymers exhibited thermotropic liquid crystalline behavior, as was observed with polarized optical microscopy, differential scanning calorimetry, and X‐ray experiments. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Phosphorus‐containing poly(ester‐imide)–polydimethylsiloxane copolymers

New phosphorus‐containing poly(ester‐imide)‐polydimethylsiloxane copolymers were prepared by solution polycondensation of 1,4‐[2‐(6‐oxido‐6H‐dibenz < c,e > < 1, 2 > oxaphosphorin‐6‐yl)]naphthalene‐bis(trimellitate) dianhydride with a mixture of an aromatic diamine (1,3‐bis(4‐aminophenoxy)benzene) and α,ω‐bis(3‐aminopropyl)oligodimethylsiloxane of controlled molecular weight, in various ratios. Poly(amic acid) intermediates were converted quantitatively to the corresponding polyimide structures using a solution imidization procedure. The polymers are easily soluble in polar organic solvents, such as N‐methyl‐2‐pyrrolidone and N,N‐dimethylformamide, as well as in less polar solvents such as tetrahydrofuran. They show good thermal stability, the decomposition temperature being above 370 °C. The glass transition temperatures are in the range 165–216 °C. Solutions of the polymers in N‐methyl‐2‐pyrrolidone exhibit photoluminescence in the blue region. Copyright © 2010 Society of Chemical Industry     

One-pot synthesis of soluble wholly aromatic liquid crystalline copoly(ester amide)s with high thermal and dimensional stability

Abstract

Thermotropic liquid crystalline polymers (LCPs) have been of great interest for electronic packaging. Herein, we introduce a series of wholly aromatic, thermotropic LCPs from copoly(ester amide)s of 6-hydroxy-2-naphthalic acid, isophthalic acid, terephthalic acid, and 4-aminophenol, prepared by a convenient one-pot melt polycondensation. Almost synthesized copoly(ester amide)s exhibited good solubility in common organic solvents at room temperature. Furthermore, they possessed high thermal stability with 2% degradation temperatures (T_id) of 359–368?°C and the char yields (at 600?°C) of 50.3–55.6%. The synthesized copoly(ester amide)s had relatively low coefficient of thermal expansion (CTE) values, which were 35.85–41.21?ppm °C^?1 in the temperature range of 50–200?°C. Furthermore, an annealing process could be employed to improve the thermomechanical properties of synthesized polymers. For instance, the CTE of sample LCP3 in range temperature of 275–315?°C was reduced by more than 90% after annealing at 320?°C for 1?h, implying the feasibility for electronic packaging.     

High and temperature-stable dielectric constants in PNb9O25 ceramic

PNb₉O₂₅ ceramic was prepared using a sparking plasma sintering (SPS) method. Microstructure, dielectric and electrical properties of the ceramic were investigated. Dense ceramic was obtained, and the ceramic exhibited a high dielectric constant (>1000) and a low dielectric loss (∼2%) in the investigated frequency range of 100 Hz-100 kHz at room temperature. Dielectric relaxations with strong frequency dispersion occurred at temperatures higher than 250°C, which were due to oxygen vacancies. A highly stable capacitance (< 10% deviation) over a wide temperature range of –30°C to –200°C was obtained. The ceramic also showed a relatively high electrical conductivity (>4 × 10⁻⁸ S/cm) with an activation energy of approximately 0.9 eV in the temperature range of >200°C.     

Novel soluble fluorine-containing polyamides derived from 2-(4-trifluoromethylphenoxy)terephthalic acid and trifluoromethyl-substituted aromatic bis(ether amine)s

A series of new fluorine-containing polyamides were prepared directly by polycondensation of 2-(4-trifluoromethylphenoxy)terephthalic acid with four trifluoromethyl-substituted aromatic bis(ether amine)s in N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride using triphenyl phosphite and pyridine as condensing agents. All the polymers showed excellent solubility in solvents such as NMP, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, pyridine, tetrahydrofuran, and acetone at room temperature. These polymers had inherent viscosities between 0.67 and 1.09 dL/g, and their weight-average molecular weights and number-average molecular weights were in the range of 48,200–68,000 and 29,500–39,400, respectively. The resulting polymers showed glass-transition temperatures between 189 and 214 °C and 10% weight loss temperatures ranging from 475 to 483 °C, and char yields at 800 °C higher than 50% in nitrogen. All polymers were amorphous and could be cast into transparent, flexible, and strong films from DMAc solutions with tensile strengths of 71–115 MPa, elongations at break of 6–9%, and tensile moduli of 2.7–3.2 GPa. These polymers had low dielectric constants of 3.14–3.31 (1 MHz), low moisture absorption in the range of 0.88–1.60%, and high transparency with an ultraviolet–visible absorption cut-off wavelength in the 320–340 nm range.     

Synthesis and characterization of new polyamides and polyimides containing dioxypyrimidine moiety in the main chain with bulky imidazole pendent group: solubility, thermal and photophysical properties

A new symmetrical diamine monomer containing dioxypyrimidine and two diaryl imidazole bulky pendent group was synthesized by the nucleophilic substitution reaction of 4,6 dihydroxy pyrimidine with the synthesized 2-(2-chloro-5-nitrophenyl)-4,5-diphenyl-1H-imidazole (I). A series of novel fluorescent imidazole-containing polyamides (PAs) with inherent viscosities of 0.52–0.78 dL/g was prepared by direct polycondensation of the diamine with various dicarboxylic acids. These PAs were readily soluble in many organic solvents and could be solution-cast into tough and flexible films. The PAs exhibited glass transition temperatures (T_g)s between 202 and 260 °C, and 10% weight loss temperatures in the range of 345–470 °C in air. In addition, three novel polyimides (PIs) with inherent viscosities of 0.38–0.56 dL/g were prepared by addition reaction of the diamine with commercially available tetracarboxylic dianhydrides and subsequent chemical imidization. The PIs exhibited good solubility in polar solvents such as NMP. These polymers exhibited T_gs in the range of 237–285 °C and their 10% weight-loss temperatures varied from 440 to 520 °C.     

Facile Synthesis of Ferrocene-Based Polyamides and Their Organic Analogues Terpolyamides: Influence of Aliphatic and Aromatic Sequences on Physico-Chemical Characteristics

Efforts have been devoted to synthesize and characterize processable polymers with desired properties. Herein, four different series of aromatic and aliphatic terpolyamides were prepared via solution phase polycondensation of 4,4′-oxydianiline and hexamethylenediamine (HMDA) with various diacids chlorides (isophthalyol dichloride, terepthalyol dichloride, 1, 1′-ferrocene dicarboxylic acid chloride and trans-azobenzene-4, 4′-dicarbonyl chloride). The structural, morphological and physico-chemical nature of as prepared polymers was explored by Fourier-transform infrared spectroscopy, scanning electron microscopy, thermal analysis (TGA and DSC), and wide-angle x-ray diffraction. Moreover, an aliphatic diamine was incorporated in varying concentration as a flexible methylene spacer and the effect of its concentration on the properties of polyamides was also studied. Changes in various physico-chemical properties such as solubility, inherent viscosity, surface morphology and flame retarding behaviour were investigated. Marked difference in morphology and solubility was observed with the change in the ratio of segments in the chain. Inherent viscosities of polymers ranged from 1.8052–1.6274 dl/g indicating reasonably moderate molecular weights. Interestingly, ferrocene based aromatic polymers were more thermally stable (T_g 260 °C, T_i 310 °C, T_h 525 °C, T_f 720 °C, for PF₀), and also found to exhibit best flame retarding behavior (limiting oxygen index value for PF₀is LOI 33.15%).

     

Thermostable soluble aromatic poly(amide-imide)s having hexafluoroisopropylidene and ether links in the main chain

An imide-containing dicarboxylic acid, 2,2-bis[4-(4-trimellitimidophenoxy)phenyl]-hexafluoropropane (I), was prepared by the condensation of 2,2-bis[4-(4-aminophenoxy)phenyl]-hexafluoropropane and trimellitic anhydride. A series of new hexafluoroisopropylidene-containing poly(amide-imide)s having inherent viscosities of 0.64–1.44 dL/g were prepared by the direct polycondensation of diimide-diacid I with various long-chain aromatic diamines using triphenyl phosphite and pyridine as condensing agents in N-methyl-2-pyrrolidone in the presence of calcium chloride. Most of the resulting poly(amide-imide)s were noncrystalline and showed good solubility in polar organic solvents. Almost all polymers afforded transparent, flexible, and tough films. The 10 % weight loss temperatures of these polymers were all above 499 °C, and the glass transition temperatures were in the range of 203–277 °C.     

Synthesis and properties of poly(amide-imide)s based on 1,5-bis(4-trimellitimido)naphthalene

1,5-Bis(4-trimellitimido)naphthalene (II) was prepared by the condensation reaction of 1,5-naphthalenediamine and trimellitic anhydride. A series of aromatic poly(amide-imide)s (IV _a–o) was synthesized by the direct polycondensation of the diimide-diacid (II) and various aromatic diamines (III _a–o). The reaction utilized triphenyl phosphite and pyridine as condensing agents in the presence of calcium chloride in N-methyl-2-pyrrolidone (NMP). The inherent viscosities of the resulting poly(amide-imide)s were in the range of 0.55∼1.39 dL/g. These polymers were generally soluble in polar solvents, such as N,N-dimethylacetamide (DMAc), NMP, N,N-dimethylformamide (DMF). Flexible and tough poly(amide-imide) films were obtained by casting from a DMAc solution and had tensile strengths of 90∼145 MPa, elongations to break of 5∼13 %, and initial moduli of 2.29∼3.73 GPa. The glass transition temperatures of some poly(amide-imide)s were recorded in the range of 206∼218 °C, and most of the polymers did not show discernible glass transition on their DSC traces. The 10% weight loss temperatures were above 522 °C in nitrogen and above 474 °C in air atmosphere.     

Design and synthesis of unsymmetric phosphinated diamines for high-Tg,transparent polyimides

Two phosphinated diamines, 1-(4-aminophenyl)-1-(3-t-butyl-4-aminophenyl) -1- (6-oxido-6H -dibenz <c,e> <1,2> oxaphosphorin-6-yl)ethane (1) and 1-(4-aminophenyl) -1-(3-methxoy-4-aminophenyl)-1-(6-oxido-6H -dibenz <c,e> <1,2> oxaphosphorin-6-yl)ethane (2), were prepared via a facile, one-pot reaction of DOPO, 4-aminoacetophenone and 2-tertbutylaniline or 2-anisidine in the presence of p-toluenesulfonic acid. Based on diamines (1–2), a series of unsymmetric polyimides (3–4) were prepared in NMP/xylene by high-temperature solution polymerization. Transparency polyimides 3–4 with flexibility, organo-solubility, high-T_g values (310–384 °C), and moderate thermal properties (T_d 5 wt%, nitrogen: 461–477 °C; air, 456–474 °C) can be achieved. We found that the transparency of polyimide films is related with the orientation of the biphenylene phosphinate pendant, and the orientation is influenced by the bulkiness of the ortho-substituted substituent.     

Aliphatic-aromatic copolyesters containing phosphorous cyclic bulky groups

A series of phosphorus-containing copolyesters was prepared by polycondensation of 2-(6-oxido-6H-dibenz<c,e><1,2>oxaphosphorin-6-yl)-1,4-naphthalene diol, 1, or of an equimolecular amount of 1 and different aliphatic diols 2, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,12-dodecanediol, with an aromatic diacid chloride containing two preformed ester groups 3, namely terephthaloyl-bis-(4-oxybenzoyl-chloride). The copolyesters exhibited good thermal stability having the decomposition temperature above 375 °C. The glass transition temperature was in the range of 96-146 °C. The polymers exhibited thermotropic liquid crystalline behavior, as was observed with polarized optical microscopy. DSC and X-ray experiments were also found in concordance with mesophase formation.     

Synthesis and characterization of new aromatic polyesters based on 8,16-methano-16H-dinaphtho[2,1-d:1′,2′-g][1,3]dioxocin-2,14-diol

The bisphenol monomer containing dinaphthodioxocin group viz., 8,16-methano-16H-dinaphtho[2,1-d:1′,2′-g][1,3]dioxocin-2,14-diol (MDDD) was synthesized from commercially available 2,7-dihydroxynaphthalene and malonaldehydetetramethyl acetal and fully characterized by FT-IR, ¹H, ¹³C NMR and mass spectroscopies. A series of new aromatic polyesters was synthesized by phase transfer-catalysed interfacial polycondensation or high temperature solution polymerization method. Optimal conditions for polyesterification were obtained via study of the model compounds. These polyesters were characterized by spectroscopic technique, viscosity measurement, solubility, thermal stability, DSC, and elemental analysis. Inherent viscosities and number average molecular weights (M_n) of polyesters were in the range 0.33–0.74 dl/g and 13,130–38,000 (Gel Permeation Chromatography, polystyrene standard). All of the new polymers show very good solubility in polar aprotic solvents and could be cast into transparent, flexible and apparently tough films. The glass transition temperature (T_g) of polyesters was in the range of 152–289 °C. Polyesters derived from MDDD and eight aromatic diacid chlorides did not show any weight loss below 330 °C and retained 23–43% weight at 600 °C. The temperature at 10% weight loss (T₁₀), determined from thermogravimetric analysis of polyesters, was in the range 420–434 °C indicating their good thermal stability.     

Synthesis and thermal properties of new polyester based on indane-1,3-diol and terephtaloyl chloride

SUMMARY New aromatic polyester was synthetized by polycondensation of indane-1,3-diol and terephthaloyl chloride. The indane-1,3-diol was synthesised by metal hydride reduction and characterized by IR, ¹H and ¹³C NMR. Two polycondensation methods was used : solution and interfacial polycondensation in presence of various quaternary ammonium salts. The obtained polymers were characterized by differential scanning calorimetry (DSC) and viscosities measurements. All polymers had glass transition temperature (Tg) in the range of 72–77°C and melting temperature (Tm) in the range of 152–184°C. Received: 19 July 2000/Revised version: 10 December 2000/Accepted: 3 January 2001     

Inexpensive synthesis of 1,4-bis(4-aminophenoxy)-2- (6-oxido-6H-dibenz <c,e> <1,2> oxaphosphorin-6-yl) phenylene and its oxygen-plasma resistant polyamides

Inexpensive synthesis of diamine, 1,4-bis(4-nitrophenoxy)-2-(6-oxido-6H-dibenz <c,e> <1,2> oxaphosphorin-6-yl) phenylene was revealed in this work. Based on the diamine, a series of organosoluble polyamides were prepared by direct polycondensation of the diamine with various aromatic diacids using triphenyl phosphite and pyridine as condensing agents. The number-average molecular weights of the resulting polyamides range from 4.2 × 10⁴ to 10.5 × 10⁴ g/mol, and the weight-average molecular weights are in the range of 7.5-28.2 × 10⁴ g/mol. The T_gs of these polyamides range from 210 to 255 °C by dynamic mechanical analysis. The resulting polyamides are tough and flexible with tensile strength, elongation at break and moduli range from 84 to 101 MPa, 4.8-7.0%, and 2.36-3.22 GPa, respectively. The degradation temperatures (T_d 5%) and char yields at 800 °C in nitrogen range from 460 to 486 °C and 59-68 wt%, respectively. The cutoff wavelength of these polyamides falls in the range of 345-366 nm, showing a very light color characteristic. In addition, these polyamides display good oxygen plasma resistance.     

Synthesis and properties of silicon-containing polyamides

A series of aromatic polyamides incorporating silicon together with phenylquinoxaline or with hexafluoroisopropylidene groups has been synthesized by solution polycondensation of a silicon-containing diacid chloride with aromatic diamines having phenylquinoxaline rings or hexafluoroisopropylidene groups. These polymers are easily soluble in polar aprotic solvents, such as N-methylpyrrolidinone and dimethylformamide, and in tetrahydrofurane, and can be solution-cast into thin, transparent films having low dielectric constant, in the range of 3.26 to 3.68. These polymers show high thermal stability with decomposition temperature being above 400°C and glass transition temperature in the range of 236°C to 275°C. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1533–1538, 1997     

Synthesis and characterization of poly(aryl ether ketone)s with fluorinated phenyl in the side chain

New bisphenol monomers, (4-fluorophenyl)hydroquinone (3b) and (3,4-difluoro phenyl)hydroquinone (3c), were synthesized in a two-step synthesis. Poly(aryl ether ketone)s (PAEKs) (4a–c) were derived from these fluorinated bisphenols and nonfluorinated bisphenol—phenylhydroquinone (3a) with 4,4′-diflourobenzophenone via a nucleophilic aromatic substitution polycondensation. The obtained polymers had inherent viscosities of 0.50–0.92 dL/g. Thermal analysis showed that the obtained PAEKs had excellent thermal properties, the glass transition temperatures ranged from 148 to 160 °C, and the temperatures at 5% weight loss (Td₅) were above 527 °C and the temperatures at 10% weight loss (Td₁₀) were above 544 °C in nitrogen. All the polymers showed excellent solubility and could dissolve in common organic solvents, such as DMSO, NMP, DMF, etc. So the films of them were easily cast from their solutions, which possessed good mechanical properties, with tensile strengths of 95.2–104.0 MPa, Young’s moduli of 2.68–3.06 GPa, and elongation at break of 15–32%. Furthermore, the prepared PAEKs displayed low dielectric constants (2.75–2.95 at 1 MHz) and hydrophobic character (contact angles for water: 83.9^o–98.4^o).     

Synthesis and characterization of novel poly(amide imide)s

Novel poly(amide imide)s having inherent viscosities in the range 0.89–1.56 dL/g were prepared by the method of low temperature polycondensation in solution of N,N-dimethylacetamide (DMA) from aromatic diamines and a new monomer: N-[4″-(chloroformylphenyl)-4′-iminobenzoyl]trimellitimide chloride. The polymers were soluble in polar aprotic solvents and essentially amorphous. They showed glass transition temperatures in the range 310–350°C and decomposition temperatures of 450–460°C. Polymer films, fabricated by casting polymer solutions in DMA, showed tensile strengths in the range 70–90 MPa and moduli values between 3000–4000 MPa. © 1996 John Wiley & Sons, Inc.