Synthesis and photoinduced transformation of helical aromatic polyamides containing atropisomeric biphenylene units and azobenzene segments in the main chain

Optically active helical polyamides were synthesized by condensation of axially dissymmetric (R)‐ or (S)‐6,6′‐diamino‐2,2′‐dimethylbiphenyl with aromatic dicarbonyl chlorides. The wholly aromatic polyamides obtained were soluble in various low‐polarity organic solvents such as tetrahydrofuran and chloroform, as well as in polar N,N‐dimethylacetamide. Excellent thermal stability of the helical structure was observed for the polyamide obtained with 4,4′‐dicarbonylbiphenyl chloride in refluxing N,N‐dimethylacetamide. Chiroptical data obtained from the circular dichroism spectra showed that the helical conformation of the polyamide containing azobenzene segments in the main chain can be transformed reversibly on irradiation with UV–visible light because of the trans–cis isomerization of the segments. Copyright © 2004 Society of Chemical Industry     

Preparation and properties of bismaleimide resins of aromatic sulfone ether diamine

Aromatic sulfone ether diamine, bis[4-(4-aminophenoxy)phenyl]-sulfone (SED), was prepared by the nucleophilic aromatic substitution of 4,4′-dichlorodiphenylsulphone by p-aminophenolate. The reaction was conducted in the presence of excess potassium carbonate as a weak base, toluene as the dehydrating agent and N-methylpyrrolidone as the dipolar aprotic solvent. SED showed good solubility in common organic solvents, such as dioxan, tetrahydrofuran, butanone and acetone. SED was reacted with maleic anhydride to obtain aromatic sulfone ether bismaleimide, bis[4-(4-maleimidophenoxy)phenyl]-sulfone (SEM). The compounds were characterized by FTIR and ¹H NMR analysis. Furthermore, copolymer resins of SED with 4,4′-bismaleimidodiphenyl methane (BMI) and SEM were prepared. After curing, crosslinked resins with better thermal stability resulted. The temperature at maximum rate of weight loss (T_max) and the heat-resistant temperature index (T_i) in air were found to be 426°C, 208°C and 579°C, 221°C for BMI/SED and SEM/SED resins, respectively. Compared with the corresponding 4,4′-diaminodiphenyl methane (DDM) system, BMI/SED and SEM/SED showed a slight decrease in T_max and T_i SED-modified BMI/amine resin based glass cloth laminates for printed circuit boards showed higher mechanical properties than those of the corresponding unmodified system. With SED instead of the original amine component in 3–5% weight fraction, the tensile strength, flexural strength and impact strength of the laminates increased markedly. Meanwhile, the stripping strength and weld resistance were also improved by the addition of SED.     

Synthesis and characterization of novel polyaspartimides derived from 2,2′‐dimethyl‐4,4′‐bis(4‐maleimidophenoxy)biphenyl and various diamines

A novel bismaleimide, 2,2′‐dimethyl‐4,4′‐bis(4‐maleimidophenoxy)biphenyl, containing noncoplanar 2,2′‐dimethylbiphenylene and flexible ether units in the polymer backbone was synthesized from 2,2′‐dimethyl‐4,4′‐bis(4‐aminophenoxy)biphenyl with maleic anhydride. The bismaleimide was reacted with 11 diamines using m‐cresol as a solvent and glacial acetic acid as a catalyst to produce novel polyaspartimides. Polymers were identified by elemental analysis and infrared spectroscopy, and characterized by solubility test, X‐ray diffraction, and thermal analysis (differential scanning calorimetry and thermogravimetric analysis). The inherent viscosities of the polymers varied from 0.22 to 0.48 dL g⁻¹ in concentration of 1.0 g dL⁻¹ of N,N‐dimethylformamide. All polymers are soluble in N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, dimethylsulfoxide, pyridine, m‐cresol, and tetrahydrofuran. The polymers, except PASI‐4, had moderate glass transition temperature in the range of 188°–226°C and good thermo‐oxidative stability, losing 10% mass in the range of 375°–426°C in air and 357°–415°C in nitrogen. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 279–286, 1999     

Synthesis and characterization of a rigid poly(amide hydrazide): effect of some reaction parameters on the viscosity of the polymer formed

A wholly aromatic all-para oriented poly(amide hydrazide) has been synthesized from N,N′-bis(4-aminobenzoyl) hydrazine (BABH) and terephthaloyl chloride (TC) by low temperature solution polycondensation. The polymer was characterized by elemental analyses, IR spectroscopy, solubility, viscosity and density measurements. The effect of various factors controlling the polymerization reaction (concentration of monomer and electrolyte (LiCl) in the reaction medium, nature of the medium and temperature at the initial stage of polymerization) on polymer viscosity was studied. To prepare a polymer of high viscosity, the optimum conditions were found to be, monomer concentration 0·25moll^-1, LiCl concentration (in DMAc) 1% (w/v), with use of N-methyl pyrrolidone (NMP) as polymerization medium. The thermal behaviour of the polymer was studied in air and nitrogen by TGA and DSC. ©1997 SCI     

Photoresponsive peptide and polypeptide systems: Part 9. Synthesis and reversible photochromism of azo aromatic poly(L-α,ω-diaminobutyric acid)

Poly(L-α,ω-diaminobutyric acid) having azo aromatic side chains was synthesized by the water-soluble carbodiimide procedure. The photoresponsive properties of the polypeptide poly[N⁷-p-(phenylazo)benzoyl-L -α,ω-diaminobutyric acid] (PPABLDBA) due to the trans (about 71%, under visible light) cis (under ultraviolet light) photoisomerization of the azo aromatic moieties in the side chains were investigated by absorption and circular dichroism spectroscopy in hexafluoro-2-propanol (HFIP). The starting slightly turbid solution of trans-PPABLDBA becomes clear on irradiation at 360 nm, accompanied by photoconversion of the conformer of the azo moieties to cis. The backbone conformation of PPABLDBA in HFIP is right-handed helical (helical content, about 60%) when the azo moieties are trans (71%), while the conformation is random coil when cis. The backbone conformational transition of PPABLDBA from helical to coil is mostly reversible under the influence of light.     

Preparation and properties of novel soluble aromatic polyetherimides from 1,1′-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane dianhydride and aromatic diamines

New aromatic polyetherimides containing the 1,1′-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane dianhydride unit were prepared by a conventional two-step method from 1,1′-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane dianhydride and several diamines. This procedure yielded high molecular weight polyetherimides with inherent viscosities of 0.22–1.29 dL/g. Most of the corresponding polyetherimides were soluble in organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N,N-dimethylacetamide, and methylene chloride under ambient temperature. The glass transition temperatures (T_g) of these polymers were in the range of 207–264°C and the temperatures of 10% weight loss were over 520°C at a heating rate 20°C/min in nitrogen. © 1996 John Wiley & Sons, Inc.     

Ambipolar and multi‐electrochromic polyimides based on N,N‐di(4‐aminophenyl)‐N′,N′‐diphenyl‐4,4′‐oxydianiline

A series of novel aromatic polyimides were synthesized from N,N‐di(4‐aminophenyl)‐N′,N′‐diphenyl‐4,4′‐oxydianiline and aromatic tetracarboxylic dianhydrides through a conventional two‐step procedure. Most of the polyimides exhibited reasonable solubility in organic solvents and could afford robust films via solution casting. The polyimides exhibited high thermal stability, with glass transition temperatures in the range 227–273 °C and 10% weight‐loss temperatures in excess of 550 °C. All the polyimide films showed ambipolar redox and multi‐electrochromic behaviors. They exhibited two reversible oxidation redox couples at 0.94–0.98 and 1.09–1.12 V versus Ag/AgCl in acetonitrile solution. A coupling reaction between the radical cations of the pendent triphenylamine units occurred during the oxidative process forming a tetraphenylbenzidine structure which resulted in an additional redox state and color change. © 2014 Society of Chemical Industry     

Molecular design,synthesis, and electro‐optic properties of novel Y‐type polyesters with high thermal stability of second harmonic generation

3,4‐Di‐(2′‐hydroxyethoxy)‐4′‐nitrostilbene was prepared and condensed with terephthaloyl chloride, adipoyl chloride, and sebacoyl chloride to yield novel Y‐type polyesters containing NLO‐chromophore dioxynitrostilbenyl groups, which constituted parts of the polymer backbone. Polymers were found soluble in common organic solvents such as acetone and N,N‐dimethylformamide. They showed thermal stability up to 300 °C in thermogravimetric analysis with glass‐transition temperatures obtained from differential scanning calorimetry in the range 110–152 °C. The second harmonic generation (SHG) coefficients (d₃₃) of poled polymer films at a 1064 cm^?1 fundamental wavelength were around 3.51 × 10^?8 esu. The dipole alignment exhibited high thermal stability even at 10 °C higher than the glass‐transition temperature, and there was no SHG decay below 120 °C for one of these polymers due to the partial main‐chain character of polymer structure, which was acceptable for NLO device applications. Copyright © 2005 Society of Chemical Industry     

Synthesis and Pyrolysis-Field Ionization Mass Spectrometric Study of an Aromatic Polyamide Having Azo Group in the Main Chain

The reductive coupling of p-nitrobenzoic acid with glucose solution gave 4,4′-azodibenzoic acid and was converted to 4,4′-azodibenzoylchloride using thionyl chloride. This aromatic diacid chloride was condensed with 4,4′-Diaminodiphenyl ether by two different techniques to yield aromatic polyamide. The low temperature polymerization method resulted in comparatively high molecular weight polymer as evidenced by intrinsic viscosity values. The structure of the material was confirmed by IR studies. Detailed pyrolysis-field ionization mass spectral studies carried out indicated two major degradations. In the temperature region (180–200°C), the mass spectrum showed intense peaks at m/z = 166 and 149 which can be explained from the fragmentation of azodicarboxylic acid formed from the polymer. The mass spectrum recorded at 465°C gave clear proof for the structure of the polyamide and also enough evidence was noted for the hydrogenation of the azo group during pyrolysis.     

Synthesis and characterization of new thermally stable poly(ester‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic dihydroxy compounds

A series of new alternating aromatic poly(ester‐imide)s were prepared by the polycondensation of the preformed imide ring‐containing diacids, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A model compound (3) was also prepared by the reaction of 2b with phenol, its synthesis permitting an optimization of polymerization conditions. Poly(ester‐imides) were fully characterized by FTIR, UV‐vis and NMR spectroscopy. Both biphenylene‐ and binaphthylene‐based poly(ester‐imide)s exhibited excellent solubility in common organic solvents such as tetrahydrofuran, m‐cresol, pyridine and dichloromethane. However, binaphthylene‐based poly(ester‐imide)s were more soluble than those of biphenylene‐based polymers in highly polar organic solvents, including N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide. From differential scanning calorimetry thermograms, the polymers showed glass‐transition temperatures between 261 and 315 °C. Thermal behaviour of the polymers obtained was characterized by thermogravimetric analysis, and the 10 % weight loss temperatures of the poly(ester‐imide)s was in the range 449–491 °C in nitrogen. Furthermore, crystallinity of the polymers was estimated by means of wide‐angle X‐ray diffraction. The resultant poly(ester‐imide)s exhibited nearly an amorphous nature, except poly(ester‐imide)s derived from hydroquinone and 4,4′‐dihydroxybiphenyl. In general, polymers containing binaphthyl units showed higher thermal stability but lower crystallinity than polymers containing biphenyl units. Copyright © 2005 Society of Chemical Industry     

Preparation and properties of organo‐soluble polyimides based on 4,4′‐diamino‐3,3‐dimethyldiphenylmethane and conventional dianhydrides

4,4′‐Diamino‐3,3′‐dimethyldiphenylmethane was used to prepare polyimides in an attempt to achieve good organo‐solubility and light color. Polyimides based on this diamine and three conventional aromatic dianhydrides were prepared by solution polycondensation followed by chemical imidization. They possess good solubility in aprotonic polar organic solvents such as N‐methyl 2‐pyrrolidone, N,N‐dimethyl acetamide, and m‐cresol. Polyimide from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane and diphenylether‐3,3′,4,4′‐tetracarboxylic acid dianhydride is even soluble in common solvents such as tetrahydrofuran and chloroform. Polyimides exhibit high transmittance at wavelengths above 400 nm. The glass transition temperature of polyimide from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane and pyromellitic dianhydride is 370°C, while that from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane and diphenylether‐3,3′,4,4′‐tetracarboxylic acid dianhydride is about 260°C. The initial thermal decomposition temperatures of these polyimides are 520–540°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1299–1304, 1999     

Synthesis of thermostable polyamideimides and their properties

Thermostable polyamideimides with inherent viscosity of 1.02–1.50 dL/g were synthesized from reacting of diamine-terminated aromatic amide prepolymer with various diisocyanate terminated imide prepolymers. The imide prepolymer was prepared by using 4,4′-diphen-ylmethane diisocyanate to react with 3,3′,4,4′ benzophenonetetracarboxylic dianhydride, 3,3′,4,4′ sulfonyl diphthalic anhydride, or 4,4′-oxydiphthalic anhydride using the direct one-pot method to improve their solubility. Almost all of the polyamideimides were generally soluble in a wide range of organic solvents such as N,N-dimethylformamide, N,N-dimeth-ylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and pyridine at room temperature. Polymers with high imide content required high temperatures to dissolve. All polyamide-imides had a glass transition temperature of 223–352°C and showed a 10% weight loss temperature of 415–575°C in air and 424–583°C in nitrogen atmosphere. The tensile strength, elongation at break, and initial modulus of polymer films ranged from 61 to 108 MPa, 5 to 10% and 1.54 to 2.50 GPa, respectively. These copolymers were partly crystalline in structure as shown by X-ray pattern. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of highly soluble poly(ether imide)s containing indane moieties in the main chain

A new indane containing unsymmetrical diamine monomer ( 3 ) was synthesized. This diamine monomer leads to a number of novel semifluorinated poly (ether imide)s when reacted with different commercially available dianhydrides like benzene‐1,2,4,5‐tetracarboxylic dianhydride (PMDA), benzophenone‐3,3′, 4,4′‐tetracarboxylic dianhydride (BTDA), 4,4′‐(hexafluoro‐isopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), and 4,4′‐(4,4′‐Isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA) by thermal imidization route. All the poly(ether imide)s showed excellent solubility in several organic solvents such as N‐methylpyrrolidone (NMP), N,N‐dimethylformamide (DMF), N,N‐dimethylacetamide (DMAc), tetrahydrofuran (THF), chloroform (CHCl₃) and dichloromethane (DCM) at room temperature. These light yellow poly (ether imide)s showed very low water absorption (0.19–0.30%) and very good optical transparency. Wide angle X‐ray diffraction measurements revealed that these polymers were amorphous in nature. The polymers exhibited high thermal stability up to 526°C in nitrogen with 5% weight loss, and high glass transition temperature up to 265°C. The polymers exhibited high tensile strength up to 85 MPa, modulus up to 2.5 GPa and elongation at break up to 38%, depending on the exact polymer structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Phase relationships of rigid rod polymer/flexible coil polymer/solvent ternary systems

Phase diagrams of two types of rigid rod polymer/flexible coil polymer/methanesulfonic acid (MSA) ternary systems were determined by polarized optical microscopy at ambient conditions. The rigid rod polymer is a wholly aromatic high temperature resistant (no measurable T_g) poly (p-phenylenebenzobisthiazole) (PPBT). One of the flexible coil polymers is a wholly aromatic high temperature resistant poly (2,5′(6′) benzimidazole) (ABPBI), the other is a thermoplastic poly[2,2′ -(1–4-phenylene)-6,6′ -bis (3-phenyl-quinoxaline)] (PPQ) with T_g of 359°C. The solvent is methane-sulfonic acid (MSA). The experimentally determined critical concentration points, C_cr, are in excellent agreement with Flory's recent theory. Total phase segregation between the polymer pair in ternary solution was predicted and observed at C > C_cr. Different decomposition mechanisms of phase separation were observed as a function of concentration.     

Studies of heterocyclic polymers. V. poly (1, 3′-benzobis (iminopyrrolenones))

The synthesis of dimethyl-2, 5-dicyanoterephthalate from 2,5-dibromo-p-xylene and its conversion to 1,3′-benzobis (iminopyrrolenone) are reported. 1,3 -Benzobis (N-phenyliminopyrrolenone) was prepared by reaction of 1,3′-benzobis (iminopyrrolenone) with aniline. The product was a bright yellow crystalline solid which was also formed when dimethyl-2,5-dicyanoterephthalate was condensed with aniline under suitable conditions. Poly (1,3′-benzobis (iminopyrrolenones)) were synthesised by the condensation of 1,3′ -benzobis (iminopyrrolenone) with aromatic diamines and with 1,6-diaminohexane at high temperatures in dimethyl sulphoxide. The degrees of polymerisation of the polymers obtained were low, as judged by the completeness of the condensation reaction. Thermogravimetric analyses of these polymers in air showed that they have 10% weight-loss temperatures in the range 420 to 520°C, for the polymers prepared from aromatic diamines, and of 350°C for the polymer derived from 1,6-diaminohexane. The insoluble, intractable nature of these polymers precluded a thorough study of their structure.     

Synthesis and characterization of Schiff‐base‐containing polyimides

Benzyl bisthiosemicarbazone and its complexes with nickel (NiLH₄) and copper (CuLH₄) were used as diamine monomers for the synthesis of new Schiff‐base polyimides. The solution polycondensation of these monomers with the aromatic dianhydrides afforded metal‐containing Schiff‐base polyimides with inherent viscosities of 0.98–1.33 dL/g (measured in N‐methyl‐2‐pyrrolidone at 25°C). The polyimides were generally soluble in a wide range of solvents such as N,N‐dimethylformamide, N,N‐dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, tetrachloroethane, hexamethylene phosphoramide, N‐methyl‐2‐pyrrolidone, ethyl acetate, and pyridine at room temperature. The initial degradation temperatures of the resultant polyimides fell in the range of 220–350°C in nitrogen with char yields ranging from 36 to 64% at 700°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of novel poly(amide imide)s based on bis(p‐amidobenzoic acid)‐n‐trimellitylimido‐L‐leucine

N‐Trimellitylimido‐L ‐leucine was reacted with thionyl chloride, and N‐trimellitylimido‐L ‐leucine diacid chloride was obtained in a quantitative yield. The reaction of this diacid chloride with p‐aminobenzoic acid was performed in dry tetrahydrofuran, and bis(p‐amidobenzoic acid)‐N‐trimellitylimido‐L ‐leucine (5) was obtained as a novel optically active aromatic imide–amide diacid monomer in a high yield. The direct polycondensation reaction of the monomer imide–amide diacid 5 with 4,4′‐diaminodiphenylsulfone, 4,4′‐diaminodiphenylether, 1,4‐phenylenediamine, 1,3‐phenylenediamine, 2,4‐diaminotoluene, and benzidine (4,4′‐diaminobiphenyl) was carried out in a medium consisting of triphenyl phosphite, N‐methyl‐2‐pyrolidone, pyridine, and calcium chloride. The resulting novel poly(amide imide)s (PAIs), with inherent viscosities of 0.22–0.52 dL g^?1, were obtained in high yields, were optically active, and had moderate thermal stability. All of the compounds were fully characterized with IR spectroscopy, elemental analyses, and specific rotation. Some structural characterization and physical properties of these new optically active PAIs are reported. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 35–43, 2002; DOI 10.1002/app.10181     

Synthesis,characterization, and gas permeability of aromatic polyimides containing pendant phenoxy group

A diamine containing a pendant phenoxy group, 1-phenoxy-2,4-diaminobenzene, was synthesized and condensed with different aromatic dianhydrides [4,4′-oxydiphthalic dianhydride, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracorboxylic dianhydride, and pyromellitic dianhydride] by one-step synthesis at a high temperature in m-cresol to obtain polyimides in high yields. Most of the polyimides exhibited good solvent solubility and could be readily dissolved in chloroform, sym-tetrachloroethane, N,N-dimethylformamide, N,N-dimethylacetamide, and nitrobenzene. Their inherent viscosities were in the range of 0.33–1.16 dL/g. Wide-angle X-ray spectra revealed that these polymers were amorphous in nature. All these polyimides were thermally stable, having initial decomposition temperatures above 500°C and glass-transition temperatures in the range of 248–281°C. The gas permeability of 4,4′-oxydiphthalic dianhydride and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride based polyimides was investigated with pure gases: He, H₂, O₂, Ar, N₂, CH₄, and CO₂. A polyimide containing a  C(CF₃)₂ linkage showed a good combination of permeability and selectivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

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.     

Order-Disorder Conformation Change of Succinoglycan in Aqueous Sodium Chloride as Studied by Static and Dynamic Light Scattering

Summary Static and dynamic light scattering measurements have been made on a sodium salt sample of succinoglycan in 0.01 M aqueous NaCl at different temperatures between 25 and 75°C where the polysaccharide undergoes a thermally induced change from an ordered (helical) to disordered conformation with raising temperature T. The weight-average molecular weight M _w, the z-average radius of gyration, and the hydrodynamic radius sharply decrease in a relatively narrow T range (around 55°C) in which the specific rotation was previously found to change sigmoidally with T. In particular, the value of M _w (4.55 × 10⁵) in the ordered state at 25°C is twice as large as that (2.27 × 10⁵) in the disordered state at 75°C, giving decisive evidence that the helical structure of the polysaccharide in aqueous NaCl is composed of paired chains. It is concluded that this structure is a double-stranded helix and breaks directly into two disordered chains with increasing T. Received: 6 July 2001 / Accepted: 24 July 2001