Synthesis and Characterization of Polyesterimides Containing Ether Linkages

Abstract

Three novel dicarboxylic acids, bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl sulfone, bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl methane, and bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl ether, were synthesized, and several polyesterimides were prepared from diacid chlorides and bisphenols by solution polycondensation. The polymers were obtained in 65–88% yield and had inherent viscosities in the 0.18 to 0.64 dL/g range. The polymers were characterized by IR, elemental analysis, x-ray, TGA, DSC, and solubility tests. All the polymers were readily soluble in polar aprotic solvents and had a 10% weight loss temperature above 375°C in nitrogen.     

Polyaromatic pyrazines: Synthesis and thermogravimetric analysis

The syntheses of five polyaromatic pyrazine polymers are described. These polymers were synthesized by the condensation of bis-α-haloaromatic ketones with ammonia in N,N-dimethylacetamide (DMAc) solvent in the presence of air or peroxides. The condensation of bis-p-(α-bromoacetyl)benzene (IIIa), bis-p,p′-(α-chloroacetyl)biphenyl (IIIb) bis-p,p′-(α-chloroacetyl)diphenyl ether (IIIc), bis-p,p′-(α-chloroacetyl)diphenylmethane (IIId), and α,α′-dibenzoyl-α,α′-dibromo-p-xylene (V) under these reaction conditions gave poly[2,5-(1,4-phenylene)pyrazine] (IVa), poly[2,5-(4,4′-biphenylene)-pyrazine] (IVb), poly[2,5-(4,4′-oxydiphenylene)pyrazine] (IVc), poly[2,5-(4,4′-methylenediphenylene)pyrazine] (IVd), and poly[2,5-(1,4-phenylene)-3,6-diphenylpyrazine] (VI), respectively. Thermogravimetric analysis (TGA) of these polymers showed them to be thermally stable up to the temperature range of 450–550°C in air for short periods of time. The inherent viscosities of these polymers ranged from 0.18 to 1.30.     

Synthesis of fluorescent hyperbranched poly(aryl ether ketones) containing biphenyl units

Hyperbranched poly(aryl ether ketones) with M _n = (8–10) × 10³ and terminal fluorine atoms have been synthesized through the polycondensation of 3,3′,5,5′-tetramethyl-4,4′-dihydroxydiphenyl(A₂) and 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene (B₃) taken at a molar ratio of (0.720–0.675): 1. The replacement of the terminal fluorine atoms by residues of m-N,N-dimethylaminophenol yields polymers demonstrating green-blue fluorescence both in solution and in the solid state. Fluorescence quenching is observed at concentrations of the said polymers in solutions above 3 g/l.     

New Poly(Bismaleimide-Ether)s Containing Functional Pendant Carboxylic Groups

Abstract

New poly(bismaleimide-ether)s with functional pendant groups were synthesized by Michael addition polymerization of two monomers with functionality f > 2 (DL tartaric acid and methylene-5,5′disalicylic acid) to various bismaleimides with flexible groups (N,N'-4,4′-diphenyl-methanebismaleimide, N,N'-4,4′-diphenyletherbismaleimide and N,N'-4,4′-dibenzylbismaleimide). The polymerization occurred in solution, through the addition of the OH groups to the C[dbnd]C double bond of the maleimide rings. The polymers were obtained in good yields and they were characterized by elemental analysis, IR and ¹H NMR spectra, thermogravimetric analysis and viscozimetry.     

Phototropic molecules. 3. Complexation between alkali metal ions andtrans- andcis p,p′-bis(polyether) azobenzenes

Three polyether complexing agents were prepared whose shapes could be photochemically altered by means of an azobenzene fragment incorporated into the middle of the polyether chain. The compounds are 1, bis-4,4-[2-(methoxyethoxy)acetamido]azobenzene,2, bis-4,4-[2-(1,3-dimethoxy-2-propoxy)acetamido]azobenzene and3,bis-4,4-{2-[2-(2-methoxyethoxy)ethoxy]acetamido}azobenzene. Extraction equilibrium constants,K _EXT, for the extraction of Li⁺, Na⁺ K⁺, and Cs⁺ ions from water into an organic solvent were measured for these three agents under irradiation and in the dark. Compounds1 and2 were found to give substantially larger KExT values on irradiation than in the dark. TheK(light)/K(dark) ratios for the three compounds ranged from 0.47 to 16.6.For part 2 see ref. [1]     

Synthesis and Structure of New Trimethylplatinum(IV) Iodide Complexes of 2,2′‐Bipyridine Ligands

The synthesis and structural characterization of four new trimethylplatinum(IV) iodide complexes of 2,2′‐bipyridine ligands {[PtMe₃(4,4′‐Clbipy)I] ( 1 ), [PtMe₃(4,4′‐Brbipy)I] ( 2 ), [PtMe₃(4,4′‐CNbipy)I] ( 3 ) and [PtMe₃(4,4′‐NO₂bipy)I] ( 4 )} are reported. The ¹H NMR spectra of the complexes reveal the presence of two chemically distinct methyl groups in the complexes. X‐ray crystal structures of complexes 1 – 4 show that the platinum metal center in each of the complexes form distorted octahedral structure being surrounded by methyl groups, bipyridine ligand, and iodine atom. Furthermore, the crystal packing study shows that self‐assembly of the complexes are governed by weak hydrogen bonding and other non‐covalent interactions such as π ··· π, halogen ··· π and C–H ··· π interactions. Complex 1 exhibits infinite one‐dimensional zigzag chain structure and other three complexes form infinite ladder type structures.     

Potential DNA bis-intercalating agents. Bridged bis-(6-chloropurines) and related compounds

Two bis-(6-chloropurines) bridged by conformationally restricted tethers were synthesized as potential DNA bis-intercalating agents. Reduction of 4,6-dichloro-5-nitropyrimidine ( 1 ) afforded 5-amino-4,6-dichloropyrimidine ( 2 ) which was then used as the starting material. Reaction of 2 with 4,4′-diaminodiphenylmethane ( 3 ) and bis-(4-aminophenyl) ether ( 4 ) yielded bis-[4-(N-5-amino-4-chloro-6-pyrimidyl)aminophenyl]methane ( 5 ) and bis-[4-(N-5-amino-4-chloro-6-pyrimidyl)aminophenyl] ether ( 6 ), respectively. Acid-catalyzed condensation of the above pyrimidines, 5 and 6 , with triethyl orthoformate in N,N-dimethylacetamide gave bis-[4-(6-chloro-9-purinyl)phenyl]methane ( 7 ) and bis-[4-(6-chloro-9-purinyl)phenyl] ether ( 8 ). The spectral data on the new compounds will be discussed.     

Metallocene monomers and polymers. Ferrocenyl and ferrocenylene derivatives

The synthesis and study of some polyenes, polýiminoimides and Schiff polybases with ferrocene obtained by either polymerization or polycondensation are reported.The following monomers were used: ethynylferrocene, 1-chloro-1′-ethynyl-ferrocene, α-chloro-β-formyl-p-ferrocenylstyrene, p-ferrocenylphenylacetylene, p-ferrocenylacetophenone, 1,1′-diacetylferrocene and 1,1′-bis[β-(2-furyl)acryloyl]ferrocene which were characterized by spectral and thermodifferential analyses and Hückel MO calculations. The polymerization was performed in the presence of benzoyl and lauroyl peroxides, triisopropylboron and complex catalysts of [P(C₆H₅)₃]₂ NiX₂ type. The ferrocene derivatives were polycondensed with biuret, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl thioether, 4,4′-diamino-2,2′-dinitrodiphenyl disulphide in the presence of metallic salts and p-toluene sulphonic acid as catalysts.Polymers with either linear or tridimensional structure showing good thermal stability and semiconducting properties have been obtained. Some polymers show catalytical activity in the polymerization of chloroformylated vinylic derivatives.     

Synthesis and characterization of certain aromatic azopolyamides

Two new aromatic diamines, 2,2′-dimethyl-4,4′-diaminoazobenzene [benzenamine-(3,3′-dimethyl-4,4′-azobis)] and 2,2′-dichloro-4,4′-diaminoazobenzene [benzenamine-(3,3′-dichloro-4,4′-azobis)] were synthesized and their structures confirmed by IR, UV-visible, ¹H-NMR, ¹³C-NMR, and mass spectra. With these diamines, 16 aromatic polyamides were synthesized by both low-temperature solution and phosphorylation polycondensation methods. The polymers were characterized by viscosity, solubility, IR, UV visible, TGA, and DTA studies.     

Polymeric organosilicon systems 14. Synthesis and some properties of alternating polymers composed of a dithienylene group and a mono-, di- or tri-silanylene unit

Poly[5, 5′ - (dimethylsilylene) - 2, 2′ - dithienylene] (4a), poly[5, 5′ -(methylphenylsilylene)-2, 2′ -dithienylene] (4b), poly[5, 5′ -(1, 1, 2, 2-tetramethyldisilanylene)-2, 2′ -dithienylene] (4c), poly[5, 5′-(1, 2-dimethyl-1, 2-diphenyldisilanylene)-2, 2′ -dithienylene] (4d), poly[5, 5′-(1, 2, 2, 2-tetramethyldisilanylene)-2, 2′-dithienylene] (4e), and poly[5, 5′-(1, 1, 2, 2, 3, 3 - hexamethyltrisilanylene) - 2, 2′ -dithienylene] were synthesized by dehalogenative coupling of the respective bis(2-bromothienyl)- substituted mono, di- and tri-silanes with magnesium in the presence of a catalytic amount of a nickel(II) complex in 16–99% yields. The polymers thus obtained are light-yellow solids and soluble in common organic solvents. Molecular weights, M_w, of the polymers were measured and found to be 7800–35 000 by gel-permeation chromatography relative to polystyrene standards. The photochemical properties of the polymers (4a–4d) having silylene and disilanylene units were investigated. Only poly[5, 5′-(1, 2-dimethyl-1, 2-diphenyl-disilanylene)-2, 2′-dithienylene] (4d) was found to be photoactive, but the others were inactive. When the thin solid films prepared from the polymers 4a–4e by spin-coating were exposed to antimony(V) fluoride in vacuo, the films became conducting; their conductivities were determined to be 10^?2 – 10^?3 S cm^?1 by the four-probe method.     

The influence of the ligands on the catalytic activity of a series of RhI complexes in reactions with phenylacetylene: Synthesis of stereoregular poly(phenyl) acetylene

The catalytic activity of a series of [Rh L-L chel]X complexes, in which we have varied the unsaturated ligand [L-L = cis, cis-cycloocta 1,5-diene(cod) or 2,5-norbornadiene(nbd) the nitrogen chelating ligand [chel = 2,2′-bipyridine(bipy), 2,2′-dipyridylamine(dipyam), 2,2′-bipyrazine (bipz), 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me₂bipy)] and the counter ion [X = PF₆, ClO₄, BPh₄], has been examined in reactions with phyenylacetylene (PA). The catalytic behaviour of the [Rh(cod)Cl₂],tmeda (tmeda = N,N,N′,N′tetramethylethylendiamine), [Rh(cod)Cl₂],teda] (teda = triethylendiamine), of the dimer [Rh(cod)Cl]₂, and the use of NaOH as cocatalyst in different reaction conditions was also examined. The influence of the ligands on the catalytic activity of these Rh^I complexes is discussed. ¹H and ¹³C NMR spectra have shown that highly stereoregular polyphenylacetilene can be obtained. Conditions for homogeneous doping of PPA, to obtain materials whose conductivity varies over 10–11 magnitude orders, are proposed. The stability of the doped polymers is also discussed.     

Coupling and Cyclization of Sydnone Compounds

Cyclization were occurred via the coupling reactions of some mercuric chloride derivatives of sydnone with LiPdCl₃-CuCl₂. A unique six-membered ring, 3,3′-ethylene-4,4′-bissydnone, was obtained by the cyclization reation of 1,2-di[3-(4-chloromercuric)sydnonyl]ethane. However, the seven-membered 3,3′-trimethylene-4,4′-bissydnone and 1,3-di[3-(4-chloro)sydnonyl]-propane were obtained from the corresponding mercuric chlroide of sydnone. Onyl substitution reaction took place when 4,4′-di[3-(4-chloromercuric)sydnonyl]biphenyl, 4,4′-di[3-(4-chloromercuric)sydnonyl]benzene, di(p-[3-(4-chloromercuric)sydnonyl]-phenyl}methane and, di(p-[3-(4-chloromercuric)sydnonyl]phenyl]ether were treated using the same process.     

A surface enhanced Raman study of the adsorption of tris(2,2-bipyridine)ruthenium(II) and substituted analogues on chemically-deposited silver films

The surface enhanced resonance Raman spectroscopy (SERRS) of a series of tris(2,2′-bipyridine)ruthenium(II) complexes on chemically produced silver films is reported. The SERR spectra of [Ru(bipy)₃]²⁺, several tris complexes of Ru(II) containing substituted 2,2′-bipyridine (4,4′-dimethyl-,4,4′diphenyl-, 4,4′-diamino- and 4,4′-diethylcarboxylate-2,2′-bipyridine) ligands and the neutral cis-bis complexes [Ru(bipy)₂(NCS)₂] and [Ru(bipy)₂Cl₂] show very high band intensities. The large enhancement arises from the combination of the inherent resonance Raman effect and the surface plasmon resonance (due to the rough nature of the silver film). The molecules are not chemisorbed on the silver surface and hence the enhancement occurs solely via the electromagnetic mechanism. Ale SERR spectra are virtually free of the fluorescence which dominates the corresponding RR spectra thus illustrating the use of SERRS in the vibrational spectroscopy of strongly luminescing species. The SERRS spectra of the substituted 2,2′-bipyridine complexes are discussed.     

Poly[[diaqua‐μ‐4,4′‐bipyridine‐dinitratodi‐μ‐l‐tyrosinato‐dicopper(II)]: a chiral two‐dimensional coordination polymer

The title compound, [Cu₂(C₉H₁₀NO₃)₂(NO₃)₂(C₁₀H₈N₂)(H₂O)₂]_n, contains Cu^II atoms and l ‐tyrosinate (l ‐tyr) and 4,4′‐bipyridine (4,4′‐bipy) ligands in a 2:2:1 ratio. Each Cu atom is coordinated by one amino N atom and two carboxylate O atoms from two l ‐tyr ligands, one N atom from a 4,4′‐bipy ligand, a monodentate nitrate ion and a water molecule in an elongated octahedral geometry. Adjacent Cu atoms are bridged by the bidentate carboxylate groups into a chain. These chains are further linked by the bridging 4,4′‐bipy ligands, forming an undulated chiral two‐dimensional sheet. O—H...O and N—H...O hydrogen bonds connect the sheets in the [100] direction. This study offers useful information for the engineering of chiral coordination polymers with amino acids and 4,4′‐bipy ligands by considering the ratios of the metal ion and organic components.     

300-MHz 1H-NMR spectra of p-cresol-formaldehyde condensates having regular repeating structures

Model p-cresol-formaldehyde condensates having regular sequences of methylene ether and methylene linkages were prepared by the self-condensation of dimethylol derivatives of p-cresol-formaldehyde condensates (2-hydroxy-5-methyl-1,3-benzenedimethanol, 3,3′-methylene-bis[2-hydroxy-5-methylbenzenemethanol] and 3,3′-[(2-hydroxy-5-methyl-m-phenylene)dimethylene]-bis[2-hydroxy-5-methylbenzenemethanol]). 300-MHz ¹H-NMR spectra of these polymers and of their acylated derivatives were recorded and used to develop resonance assignments for the various types of protons present in these polymers. The spectra were found to be sensitive to end-group and sequence distribution effects.     

Synthesis,characterization, photocleavage,antimicrobial activity and DNA binding of [Co(bpy)2MHPIP]3+, [Co(dmb)2MHPIP]3+, and [Co(phen)2MHPIP]3+ complexes

4-Methyl-2-(2-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline) (MHPIP) and its complexes [Co(bpy)₂MHPIP]³⁺ (1) (bpy = 2,2′-bipyridine), [Co(dmb)₂MHPIP]³⁺ (2) (dmb = 4,4′-dimethyl-2,2′-bipyridine), and [Co(phen)₂MHPIP]³⁺ (3) (phen = 1,10-phenanthroline) have been synthesized and characterized by UV/VIS, IR, EA, ¹H, ¹³C-NMR, and mass spectra. The binding of the three complexes with calf-thymus-DNA (CT-DNA) has been investigated by absorption and emission spectroscopy, DNA-melting techniques, viscosity measurements, and DNA cleavage assay. The spectroscopic data and viscosity results indicate that these complexes bind to CT-DNA via an intercalative mode. The complexes also promote photocleavage of plasmid pBR322 DNA and were screened for antimicrobial activity.     

Synthesis,crystal structure and third-order non-linear optical properties of a Zn(II) two-dimensional polymer

Two-dimensional (2-D) metal-organic polymer [Zn₃(μ₂-4,4′-bipy)₂(μ₂-be)₂(be)₂(μ₂-N₃)₂]_n 1 (4,4′-bipy = 4,4′-bipyridine, be = benzoate, N₃^? = azide anion) has been synthesized by low-hot reaction and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra and UV–visible spectra. The 2-D structure is built from the linkage of secondary building units of trinuclear [Zn₃(μ₂-4,4′-bipy)₂(μ₂-be)₂(be)₂(μ₂-N₃)₂] clusters by a mixed connector of 4,4′-bipyridine, benzoate and azide. The third-order non-linear optical (NLO) properties of the 1 were also investigated with modulus of the hyperpolarizability (γ) 8.51 × 10^?30 esu for 1 in a 3.17 × 10^?4 mol dm^?3 DMF solution.     

Synthesis and characterization of silicon-containing polyamides from aromatic sulfone ether diamines and aromatic organosilicon diacid chlorides

New polymides and copolyamides containing silicon and sulfone ether linkages, soluble in common aprotic solvents and having inherent viscosities of 0.3–0.6 dL/g have been synthesized by solution condensation of bis-(4-chlorocarbonyl phenyl) dimethylsilance (DMSC) and/or bis-(4-chlorocarbonyl phenyl) diphenylsilance (DPSC) with 4,4′-[sulfonylbis-(4,1-phenylenoxy)] bisbenzenamine, 3,3′-[sulfonylbis (4,1-phenyleneoxy)] bisbenzenamine, and bis (4-aminophenyl) ether. These polymers were characterized by infrared spectra, solution viscosity, thermooxidative degradation, differential scanning calorimetry, and x-ray diffraction. These polymers show good thermal stability.     

Polyether azomethines. I. Synthesis and characterization

Six new polyether azomethines were synthesized by melt and solution polycondensation of six different diamines with 4,4′-[1,4-phenylene bis(oxy)] bisbenzaldehyde. The polymers synthesized by solution method are yellow to white in color and had inherent viscosities up to 0.59 dL/g in concentrated H₂SO₄. The polymers obtained by melt condensation show higher viscosity. Except polymer IV , others are insoluble in common organic solvents. The polymers were characterized by IR, x-ray, elemental analysis, and DSC study. The thermal stability of the polymers was evaluated by TGA and IGA study. Polymers I-III are highly thermally and thermooxidatively stable and exhibit no appreciable decomposition up to 420°C both in air and nitrogen atmosphere. It was shown that the curing of the polyazo-methines takes place by opening up of the ? CH?N? linkages at higher temperature. The electrical conductivities of the virgin and iodine doped polymers were as high as 10^?11?10^?16 and 10^?6?10^?8S cm^?1, respectively, at 30°C. Electronic spectra of the undoped polymers ( I-III ) indicated a large bathochromic shift of the ? – ?^* absorptions band (376 nm) due to ? C?N? bonds of the model compound. This can be attributed to extensive delocalization of the electrons along the polymer chain. © 1995 John Wiley & Sons, Inc.     

Preparation and characterization of aromatic polyamides based on ether-sulfone-dicarboxylic acids

Two ether-sulfone-dicarboxylic acids, 4,4′-[sulfonylbis(2,6-dimethyl-1,4-phenylene)dioxy]dibenzoic acid (Me- III ) and 4,4′-[sulfonylbis(1,4-phenylene)dioxy]-dibenzoic acid ( III ), were prepared by the fluorodisplacement of 4,4′-sulfonylbis(2,6-dimethylphenol) and 4,4′-sulfonyldiphenol with p-fluorobenzonitrile, and subsequent alkaline hydrolysis of intermediate dinitriles. Using triphenyl phosphite (TPP) and pyridine as condensing agents, aromatic polyamides containing ether and sulfone links were prepared by the direct polycondensation of the dicarboxylic acids with various aromatic diamines in the N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride. The inherent viscosities of the resulting polymers were above 0.4 dL/g and up to 1.01 dL/g. Most of the polyamides were readily soluble in polar solvents such as NMP, N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO), and afforded tough and transparent films by solution-casting. Most of the polymers showed distinct glass transition on their differential scanning calorimetry (DSC) curves, and their glass transition temperatures (T_g) were recorded between 212–272°C. The methyl-substituted polyamides showed slightly higher T_gs than the corresponding unsubstituted ones. The results of the thermogravimetry analysis (TGA) revealed that all the polyamides showed no significant weight loss before 400°C, and the methyl-substituted polymers showed lower initial decomposition temperatures than the unsubstituted ones. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2421–2429, 1997