Synthesis of novel ordered poly(ester-amide)s

Five different completely aromatic, ordered poly(ester-amide)s 6a — e were prepared from diphenols 5 and 4,4′-carbonyliminodibenzoyl dichloride ( 3 ). This bifunctional “amide-acid chloride” was synthesized in two steps by oxidation of 4,4′-dimethylbenzanilide ( 1 ) with permanganate under neutral conditions and subsequent reaction with thionyl chloride. The polymers obtained were characterized by IR spectroscopy and viscosity measurements. Their physical properties like density, solubility, and thermal behaviour were also studied.     

Preparation of poly(amide-imide)s by direct polycondensation with triphenyl phosphite, 3. Poly(amide-imide)s based on bis(trimellitimide)s

Six dicarboxylic acids ( 1a–f ) were prepared from trimellitic anhydride and 4,4′-oxydianiline, 4,4′-methylenedianiline, 4,4′-sulfonyldianiline, benzidine, 1,6-hexamethylenediamine, and 4,4′-methylenedicyclohexylamine. These diacids were condensed directly with various aromatic diamines using triphenyl phosphite in 1-methyl-2-pyrrolidone/pyridine solution in the presence of calcium chloride. The inherent viscosity of the polymers is affected by the nature of the diamine and the solubility of the resulting polymers in the reaction media. The highest η_inh-value of a poly(amide-imide) obtained was 1,41 dl/g (in N,N-dimethylacetamide/5% LiCl at 30°C). Among the polymers, the wholly aromatic ones show better solubility, higher glass transition temperatures, and higher thermostability than the aliphatic-aromatic ones. Well-defined melting points (T_m) of most wholly aromatic poly(amide-imide)s were not obtained by differential scanning calorimetry (DSC); however, some poly(amide-imide)s containing aliphatic chains showed clear T_m in the first DSC heating traces. Measurements of wide-angle X-ray diffraction revealed that those polymers containing biphenyl or linear hexamethylene groups are partially crystalline. Flexible films with excellent tensile properties were cast from N,N-dimethylacetamide solutions of most of the wholly aromatic poly(amide-imide)s.     

Liquid crystalline poly(β-aminoester)s containing different mesogenic groups

Four series of new poly(β-aminoester)s based on different mesogenic units and amino spacers were prepared and their properties examined. The polymers were obtained by a Michael-type polyaddition reaction of the diamines piperazine ( 5a ), 2-methylpiperazine ( 5b ), N,N′-dimethylhexamethylenediamine ( 5c ), and 4,4′-trimethylenedipiperidine ( 5d ) to diacrylates containing the anisotropic group, trans-4,4′-vinylenedi-p-phenylene diacrylate ( 1 ), 4-(4-acryloyloxybenzylideneamino)phenyl acrylate ( 2 ), 4,4′-diphenylylene diacrylate ( 3 ), and 4,4′-azoxydi-p-phenylene diacrylate ( 4 ). The mesophase behaviour of the resulting polymers 6–9 was strongly influenced by the nature of both the anisotropic and spacer groups. The 4,4′-azoxydi-p-phenylene unit appeared to be the most efficient in promoting liquid crystal properties, whereas no mesophases could be observed in polymers incorporating the 4,4′-biphenylylene unit. Doping of poly(β-aminoester)s, based on 4,4′-azoxydi-p-phenylene units, with a low-molar-mass cholesterogen allowed to obtain cholesteric structures extending over wide ranges of temperature. The molecular weight of the polymers was found to play a role in determining thermotropic mesomorphism by affecting the melting temperature of the polymer. In this context, some non-macromolecular model compounds were analyzed in respect of their thermal behaviour.     

Reactive poly(2-vinyl-4,4-dimethyl-5-oxazoione) and poly[(2-vinyl-4,4-dimethyl-5-oxazolone)-co-(methyl methacrylate)]s. Synthesis,characterization and chemical modification with 4-methoxy-4′-(β-aminoethoxy)biphenyl

Poly(2-vinyl-4,4-dimethyl-5-oxazolone) ( P₀ ) and poly[(2-vinyl-4,4-dimethyl-5-oxazolone)-co-(methyl methacrylate)]s with increasing content of methyl methacrylate units ( P₁–P₄ ) were synthesized and characterized. NMR spectra were discussed in terms of monomer sequence distribution and tacticity effects. The reaction of 4-methoxy-4′-hydroxybiphenyl ( 1 ) with 2-ethyl-2-oxazoline was utilized to prepare 4-methoxy-4′-(β-aminoethoxy)biphenyl ( 3 ) through the intermediate 4-methoxy-4′-[(N-propanoyl)-β-aminoethoxy]biphenyl ( 2 ). The homopolymer P ₀ and two copolymers P ₂ and P ₃ were functionalized with 4-methoxybiphenyl side groups by reaction with 3 via a ring-opening process in N,N-dimethylformamide (DMF) or 1,2-dichloroethane. The resulting copolymers P₅–P₈ were characterized by ¹H and ¹³C NMR. The highest degree of functionalized units was obtained in DMF at 80°C.     

Preparation of poly(ethylene glycol) grafted poly(3-hydroxyalkanoate) networks

Poly(3-hydroxyalkanoate)-g-poly(ethylene glycol) crosslinked graft copolymers are described. Poly(3-hydroxyalkanoate)s containing double bonds in the side chain (PHA-DB) were obtained by co-feeding Pseudomonas oleovorans with a mixture of nonanoic acid and anchovy (hamci) oily acid (in weight ratios of 50/50 and 70/30). PHA-DB was thermally grafted with a polyazoester synthesized by the reaction of poly(ethylene glycol) with MW of 400 (PEG-400) and 4,4′-azobis(4-cyanopentanoyl chloride). Sol-gel analysis and spectrometric and thermal characterization of the networks are reported.     

Polymer modification and synthesis using sulphenyl derivatives, 1. Preparation of poly(ß-chlorothioethers)

The preparation and characterization of some novel poly(ß-chlorothioethers), from reaction of 4,4′-biphenyldisulphenyl chloride ( 1 ) or benzene-1,3-disulphenyl chloride ( 2 ) with diolefins, are described.     

Synthesis and characterization of new halogen-containing poly(azomethine-urethane)s

A series of fluorine- and chlorine-containing bisphenols and their non-halogenated analogues were synthesized from various hydroxyaldehydes ( 1 ) and diamines ( 2 ). The structures of the corresponding bisphenols ( 3 ) were confirmed by ¹H NMR, ¹⁹F NMR and IR spectra. Poly(azomethine-urethane)s were prepared by reacting these monomeric bisphenols ( 3 ) with diisocyanates such as 4,4′-methylenedi(phenyl isocyanate) ( 4 ), 2,4-toluylene diisocyanate ( 6 ) and hexamethylene diisocyanate ( 8 ). Poly(azomethine-urethane)s ( 5 , 7 and 9 ) thus obtained were characterized by IR, UV, solubility, viscosity and thermal analysis (TG).     

Synthesis and 1H NMR study of aromatic poly(amide-thioether)s

The synthesis of aromatic poly(amide-thioether)s by reaction between 4,4′-thiodianiline, 4,4′-thiodibenzoic acid and 4-(4-aminophenylthio)benzoic acid is studied. Depending on the initial monomer ratio, polymers with head-to-head, head-to-tail or statistical distribution of amido groups along the polymer chains were obtained. Corresponding triads effects were observed in the ¹H NMR spectra and assigned. The synthesis of the same aromatic poly(amidethioether)s by reaction between dichlorobenzanilides and Na₂S is also studied. Only the Cl substituents in para position to a carbonyl groups are reactive and a head-to-head poly(amidethioether) was obtained by reaction of N,N′-thiobis(1,4-phenylene)-di-4-chlorobenzamide (2f) with Na₂S.     

Synthesis and permeation behavior of membranes from segmented multiblock copolymers containing poly(ethylene oxide) and poly(β-benzyl L-aspartate) blocks

Novel segmented multiblock copolymers ( 7 ) were synthesized by linking poly(ethylene oxide) (PEO) blocks with poly(β-benzyl L -aspartate)(PBLA) blocks via urethane and urea bonds, which were formed by the reaction of 4,4′-methylenediphenyl isocyanate ( 5 ) with the terminal hydroxyl groups of α-hydro-ω-hydroxypoly(oxyethylene) ( 4 ) and the terminal amino groups of poly(β-benzyl L -aspartate)-block-iminohexamethyleneimino-block-poly(β-benzyl L -aspartate) ( 3 ) [prepared from 1,6-hexanediamine ( 1 ) and β-benzyl L -aspartate N-carboxy anhydride ( 2 )], respectively. Membranes with various water contents were obtained from these copolymers by changing the lengths of the PEO and PBLA segments. The study of the permeation of 1-phenyl-1,2-ethanediol, vitamin B₁₂ and myoglobin through the membranes showed a high dependency of the permeability on the molecular weight of the solutes.     

Sodium sulfonate-functionalized poly(ether ether ketone)s

A new monomer, sodium 5,5′-carbonylbis(2-fluorobenzenesulfonate) ( 1 ), was synthesized by sulfonation of 4,4′-difluorobenzophenone ( 2 ) with fuming sulfuric acid. Poly(ether ether ketone)s containing sodium sulfonate groups were synthesized directly via aromatic nucleophilic substitution from the sodium sulfonate-functionalized monomer 1 and Bisphenol A ( 3 ) in the presence of potassium carbonate in dimethyl sulfoxide. The polycondensation proceeds without any side reactions. The differential scanning calorimetry measurement indicated that the polymers are amorphous and the glass transition temperatures increase with the content of sodium sulfonate groups in the polymer chain. The degree of substitution with sodium sulfonate groups has strong influence on their thermal stability and solubility.     

New polymer syntheses, 72. Telechelic and star-shaped poly(ether-sulfone)s by polycondensation of 4-fluoro-4′-trimethylsiloxy(diphenyl sulfone)

The homopolycondensation of 4-fluoro-4′-trimethylsiloxy(diphenyl sulfone) ( 2 ) in bulk and its cocondensation with 4-fluoro-4′-trimethylsiloxybenzophenone ( 1 ) yielded high-molecular-weight, amorphous (co)poly(ether-sulfone)s. The cocondensation with 4,4′-difluoro(diphenyl sulfone) ( 4 ) afforded telechelic oligomers or polymers with two fluorobenzophenone end-groups. Cocondensation with 4,4′-bis(2,4-difluorobenzoyl)[diphenyl ether] ( 5 ) gave star-shaped polymers with four branches. Cocondensation with 1,3,5-tris(trimethylsiloxy)benzene ( 6 ) yielded star-shaped poly(ether-sulfone)s with three longer than calculated star arms. Cocondensations with 2,2′,4,4′-tetrakis(trimethylsiloxy)benzophenone ( 7 ) did not result in the formation of star-shaped polymers, but yielded telechelic linear poly(ether-sulfone)s with two trimethylsiloxy end-groups. It was found that rapid cyclization of the benzophenone derivative (yielding a bis(trimethylsiloxy)xanthone) precedes the polycondensation.     

Dehydrochlorination of poly(sulfonyl-co-2-chloroethylene)

Poly(sulfonyl-co-2-chloroethylene)s were shown to have an enhanced tendency to undergo dehydrochlorination compared with poly(vinyl chloride). Dehydrochlorination was observed under the following conditions: (a) during preparation of the copolymers by γ-radiation initiated copolymerization of vinyl chloride and sulfur dioxide, (b) by γ-irradiation of the polymer, (c) during ageing, (d) on heating and (e) in solution in basic solvents, such as DMSO. The dehydrochlorination was studied by microanalysis, by IR and UV spectroscopy and by ¹H and ¹³C NMR. Hydrogen chloride was eliminated preferentially from chloroethylene units occurring between two sulfonyl units. The proportion chloroethylene units: sulfonyl units in poly(sulfonyl-2-chloroethylene) decreased from ≈ 2:1 at a copolymerization temperature of 0°C to ≈ 1:1 at a temperature of ?78°C. The results show, that dehydrochlorination of copolymers prepared at low temperatures is a serious problem, especially with initiation by γ-irradiation.     

Synthesis of segmented poly(ether urethane)s and poly(ether urethane urea)s incorporating various side-chain or backbone functionalities

A series of linear and branched functionalized high-molecular-weight segmented poly (ether urethane)s and poly(ether urethane urea)s were prepared by chain-extending isocyanate pre-polymers based on poly(tetramethylene oxide) with molecular weight 1000 and 4,4'-diphenylmethane diisocyanate. Different functional groups were incorporated within the polymer backbone or on side-chains by using several chain extenders during the synthesis: glycerol, 2,2-bis (hydroxymethyl) propionic acid, 1H, 1H,2H,3H,3H-perfluoroundecane-1,2-diol, 1H,1H,8H,8H-dodecanefluoro-1,8-octanediol, 1,3-diamino-2-hydroxypropane and 3,5-diaminobenzoic acid, using the method of gradual approach to stoichiometry. In some cases, pendant functional groups were used as reactive sites for the further attachment of side groups. Polymers were characterized using 1H-NMR and FT-IR spectroscopies and GPC in conjunction with chemical structural confirmation by a model compound comparison study of 4,4'-diphenylmethane diisocyanate or trifluoro-p-tolyl isocyanate reacted with 1,3-diamino-2-hydroxypropane and 1,4-butanediol.     

A novel synthetic route to poly(β-ketone)s via poly(alkoxyethyne)s

Isopropoxyethyne (1a) and tert-butoxyethyne (1b) were polymerized using group 5 and 6 transition metal catalysts to give poly(isopropoxyethyne) (2a) and poly(tert-butoxyethyne) (2b) , respectively. The weight-average molecular weight (M?_w) of the resulting poly(alkoxyethyne)s was up to 1.0 × 10⁴. Among the transition metal catalysts, a tungsten alkoxide or a molybdenum alkoxide having low Lewis acidity were found to effectively promote the polymerization without causing side reactions. Poly(tert-butoxyethyne) was successfully converted to poly(β-ketone) 3 by acid hydrolysis of the tert-butyl vinyl moiety.     

Synthesis of poly(2-ethyl-2-hydroxymethyltrimethylene carbonate)

2-Ethyl-2-hydroxymethyltrimethylene carbonate (5-ethyl-5-hydroxymethyl-1,3-dioxan-2-one) ( 1 ) was treated with trimethylsilyl chloride, benzyl chloroformate and phenyl isocyanate to give the corresponding 5,5-disubstituted 1,3-dioxan-2-ones 2 , 3 and 4 . These monomers were subjected to anionic ring-opening polymerization reactions with lithium alcoholates as initiators. The polymers obtained usually exhibit linear structure; under special conditions slightly branched polymers were obtained. Poly( 2 ) and poly( 3 ) were subjected to polymer-analogous reactions—hydrolysis and hydrogenation—by which the protective groups are removed and poly( 1 ) was obtained. The hydroxyl groups in poly(1) are susceptible to a polymer-analogous reaction. Poly( 4 ) obtained by reaction of poly( 1 ) with phenyl isocyanate was identical with poly( 4 ) obtained by ring-opening polymerization of the corresponding monomer 4 . All these new monomers were characterized by means of ¹H and ¹³C NMR spectroscopy as well as elemental analysis. The polymers were analyzed with respect to their primary structure, their molecular weight and molecular weight distribution. The thermal properties of some of the polymers are discussed.     

Preparation,properties and complex formation ability of poly(ether-ester)s of poly(ethylene glycol)s and 2,6-pyridinedicarboxylic acid

Poly(ether-ester)s of poly(ethylene glycol)s (PEGs) and 2,6-pyridinedicarboxylic acid (PDA) were synthesized by polycondensation of PDA and PEG in the presence of dicyclohexylcarbodiimide and dimethylaminopyridine and by polycondensation of acyl chloride of PDA and PEG in the presence of triethylamine at 45°C. The polymers were characterized by GPC, UV, IR and ¹H and ¹³C NMR spectroscopy. The complex formation between poly(acrylic acid) (PAA) or poly(methacrylic acid) (PMA) and the poly(ether-ester)s was studied. It occurs below the critical polyether chain length necessary for complex formation because of the stabilizing effect of the PDA hydrophobic residues.     

New poly(amide-imide) syntheses, 19. Preparation and properties of poly(amide-imide)s derived from N-phenyl-3,3-bis[4-(4-aminophenoxy)phenyl]-1-oxoisoindoline and various bis(trimellitimide)s

A series of novel bis(phenoxy)-1-oxoisoindoline-containing poly(amide-imide)s 3 were synthesized by the direct polycondensations of N-phenyl-3,3-bis[4-(4-aminophenoxy)-phenyl]-1-oxoisoindoline ( 1m , NPBA) with various aromatic bis(trimellitimide)s 2 in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide-imide)s 3 having inherent viscosities up to 1,06 dL/g were obtained in quantitative yields. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvent such as NMP and N,N-dimethylacetamide. All of the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 277–327°C, and the 10% weight loss temperatures were above 500°C in nitrogen. The properties of poly(amideimide)s 3 were compared with those of the corresponding isomeric poly(amide-imide)s 3 ′ prepared from NPBA and various aromatic diamines.     

Synthesis and characterization of isomeric biphenyl-containing poly(aryl ether bisketone)s, 3. Polymers derived from 3,4′-bis(4-fluorobenzoyl)biphenyl and bisphenols

A series of high-molecular-weight amorphous and semicrystalline poly(aryl ether bisketone)s were prepared from bisphenols and 3,4′-bis(4-fluorobenzoyl)biphenyl via nucleophilic aromatic substitution reactions. Model compound studies were carried out with several substituted monohydric phenols, 3,4′-bis(4-fluorobenzoyl)biphenyl and 3,4′-bis(4-Chlorobenzoyl)biphenyl. The dihalo-substituted aromatic ketones were synthesized by the reaction of 3,4′-biphenyldicarboxylic acid with thionyl chloride, followed by Friedel-Crafts acylation with the appropriate aryl halide. The required dicarboxylic acid was prepared starting from 4-bromotoluene and 3-methylcyclohexanone. Potassium carbonate mediated reaction of the monomers in dimethylacetamide or diphenyl sulfone gave high-molecular-weight polymers in excellent yield. The glass transition temperatures of the polymers are in the 170 to 190°C range. In addition, the polymers exhibit excellent thermal stability, as evidenced by both dynamic and isothermal thermogravimetric analysis, and afford tough films by compression molding.     

Functional metal-porphyrazine derivatives and their polymers, 4. Synthesis of poly(styrene) bonded Fe(III)- as well as Co(II)-4,4′,4″,4″′-tetracarboxyphthalocyanine and their catalase-like activity

Metal-4,4′,4″,4″′-tetracarboxyphthalocyanine [Metal = Fe(III), Co(II), Mt-taPc] were synthesized by the hydrolysis of metal-4,4′,4″,4″′-tetracarboxamidephthalocyanine (Mt-tamPc). These metal-taPc are soluble in water and in aprotic polar solvents such as N,N′-dimethylformamide. Poly(styrene) bonded Mt-taPc was synthesized by Friedel-Crafts reaction of poly(styrene) with Mt-taPc tetraacid chloride. The polymers contain about 4 mole-% Mt-Pc rings which are covalently bonded to poly(styrene). The decomposition reaction of hydrogen peroxide by catalysis with polystyrene containing Mt-Pc rings was carried out in heterogeneous aqueous media at pH 7,0. The polymer catalysts show a catalase-like activity. The activation energies with the polymer bonded Mt-Pc were found to be about half of those with Mt-taPc. From continuous flow experiments in a column, the polymer attached catalyst was found to be very stable, compared with free Mt-taPc.     

New poly(amide-imide)s synthesis, 16. Preparation and properties of poly(amide-imide)s derived from 3,3-bis[4-(4-aminophenoxy) phenyl]phthalide and various bis(trimellitimide)s

A series of novel bis(phenoxy)phthalide-containing poly(amide-imide)s 3 were synthesized via direct polycondensation of 3,3-bis[4-(4-aminophenoxy)phenyl]phthalide (BAPP) with various aromatic bis(trimellitimide)s 2 in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide-imide)s 3 having inherent viscosities up to 1,68 dL/g were obtained in quantitative yields. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 237–292°C and the 10% weight loss temperatures were above 500°C in nitrogen. The properties of poly(amide-imide)s 3 were compared with those of the corresponding isomeric poly(amide-imide)s 3′ prepared from 3,3-[4-(4-trimellitimido-phenoxy)phenyl]-phthalide and various aromatic diamines.