Synthesis and study of new poly(ester‐imide)s containing triptycene groups

A new triptycene‐containing dicarboxylic acid monomer was successfully synthesized by refluxing the diamine, bis(4‐aminophenoxy)phenyl triptycene with trimellitic anhydride in glacial acetic anhydride. A series of novel thermally stable poly(ester‐imide)s were prepared from dicarboxylic acid, bis(4‐trimellitimido phenoxy)phenyl triptycene with various diols by the direct polycondensation. The polymers were obtained in quantitative yields with inherent viscosities of 0.27–0.74 dL g^?1. The resulting polymers dissolved in N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide, N,N‐dimethylformamide, dimethyl sulfoxide, and pyridine. These polymers were fairly stable up to a temperature >450°C and lost 10% weight in the range of 477°C and 575°C in nitrogen. The UV–V is absorption spectra revealed that most of the polymers had absorption maxima around 310 and 341 nm. POLYM. ENG. SCI., 54:2252–2257, 2014. © 2013 Society of Plastics Engineers     

Synthesis and antitumour and antiangiogenesis activity of polymers containing methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid

A new monomer, methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid (MTCA), was synthesized from citric acid and methacrylic anhydride. Poly(methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid) and poly(methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid)‐co‐(maleic anhydride) were prepared by radical polymerizations. Terpoly(methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid–maleic anhydride–furan) was obtained by in situ terpolymerization of MTCA and exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalic anhydride. The synthesized samples were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The number‐average molecular weights of the fractionated polymers determined by GPC were in the range 14 900–16 600 and polydispersity indices were less than 1.14. The in vitro IC₅₀ values of the monomer and polymers against cancer and normal cell lines were much higher than those of 5‐fluorouracil (5‐FU). The in vivo antitumour activities of the synthesized samples at a dosage of 0.8 mg kg⁻¹ against mice bearing the sarcoma 180 tumour cell line decreased in the order terpoly(MTCA‐MAH‐FUR) > poly(MTCA‐co‐MAH) > poly(MTCA) > MTCA > 5‐FU. The synthesized samples inhibited DNA replication and angiogenetic activity more than did 5‐FU. © 2001 Society of Chemical Industry     

Effect of pH on the drug release rate from a new polymer–drug conjugate system

The corresponding N‐hydroximide and N‐methyl‐N‐hydroximide of poly[ethylene‐alt‐(maleic anhydride)] (weight average molecular weight (M_w) of 100–500 g mol^?1) were prepared as a new oral drug delivery system. Syntheses of N‐hydroximide and N‐methylhydroxamic acid of poly[ethylene‐alt‐(maleic anhydride)] were carried out by chemical modification of polymer with hydroxylamine and N‐methylhydroxylamine, respectively, to give water‐soluble polymers. These activated polymers were immobilized with ketoprofen in the presence of dicyclohexylcarbodiimide to give the corresponding water‐insoluble ketoprofen conjugates. All products were characterized by elemental analysis as well as Fourier transform infrared and ¹H NMR spectra. In vitro release of ketoprofen was studied by measuring UV absorption at λ_max = 260 nm as a function of time. This study demonstrated the potential use of N‐hydroximide and N‐methyl‐N‐hydroxamic acid of poly[ethylene‐alt‐(maleic anhydride)] as a drug delivery system. Controlled release was studied at different pH values and at different temperatures. At physiological temperature, the amount of drug released increased with increasing pH. The copolymer‐drug adducts released the drug very slowly at the low pH found in the stomach thus protecting the drug from the action of high acid conditions and resident digestive enzymes. These N‐hydroxamic acid polymer‐drug conjugates were found to be potentially useful in the delivery of macromolecular drugs to targeted sites in the lower gastrointestinal tract and the colon area. Copyright © 2007 Society of Chemical Industry     

Synthesis and Modification of Amine-Terminated Maleic Anhydride-Ethylene Copolymers by Benzaldehyde Derivatives: Characterization and Antimicrobial Properties

Antimicrobial polymers based on poly(ethylene-alt-maleic anhydride) (PEMA) were prepared. Amination of poly(ethylene-alt-maleic anhydride) using diamines of different chain lengths such as ethylenediamine (EDA) and hexamethylenediamine (HMDA) afforded terminal amino groups on the polymers. Antimicrobial polymers were obtained by immobilization of benzaldehyde and its derivatives, which include 4-hydroxybenzaldehyde and 2,4-dihydroxybenzaldehyde onto amine-terminated polymers. The antimicrobial activity of the prepared polymers were examined against different types of microorganisms including Gram-positive and Gram-negative bacteria as well as some fungi. The obtained results revealed that the antimicrobial activity increased with increasing the number of phenolic hydroxyl group and with increasing the spacer length.     

Synthesis,degradation, and drug delivery of cycloaliphatic poly(ester anhydride)s

The high melting point of poly(1,4‐cyclohexanedicarboxylic anhydride) [poly(CHDA)] is a disadvantage, in that it is intractable in the melting process of a drug delivery system. This report relates to diols introduced into the polyanhydride main chain to decrease its melting point. Various poly(ester anhydride)s containing ethylene glycol, 1,3‐propanediol, 1,4‐butanediol, or 1,6‐hexandiol [poly(CHDA–XDO)] were synthesized by the esterification reaction and melt polycondensation. FTIR, DSC, WAXD, and intrinsic viscosity of polymers were recorded and hydrolytic degradation, as well as in vitro drug delivery, was conducted. The results show that the samples are stable in an anhydrous environment at room temperature and degrade in water following a surface erosion mechanism. The degradation period of poly(CHDA–XDO) ranged from 130 to 320 h as a result of the different diols and amounts of XDO introduced. The in vitro drug delivery gave 130–350 h of stable delivery along with the typical surface erosion mechanism. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2509–2514, 2002     

Lipase‐catalyzed synthesis of aliphatic poly(β‐thioether ester) with various methylene group contents: thermal properties,crystallization and degradation

A series of novel aliphatic poly(β‐thioether ester)s with various methylene group contents were prepared by direct lipase‐catalyzed polycondensation of the monomer with an acid‐labile β‐thiopropionate group. The polycondensation reaction using immobilized lipase B from Candida antarctica was carried out in diphenyl ether at 90 °C. Poly(β‐thioether ester)s with high molecular weights of 20 500–57 000 Da and narrow polydispersities in the range 1.40–1.48 were obtained. Thermogravimetric analysis, differential scanning calorimetry and wide‐angle X‐ray diffraction were used to investigate the thermal properties and crystal structures of these polyesters. All the poly(β‐thioether ester)s were semicrystalline polymers and thermally stable up to at least 200 °C. In vitro degradation studies showed that they can rapidly degrade under acidic conditions by the hydrolysis of the β‐thiopropionate groups, suggesting their potential as acid‐degradable polymeric materials. © 2019 Society of Chemical Industry     

Biodegradable poly(sebacic acid‐co‐ricinoleic‐ester anhydride) tamoxifen citrate implants: Preparation and in vitro characterization

The aim of this study was to prepare tamoxifen citrate loaded cylindrical polymeric implants for application at tumor sites. The implant was based on poly (sebacic acid‐co‐ricinoleic‐ester anhydride) 70 : 30 w/w [poly(SA‐RA) 70 : 30 w/w], a low‐melting, biodegradable, and biocompatible polymer. Implants were prepared by a standardized melt manufacturing method. Differential scanning calorimetry and scanning electron microscopy were used for implant characterization. In vitro drug release studies were performed in phosphate‐buffered saline (pH 7.4) at 37 ± 2°C. The drug content was estimated by high‐performance liquid chromatography. The differential scanning calorimetry studies showed that the tamoxifen citrate in the implants was in the amorphous state. The cumulative percentage of drug release from 10 and 20 wt % drug‐loaded poly(SA‐RA) 70 : 30 w/w implants after 30 days was found to be 42.36 and 62.60%, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polymeric prodrug: Synthesis,release study and antimicrobial property of poly(styrene-co-maleic anhydride)-bound acriflavine

The release behaviour of poly(methyl methacrylate-co-maleic anhydride)-bound acriflavine was compared with that of acriflavine bound to poly(styrene-co-maleic anhydride), the latter copolymer was prepared by solution polymerization and characterised. Acriflavine was covalently bound on the surface of the copolymer matrix in N,N-dimethylformamide using triethylamine as catalyst. The amount of acriflavine covalently bound to poly(styrene-co-maleic anhydride) was studied as a function of time and concentration. The in vitro drug release kinetics of acriflavine in weakly basic medium and the antimicrobial activity of the released drug were established.     

Influence of molecular structure on the degradation mechanism of degradable polymers: In vitro degradation of poly(trimethylene carbonate), poly(trimethylene carbonate-co-caprolactone), and poly(adipic anhydride)

Relationships between molecular structure and the degradation mechanism of degradable polymers are of special interest for temporary medical applications. The in vitro degradation study of three aliphatic polymers—poly(trimethylene carbonate) (PTMC), poly(trimethylene carbonate-co-caprolactone) (PTMC-PCL), and poly(adipic anhydride) (PAA)—revealed that these polymers exhibit degradation times from several years (PTMC) to 1 day (PAA). PTMC degraded unexpectedly slow, accompanied by very small changes in weight loss, molecular weight (SEC), and in morphology (DSC, SEM). The degradation was independent of initial molecular weight, ionic strength of the water solution, temperature, and shaking motions. The copolymer PTMC-PCL showed a higher degradation rate compared to PTMC, with preferential degradation of amorphous parts leading to an increase in % crystallinity. The surprisingly rapid degradation of PAA showed characteristics typical for a surface-like eroding system in contrast to PTMC and PTMC-PCL. The degradation products corresponded to the repeating unit of the polymers. The hydrolysis rate increases in the order carbonate, ester, anhydride, and by combining different molecular structures we achieve specific degradation behavior. A change in hydrolysis rate of the labile bond is predicted by altering the electronegativity of groups near the carbonyl-oxygen region. © 1995 John Wiley & Sons, Inc.     

Structure and properties of p-carboxysuccinanilic polyester resins

Polyester resins were prepared by the reaction of p-carboxysuccinanilic acid ethyl ester with ethylene glycol and 1,4-butenediol. Also, unsaturated polyester resins were prepared by the copolymerization of p-carboxysuccinanilic acid ethyl ester and maleic anhydride with ethylene glycol, 1,6-hexanediol, 1,4-butenediol, and 2-butyne-1,4-diol. All the polyester resins and the copolyesters have been characterized and were found to cure with styrene, except those prepared in the absence of maleic anhydride. The properties of the cured products in the form of films were determined. Infrared and nuclear magnetic resonance (NMR) spectroscopy were used for both qualitative and quantitative analyses of the polyester resins and their hydrolyzate products after curing with styrene.     

Nitriles in heterocyclic synthesis. Part II: Synthesis and application of pyrano[3,2-h]quinoline sulphonamide derivatives

5-Sulphonamido-8-quinolinol reacts with cinnamonitrile derivatives in the presence of a basic catalyst to give pyrano[3,2-h]quinoline sulphonamide derivatives ( 8_a-d-13_a-d ). The reaction of 8_b, 9_b with some reagents such as acetic anhydride, acetic anhydride/pyridine mixture, formamide and formic acid/formamide mixture gave the fused heterotetracyclic systems pyrimido-[4′, 5′: 6, 5]pyrano[3, 2-h] quinoline sulphonamide derivatives. The structures of all newly synthesized compounds were confirmed by elemental analyses and spectral data. These compounds showed antimicrobial activity against some selected bacteria in vitro.     

Highly diastereoselective synthesis of novel polymers via tandem Diels–Alder–ene reactions

Cis -9,10-dihydro-9,10-ethanoanthracene-11-12-dicarboxylic acid anhydride (1) was converted into its amic acid derivative by reaction with L -leucine. The cyclization reaction was carried out in situ using triethylamine to give the succinic imide-acid derivative (2). Compound (2) was converted to the acid chloride (3) by reaction with thionyl chloride. The reaction of acid chloride (3) with isoeugenol (4) was carried out in chloroform and a novel optically active isoeugenol ester derivative (5) was obtained in high yield. 4-Phenyl-1,2,4-triazoline-3,5-dione (PhTD) (6) was allowed to react with compound (5). The reaction is very fast and gives only one diastereoisomer of (7) via Diels–Alder and ene pathways in quantitative yield. Compound (7) was characterized by ¹H NMR, IR, specific rotation and elemental analysis, and was used as a model for the polymerization reactions. The polymerization reactions of compound (5) with bis-triazolinediones (8), (9) were performed in N,N-dimethylacetamide (DMAc) at room temperature. The reactions are exothermic and fast, and give novel optically active polymers. Some physical properties and structural characterizations of these new polymers have been studied, and are reported. © 1999 Society of Chemical Industry     

Syntheses and characterization of maleic anhydride–styrene–allyl propionate terpolymer ester derivatives

In this study, maleic anhydride (MA)–styrene (St)–allyl propionate (AP) was produced with MA, St, and AP. It was then reacted with n‐propyl alcohol (Pr), n‐butyl alcohol (Bu), n‐pentyl alcohol (Pn), and benzyl alcohol (Bz) under certain conditions to produce ester derivatives of the terpolymer. These ester derivatives were designated alkyl maleate terpolymers (PrMA–St–AP, BuMA–St–AP, PnMA–St–AP, and BzMA–St–AP). The polymers were investigated by solubility and viscosity experiments, with the number of ester groups in the polymers determined by chemical analysis. They were also characterized by Fourier transform infrared spectroscopy, with thermomechanical properties measured via stress–strain curves. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 296–299, 2003     

Preparation and characterization of biodegradable poly(sebacic anhydride) chain extended by glycol as drug carrier

Glycol modified poly(sebacic anhydride) (PSA), a biodegradable poly(ester anhydride) copolymer, was prepared by melt bulk reaction of PSA and glycol. The structure of PSAG was characterized by FTIR, ¹H NMR, and GPC. The results indicate the formation of ester bonds along the polyanhydride backbone. The thermal properties and crystallinity changes of the polyanhydrides were investigated using DSC and XRD. In vitro degradation experiments show that the degradation rate of PSAG is slower than that of PSA because of the introduction of the glycol. Using dexamethasone as a model drug, the in vitro release rate of a drug from PSAG discs was shown to be slower than that from PSA discs, and no initial burst releases were observed for 13 days. PSAG is therefore a promising candidate, which control the release of an incorporated drug over a sustained period of time. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and antitumor activity of poly(3,4‐dihydro‐2H‐pyran‐co‐maleic anhydride‐co‐vinyl acetate)

The radical‐initiated terpolymerization of 3,4‐dihydro‐2H‐pyran (DHP), maleic anhydride (MA), and vinyl acetate (VA), which were used as a donor–acceptor–donor system, was carried out in methyl ethyl ketone in the presence of 2,2′‐azobisisobutyronitrile as an initiator at 65°C in a nitrogen atmosphere. The synthesis and characterization of binary and ternary copolymers, some kinetic parameters of terpolymerization, the terpolymer‐composition/thermal‐behavior relationship, and the antitumor activity of the synthesized polymers were examined. The polymerization of the DHP–MA–VA monomer system predominantly proceeded by the alternating terpolymerization mechanism. The in vitro cytotoxicities of poly(3,4‐dihydro‐2H‐pyran‐alt‐maleic anhydride) [poly(DHP‐alt‐MA)] and poly(3,4‐dihydro‐2H‐pyran‐co‐maleic anhydride‐co‐vinyl acetate) [poly(DHP‐co‐MA‐co‐VA)] were evaluated with Raji cells (human Burkitt lymphoma cell line). The antitumor activity of the prepared anion‐active poly(DHP‐alt‐MA) and poly(DHP‐co‐MA‐co‐VA) polymers were studied with methyl–thiazol–tetrazolium testing, and the 50% cytotoxic dose was calculated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2352–2359, 2005     

Synthesis of poly(ester‐anhydride)s based on poly(ϵ‐caprolactone) prepolymer

The objective of this study was to prepare high molecular weight poly(ester‐anhydride)s by melt polycondensation. The polymerization procedure consisted of the preparation of carboxylic acid terminated poly(?‐caprolactone) prepolymers that were melt polymerized to poly(?‐caprolactone)s containing anhydride functions along the polymer backbone. Poly(?‐caprolactone) prepolymers were prepared using either 1,4‐butanediol or 4‐(hydroxymethyl)benzoic acid as initiators, yielding hydroxyl‐terminated intermediates that were then converted to carboxylic acid‐terminated prepolymers by reaction with succinic anhydride. Prepolymers were then allowed to react with an excess of acetic anhydride, followed by subsequent polycondensation to resulting high molecular weight poly(ester‐anhydride)s. Upon coupling of prepolymers, size exclusion chromatography analyses showed an increase from 3600 to 70,000 g/mol in number‐average molecular weight (M_n) for the 1,4‐butanediol initiated polymer, and an increase from 7200 to 68,000 g/mol for the 4‐(hydroxymethyl)benzoic acid‐initiated polymer. 4‐Hydroxybenzoic acid and adipic acid were also used as initiators in the preparation of poly(?‐caprolactone) prepolymers. However, with these initiators, the results were not satisfactory. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 176–185, 2001     

Antimicrobial poly(N‐vinyl‐2‐pyrrolidone‐alt‐maleic anhydride)/poly(ethylene imine) macrocomplexes

The antimicrobial polymer/polymer macrocomplexes were synthesized by radical alternating copolymerization of N‐vinyl‐2‐pyrrolidone with maleic anhydride [poly(VP‐alt‐MA)] with 2,2′‐azobis‐isobutyronitrile as an initiator at 65°C in dioxane solutions under nitrogen atmosphere, and interaction of prepared copolymer with poly(ethylene imine) (PEI) in aqueous solutions. The susceptibility of some Gram‐negative (Salmonella enteritidis and Escherichia coli) and Gram‐positive (Staphylococcus aureus and Listeria monocytogenes) bacteria to the alternating copolymer and its PEI macrocomplexes with different compositions in microbiological medium was studied using pour‐plate technique. All the studied polymers, containing biologically active moieties in the form of ionized cyclic amide, and macrobranched aliphatic amine groups and acid/amine complexed fragments, were more effective against L. monocytogenes than those for Gram‐positive S. aureus bacterium. This fact was explained by different surface layer structural architectures of biomacromolecules of tested bacteria. The resulting polymeric antimicrobial materials are expected to be used in various areas of medicine and food industry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5841–5847, 2006     

Synthesis,characterization and properties of a castor oil modified biodegradable poly(ester amide) resin

A biodegradable poly(ester amide) resin was synthesized from N,N-bis(2-hydroxy ethyl) fatty amide of castor oil with maleic anhydride, phthalic anhydride and isophthalic acid (100:30:35:35 mole ratio) by the polycondensation process. The fatty amide of the oil was obtained for the first time with 95% yield. The chemical structure of the synthesized resin was characterized by spectroscopic techniques like FTIR, ¹H NMR and ¹³C NMR. Various physical properties such as acid value, saponification value, iodine value, specific gravity and viscosity of the resin were also determined. Further the rheological behavior, studied in the steady shear mode showed shear thinning behavior of the resin. The epoxy cured poly(ester amide) thermoset using poly(amido amine) hardener exhibited better properties than with the cycloaliphatic amine hardener cured system. TGA studies also revealed higher thermal stability of the former system than the latter. In vitro-biodegradation study of the poly(ester amide) thermoset using Pseudomonas aeruginosa and Bacillus subtilus bacteria revealed superior biodegradability of the thermoset using the former bacterial strain. Excellent chemical resistance against various chemical media including alkali was observed for epoxy-poly(amido amine) cured poly(ester amide) resin over epoxy-cycloaliphatic amine one. The epoxy-poly(amido amine) cured poly(ester amide) thermoset thus has the potential to be used as surface coating material.     

Properties of amylopectin/montmorillonite composite films containing a coupling agent

The addition of clay to polymers has the combined effects of enhancing both the strength/stiffness and the barrier properties. This investigation presents a novel approach to further enhance the strength/stiffness of cast plasticized amylopectin (AP)/Na⁺‐montmorillonite clay films using a water‐soluble coupling agent, poly[(isobutylene‐alt‐maleic acid, ammonium salt)‐co‐(isobutylene‐alt‐maleic anhydride)], between the filler and the matrix. The addition of clay increased the strength and stiffness of the film and the addition of 0.4 parts of a coupling agent per 1 part clay further increased these properties. The trends were the same after each treatment, and there were always significant differences in stiffness and strength between the films without clay and with clay with 0.4 parts of the coupling agent. The increase in stiffness/strength in the presence of a small amount of the coupling agent suggested that it had a bridging effect, presumably through strong secondary bonds to the clay and to the matrix. Infrared spectroscopy and moisture swelling experiments indicated that ester bonds were formed between the coupling agent and AP. X‐ray spectroscopy and transmission electron microscopy revealed that the clay‐particle/polymer structure was qualitatively independent of the presence of the coupling agent showing a mixture of intercalated clay stacks and exfoliated platelets. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4160–4167, 2007     

Novel low refractive index self-cross-linking fluoroterpolymers with very low surface tension and good adhesion to substrates

A novel family of fluoroterpolymers was prepared, containing perfluoroalkylethyl methacrylate (PFAEM), methacrylic acid (MAA), and 2-hydroxyethyl methacrylate (2-HEM) residues. The refractive index of the fluoroterpolymers is in the range of 1.3675 ≤ n ≤ 1.4275. The surface tension of cured thin films falls in the interval from 15 mN/m to as low as 8 mN/m. Upon heating, these polymers undergo thermally initiated self-crosslinking and develop tenacious bonding to substrates. The associated chemical reactions and products were identified by IR spectroscopy and some thermogravimetric scans. The spectra indicate that the reaction products are ester and anhydride groups. In general, the formation of esters occurs more rapidly and requires lower temperatures (≥ 110°C) than does the formation of anhydrides. Prolonged heating, especially at higher temperatures (≤ 150°C), favors the formation of anhydrides. When the molar ratio of MAA to 2-HEM is substantially larger than 1.0, the formation of anhydride is favored; when the ratio is 1 : 1, the formation of ester is favored; and when the molar ratio is much smaller than 1.0, the rate of formation of both esters and anhydrides is greatly reduced. In the case of the fluoroterpolymers, the formed esters and anhydrides essentially originate exclusively from the MAA and 2-HEM and seem not to involve any attack on the PFAEM residues. Only after very long heating at the higher temperatures employed, some loss of C? F band intensity was noted. In a copolymer of PFAEM and MAA, a substantial and rapid attack by the acid on the ester group in the PFAEM residues takes place under relatively mild conditions. Such and more drastic conditions appear not to affect at all a homopolymer of PFAEM alone. This suggests that in the fluoroterpolymers the more polar MAA and 2-HEM tend to aggregate close together, so that, when heated, they preferentially react with each other, forming both esters and anhydrides. In the absence of 2-HEM, the MAA may react with itself or with PFAEM, producing only anhydride groups. Both esters and anhydrides may be intermolecular and/or intramolecular, resulting in a cross-linked system in which the cross-link concentration is directly related to the combined amount of ester and anhydride groups. © 1993 John Wiley & Sons, Inc.