Synthesis,exchange reactions,and biological activity of poly(8‐methacryloxyquinoline)

8‐Methacryloxyquinoline (MAQ) was prepared through the reaction of 8‐hydroxyquinoline with either methacryloyl chloride or methacrylic acid in the presence of triethylamine or N,N‐dicyclohexylcarbodiimide, respectively. MAQ was polymerized in dimethylformamide with 2,2‐azobisisobutyronitrile as the initiator. The reactions of the resulting polymers with hydroxyl and amino compounds were studied. The polymers were characterized with IR, ¹H‐NMR, and mass spectroscopy. Some of the synthesized polymers were tested for their antimicrobial activity against bacteria and fungi. Generally, all the polymers were effective against the tested microorganisms, but their growth‐inhibition effects varied. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and antimicrobial activity of metronidazole containing polymer and copolymers

Homopolymer and copolymers containing metronidazole (MTZ) drug were synthesized. Acryloyl chloride was reacted with MTZ (drug) to produce monomer containing MTZ, and then the monomer was copolymerized with various amounts of methyl methacrylate. The produced monomer, homopolymer, and copolymers were characterized by elemental analysis, IR, and ¹H‐NMR. The antimicrobial activities of the synthesized polymers were tested against Kelpsilic as fungal organisms, and Escherichia coli, Bacillus subitilus, and Pesudomonus areuginosa as bacteria organisms. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Methyl Methacrylate-8-Quinolinyl Acrylate Copolymers-I: Synthesis and Characterization

Abstract

The monomer, 8-quinolinyl acrylate (8-QA) was synthesized and characterized by IR and ¹H-NMR spectroscopy, high performance liquid chromatography (HPLC) and elemental analysis. The homopolymer, poly (8-QA) and its copolymers with methyl methacrylate (MMA) in different monomer feed ratio were prepared by free radical polymerization using dimethyl formamide (DMF) as a solvent and 2,2′-azobis-isobutyronitrile (AIBN) as an initiator. The resulting polymers were characterized by IR spectroscopy, UV-visible spectrophotometry, gel permeation chromatography (GPC), solution viscosity and thermal analysis (TG and DSC). It was observed from the GPC results that as the 8-QA content in the copolymer increases, the molecular weight decreases whereas polydispersity increases with increasing 8-QA content in the copolymers. It was also observed from the TG data that the initial decomposition temperature (IDT) of the copolymers decreases with increasing 8-QA content in the copolymers.     

Chromophoric poly(urea‐urethane)s with pendent 3‐hydroxynaphthalene group: Synthesis and characterization

The reaction of 4‐(3‐hydroxynaphthalene)‐1,2,4‐triazolidine‐3,5‐dione ( 3HNTD ) with n‐propylisocyanate was performed at different molar ratios. The resulting monosubstituted urea and disubstituted urea‐urethane derivatives were obtained in high yields and were used as model compounds for polymerization reactions. 3HNTD as a monomer was used in the preparation of heterocyclic poly(urea‐urethane)s to produce photoactive polymers, by polycondensation with different diisocyanates in N,N‐dimethylacetamide (DMAc) solution. Chromophoric heterocyclic polymers containing naphthalene group, obtained in quantitative yields, possessed inherent viscosities in the range of 0.14–0.38 dL/g. The resulting poly(urea‐urethane)s is insoluble in most organic solvents, but easily soluble in polar solvents such as dimethyl sulfoxide (DMSO), DMAc, and N‐methylpyrrolidone (NMP). The polymers were characterized by IR, ¹H‐NMR, elemental analysis, and TGA. Fluorimetric and UV–vis studies of the monomer as well as polymers were performed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Acrylic Homo- and Co-polymers Based on 2, 4-dichlorophenyl Methacrylate and 8-quinolinyl Methacrylate

The monomer 2, 4-dichlorophenyl methacrylate (2,4-DMA) was synthesized from 2, 4-dichlorophenol and characterized by conventional methods. The homopolymers of 2,4-dichlorophenyl methacrylate and its copolymers with 8-quinolinyl methacrylate (8-QMA) in different feed ratio were prepared by free radical polymerization using dimethyl formamide (DMF) as a solvent and 2,2-azobis iso butyronitrile (AIBN) as an initiator. The resulting polymers were characterized by using IR spectroscopy. Reactivity ratios of monomer were evaluated using UV-spectroscopy. Average molecular weights and polydispersity were determined by gel permeation chromatography (GPC). Solution viscosity was also obtained. The thermal analysis was carried out using TGA and DSC. The homo- and co-polymers were also tested for their antimicrobial properties against selected microorganism. The metal ion uptake capacity of synthesized copolymers was estimated by batch equilibration method using different metal ion solution under different experimental conditions. It is observed that due to the presence of pendant ester bound quinoline group, the copolymers are capable of adsorbing cations from their aqueous solution.     

Stereoregularity in poly[methyl(3,3,3-trifluoropropyl)siloxane]

Anionic ring-opening polymerization of the cis and trans isomers of 1,3,5-trimethyl-1,3,5-tris(3′,3′,3′-trifluoropropyl)cyclotrisiloxane (cis- and trans-F₃) and their mixtures was conducted under conditions that suppressed siloxane bond redistribution in order to preserve stereoregularity formed in the resulting poly[methyl(3,3,3-trifluoropropyl)siloxane] (PMTFPS). Proton decoupled ¹⁹F NMR of the resulting polymers was interpreted by assuming that the original stereoconfiguration of the monomer was preserved and that the monomer inserted with a roughly equal probability of forming meso or racemic configurations relative to the configuration of the reacting chain end. Polymers from cis-F₃ were solid and crystalline at room temperature while the more typical polymers from mixtures of isomers containing greater than 50% trans-F₃ were liquid and amorphous.     

Preparation and properties of ester or cyano group substituted ring-opening polymers and their hydrogenated derivatives

Ester or cyano substituted tetracyclo [4.4.0.1^2,5.1^7,10]dodec-3-enes (1) were synthesized and their metathesis ring-opening polymerization was examined. The tungsten-based ternary catalyst system polymerized them very well. The polymers showed high glass transition temperatures (T_g) and no evidence of crystallization (e.g., the T_g of the polymer derived from 8-methyl-8-methoxycarbonyl substituted monomer (1a) was 207°C, and colorless transparent films could be casted from the solution of the polymer). The stability of these high T_g polymers were too unstable, so practical thermal molding methods could not be applied to them. The hydrogenation of these polymers with a palladium catalyst decreased T_g and greatly increased thermal stability. The physical and thermal properties of the hydrogenated polymers were thoroughly investigated. Monomer 1 was successfully copolymerized with other cyclic olefins. The resultant copolymers were hydrogenated, giving thermally stable polymers. In all cases examined in this study, a decrease of T_g by hydrogenation was about 35°C, regardless of the monomer structure. These results indicate that the main-chain mobility is the major contribution to the decrease of T_g. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 367–375, 1997     

Synthesis and characterization of novel fluoropolymers containing sulfonyl and perfluorocyclobutyl units

A novel sulfonyl-containing monomer, 4,4′-sulfonyl-bis(trifluorovinyloxy)biphenyl, and the resulting fluoropolymers with good thermal stability have been prepared. The monomer was synthesized by two steps using 4,4′-sulfonyldiphenol as starting material and characterized by FT-IR, ¹H NMR, ¹³C NMR, ¹⁹F NMR and element analysis in detail. Fluoropolymers containing sulfonyl and perfluorocyclobutyl units were prepared by different polymerization methods. A series of fluoropolymers with higher molecular weights were obtained by solution polymerization in diphenyl ether. The molecular weight is dependent on the polymerization time, polymerization temperature and the concentration of the monomer. The resulting polymers show excellent solubility in conventional solvents and good thermal stability with a high decomposition temperature about 500 °C measured by TGA.     

Synthesis,characterization, and evaluation of antifouling polymers of 4‐acryloyloxybenzaldehyde with methyl methacrylate

In recent years, antifouling (AF) polymers are widely used in marine paints to protect the ship hulls from biofouling. The AF polymer coatings have better leaching characteristics and long lasting efficiency than other conventional formulations. In this study, an attempt has been made to prepare new p‐acryloyloxybenzaldehyde(AcBA) polymers to assess their AF efficiency against marine microfoulers. The monomer, AcBA was prepared by the esterification reaction between p‐hydroxybenzaldehyde (HBA) and acryloyl chloride (Ac) in presence of triethylamine (TEA) in MEK at 0°C. The reaction was monitored by TLC and the prepared monomer was characterized by UV, IR, ¹H‐NMR and GC‐MS. The homo‐[poly(AcBA)] and co‐polymers [poly(AcBA‐co‐MMA)] were prepared by solution polymerization using BPO as initiator. To find out the AF activity of prepared polymers, representatives of marine microfoulers, shipfouling bacteria (Bacillus macroides and Pseudomonas aeruginosa) and microalgae (Amphora coffeaeformis and Navicula incerta) were screened. The contact toxicity and diatom attachment assays were conducted with prepared polymers and microfouling formation on coatings was also investigated using a tubular biofilm reactor. AF potential of these polymers coating is demonstrated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanochemical polymerization of acetylene

Gamma alumina, γ-Al₂O₃, was fractured in an atmosphere of acetylene monomer at room temperature to test whether they would be polymerized by mechanochemistry method on the surface of the alumina. The experimental results were obtained by serveral different methods, including CP–MAS ¹³C-NMR, ESR, pressure drop measurements of the monomer, optical absorption spectroscopy, and solvancy. The results proved the mechanochemical polymerization of acetylene monomer on surfaces of the fractured alumina. Several other combinations of either silica and acetylene monomer or polymers and acetylene monomer were tested for mechanochemical polymerization. This process proceeded with less efficiency in the silica system but no mechanochemical polymerization of acetylene was found in the combinations of the polymers and acetylene monomer.     

Photo-reactive particle prepared from natural rubber and 3-acryloyloxy-2-hydroxypropyl methacrylate

Photo-reactive particle was prepared by graft-copolymerization of 3-acryloyloxy-2-hydroxypropyl methacrylate (AHM) as a bi-functional monomer onto natural rubber (NR) in latex stage with potassium persulfate (KPS) as an initiator, after deproteinization with urea in the presence of surfactant. A terminal vinyl group of AHM was used for the graft-copolymerization, while the other remained in the resulting graft-copolymer, due to different reactivities of vinyl groups in the end of the bi-functional monomer. After graft-copolymerization, the resulting latex was UV-crosslinked to make chemical linkages between the residual pendant vinyl groups of grafted polymers linking up to the rubber particle. The resulting products were characterized by ¹H NMR and ¹³C NMR measurements. Effects of amount of rubber, monomer concentration and reaction time on conversion, grafting efficiency and amount of residual carbon-carbon double bond after graft-copolymerization were investigated. Under the optimum condition, high conversion of monomer and high amount of residual carbon-carbon double bond after graft-copolymerization were achieved without side reaction. A dramatic increase in modulus after UV-irradiation was associated with the connection of the functional polymer linking up to NR particle.     

Synthesis and polymerisation of maleoyl-L-histidine monomers and addition of histidine to an ethylene-alt-maleic co-polymer

This work has investigated two routes of synthesising polymers containing L-histidine using maleimide chemistry; grafting of histidine onto an ethylene-alt-maleic anhydride copolymer and AIBN (azobisisobutyronitrile) initiated radical polymerisation of the monomer maleoyl-L-histidine. The grafting technique and monomer synthesis are utilising the maleimide formation between the primary amine of histidine and maleic anhydride. The reactions are conveniently carried out in one step with good yields. The copolymers containing L-histidine were prepared by reacting L-histidine or L-histidine methyl ester with poly(ethylene-alt maleic anhydride) in DMSO at 50 °C for 8–16 h with 80% yields independent of the degree of substitution. The monomer maleoyl-L-histidine was synthesised by reacting histidine and maleic anhydride in acetic acid and the monomer was subsequently polymerised by AIBN radical initiation in DMSO at 80 °C for 48 h to yield poly(N-histidyl maleimide). The resulting polymer had a different optical rotation ([α]_D²⁰ = −11) than the monomer ([α]_D²⁰ = +25), which is ascribed to the threo-diisotactic and/or threo-disyndiotactic stereoregularity of the polymer.     

Preparation of hyperbranched copolymers of maleimide inimer and styrene by ATRP

Novel hyperbranched copolymers were prepared by the atom transfer radical copolymerization of N-(4-α-bromobutyryloxy phenyl) maleimide (BBPMI) with styrene in 1-methyl-2-pyrrolidone (NMP) using the complex of CuBr/2,2′-bipyridine as catalyst. The copolymerization behavior was investigated by comparison of the conversion of double bond of BBPMI determined by ¹H NMR with that of styrene. The hyperbranched structure of resulting copolymers was verified by gel permeation chromatography (GPC) coupled with multi-angle laser light scattering (MALLS). The influences of dosage of catalyst and monomer ratio on the polymerization rate and structure of the resulting polymers were also investigated. The glass transition temperature of the resulting hyperbranched copolymer increases with increasing mole fraction of BBPMI, f_BBPMI. The resulting copolymers exhibit improved solubility in organic solvents; however, they show lower thermal stabilities than their linear analogues.     

Microwave‐assisted and classical heating polycondensation reaction of bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L‐leucine with diisocyanates as a new method for preparation of optically active poly(amide imide)s

A new class of optically active poly(amide imide)s were synthesized via direct polycondensation reaction of diisocyanates with a chiral diacid monomer. The step‐growth polymerization reactions of monomer bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L‐leucine (BPABTL) (5) as a diacid monomer with 4,4′‐methylene bis(4‐phenylisocyanate) (MDI) (6) was performed under microwave irradiation, solution polymerization under gradual heating and reflux condition in the presence of pyridine (Py), dibuthyltin dilurate (DBTDL), and triethylamine (TEA) as a catalyst and without a catalyst, respectively. The optimized polymerization conditions according to solvent and catalyst for each method were performed with tolylene‐2,4‐diisocyanate (TDI) (7), hexamethylene diisocyanate (HDI) (8), and isophorone diisocyanate (IPDI) (9) to produce optically active poly(amide imide)s by the diisocyanate route. The resulting polymers have inherent viscosities in the range of 0.09–1.10 dL/g. These polymers are optically active, thermally stable, and soluble in amide type solvents. All of the above polymers were fully characterized by IR spectroscopy, ¹H NMR spectroscopy, elemental analyses, specific rotation, and thermal analyses methods. Some structural characterization and physical properties of this new optically active poly(amide imide)s are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1647–1659, 2004     

Development and Applications of Novel Acrylic Copolymers

The monomer 2,4-dichlorophenylacrylate was synthesized from 2,4-dichlorophenol and characterized by conventional methods. Homo- and copolymers of 2,4-dichlorophenylacrylate and butylmethacrylate were synthesized with different feed ratios using N,N-dimethylformamide as a solvent and 2,2′-azobisisobutyronitrile (AIBN) as an initiator at 70°C. The resulting polymers were characterized by infrared spectroscopy. Copolymer compositions were determined by ultraviolet (UV) spectroscopy. The monomer reactivity ratios were determined by applying the conventional linearization method of Fineman-Ross and Kelen-Tudos. The reactivity ratios values of 2,4-dichlorophenylacrylate and butylmethacrylate obtained from F-R plot are 0.91 and 1.15 respectively and from K-T plot, 0.97 and 1.24 respectively. The molecular weight and polydispersity of copolymers were determined by gel permeation chromatography (GPC). Thermo gravimetric analyses of the polymers were carried out in a nitrogen atmosphere. Thermal data suggest that the polymers underwent double decomposition. Homo and copolymers were tested for their antimicrobial properties against various microorganisms and showed strong inhibitory effects.     

Poly(ester)s and poly(amide)s with fluorene and diphenyl-silane units in the main chain: Effects of iodine doping on the structure and electrical conductivity

Intramolecular charge transfer interaction between the electron donor and electro acceptor units within the polymeric structure and its optoelectronic properties were studied. The monomer, 9H-fluorene-2,7-dicarboxylic acid, was prepared from 9H-fluorene-2,7-dicarbonitrile using CuCN/N,N-dimethylformamide followed by the decomposition of the complex with FeCl₃x6H₂O in HCl and KOH/H₂O. The formation of two new classes of polymers was reported at different reaction times. The poly(ester) (PEF) was synthesized by the reaction of the diacid monomer with bis(4-hydroxiphenyl)diphenylsilane using tosyl chloride/pyridine/dimethylformamide system as condensing agent. Alternatively, the poly(amide) (PAF) was synthesized by the direct polycondensation of the diacid monomer and bis(4-aminophenyl)diphenylsilane in N-methyl-2-pyrrolidine solution containing dissolved calcium chloride. The resulting new polymers were obtained in good yields and were characterized by FTIR, NMR (¹H, ¹³C, and ²⁹Si), ESI, Raman, UV (optical gap) and fluorescence spectroscopy. The thermal properties were characterized by DSC and TGA. The electrical conductivity of the polymers was measured before and after exposure to iodine vapor, utilizing films of different thickness. Ellipsometric studies were used for the determination of the film thickness. Morphological differentiation was carried out by SEM-EDX analysis. Oxidation of the polymer films of low thickness decreased their conductivities, mainly due to the small structural changes. For a polymeric sample with a higher thickness, the doping process slightly increased the conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and radical scavenging ability of new polymers from sterically hindered phenol functionalized norbornene monomers via ROMP

Norbornene derivatives, including four novel structure compounds, bearing sterically hindered phenol (SHP) were prepared as functional monomers (1-3). The ring-opening metathesis polymerization (ROMP) of these functional monomers was carried out with typical ruthenium catalyst [bis(tricyclohexylphosphine)benzylidene ruthenium(IV) dichloride] that was so called as first-generation Grubbs catalyst to prepare hindered phenol functionalized polymers possessing radical scavenging function. The resulting polymers were characterized by means of gel permeation chromatography (GPC), ¹H and ¹³C NMR, and differential scanning calorimetry (DSC). The radical scavenging ability of polymer was evaluated by determining RSA using the α,α-diphenyl-β-picrylhydrazyl (DPPH) free radical. The results show that the resulting polymers have different radical scavenging ability with the difference in structure of side chain. Polymers bearing 3,5-di-tert-butyl-4-hydroxyphenyl-propionate (DBHP) side chain have a higher radical scavenging ability than the polymers bearing 3,5-di-tert-butyl-4-hydroxy-benzoate (DBHB) as side chain. The molecular weight of polymers is dependent on the ratio of molar concentration of monomer to catalyst ([M]/[C]); monomers bearing DBHP group have a higher activity for ROMP than the monomers bearing DBHB group comparatively.     

(S)-2-(ethyl propionate)-(O-ethyl xanthate)- and (S)-2-(Ethyl isobutyrate)-(O-ethyl xanthate)-mediated RAFT polymerization of vinyl acetate

(S)-2-(Ethyl propionate)-(O-ethyl xanthate) (X1) and (S)-2-(Ethyl isobutyrate)-(O-ethyl xanthate) (X2) were used as the reversible addition-fragmentation chain transfer (RAFT) agents for the radical polymerization of vinyl acetate (VAc). The former showed the better chain transfer ability in the polymerization at 60°C. Kinetic study with both RAFT agents showed pseudo-first order kinetics up to around 85% monomer conversion. Molecular weight of the resulting polymer increased linearly with increase in the monomer conversion up to around 85%. The observed molecular weights calculated from ¹H-NMR spectrum [M_n(NMR)] are close to the corresponding theoretical molecular weights [M_n(theor)]. The corresponding polydispersity index (PDI) of the resulting polymers remained almost constant at around 1.2 up to ∼ 65% monomer conversion and then increased gradually with the further increase in the monomer conversion. Chain-end analysis of the resulting polymers by ¹H-NMR showed clearly that polymerization started with the radical forming out of the xanthate mediator. The negligible homo-chain extension and the hetero-chain extension involving synthesis of poly(VAc)-b-poly(NVP) diblock copolymer were occurred. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of copolymers from 3,5-dioxo-4,10-dioxatricyclo-[5.2.02,6]dec-8-ene and vinyl monomers by photopolymerization and their biological activities

Photocopolymerizations of 3,5-dioxo-4,10-dioxatricyclo[5.2.0^2,6]dec-8-ene (DDTD) with methacrylic acid (MA) acrylamide (AAm) and vinyl pyrrolidone (VP) were carried out in 2-butanone using dimethoxy benzoin (DMB) as an initiator at 25°C. The structures of the polymers obtained from photopolymerizations of corresponding monomer pairs were confirmed to be poly(DDTD-co-MA), poly(DDTD-co-AAm) and poly(DDTD-co-VP) by ¹H NMR and ¹³C NMR spectroscopies, and the average molecular weights were determined by gel permeation chromatography (GPC). The weight average molecular weights (M_w) of the polymers were in the range 9500–17300. The polymers were soluble in water, dimethyl sulphoxide (DMSO) and dimethyl formamide (DMF). The contents of DDTD units in the copolymers were 19, 37 and 45%. The in vitro cytotoxicities of the polymers were evaluated using mouse mammary carcinoma (FM-3A), mouse leukaemia (P-388) and human histiocytic lymphoma (U-937) cell lines. The in vivo antitumour activities of the polymers were estimated by the survival time of sarcoma 180 tumour-bearing mice. The in vivo antitumour activities of the polymers were greater than those of 5-fluorouracil (5-FU) and monomeric DDTD at a dose of 0·8mgkg^-1. Poly(DDTD-co-AAm) and poly(DDTD-co-VP) showed higher antitumour activity than 5-FU and monomeric DDTD at all doses tested. © 1998 SCI.     

Microbial screening of copolymers of 2,4‐dichlorophenyl methacrylate with N‐vinylpyrrolidone: synthesis and characterization

Copolymers of 2,4‐dichlorophenyl methacrylate and hydrophilic monomer (N‐vinylpyrrolidone) were synthesized with different feed ratios using dimethylformamide as solvent and 2,2′‐azobisisobutyronitrile as initiator at 70 °C. The copolymers were characterized by IR spectrometry. Copolymer compositions were determined by UV spectrometry. The monomer reactivity ratios were determined by applying the conventional linearization method of Fineman‐Ross. Gel permeation chromatography was employed for determining molecular weights and polydispersity indexes. Thermogravimetric analyses of polymers were carried out in nitrogen atmosphere. Homo‐ and copolymers were tested for their antimicrobial properties against selected microorganisms. © 2003 Society of Chemical Industry