Activated polymers. II: Synthesis and exchange reactions of biologically active poly(8-acryloxyquinoline)

The monomer 8-acryloxyquinoline (8-AQ) was prepared through the reaction of 8-hydroxyquinoline with either acryloyl chloride or acrylic acid in the presence of triethylamine or N,N-dicyclohexylcarbodiimide, respectively . The resulting monomer was polymerized by free radical polymerization using dimethylformamide (DMF) as a solvent and 2,2^'-azobisisobutyronitrile (AIBN) as an initiator. The reactions of the resulting polymers with hydroxyl and amino compounds have been studied. The polymers were characterized by IR and ¹HNMR 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.     

Biologically active polymers. IV. Synthesis and antimicrobial activity of polymers containing 8‐hydroxyquinoline moiety

Polymers containing 8‐hydroxyquinoline moiety were prepared. Modifications of the base polymer of glycidyl methacrylate were carried out in order to introduce chloromethyl groups, either by the hydrolysis of the poly(glycidyl methacrylate) and the chloroacetylation of the hydrolyzed polymer by the reaction with chloroacetyl chloride or by aminating the poly(glycidyl methacrylate) either with ethylenediamine or with hexamethylenediamine, followed by reacting the aminated polymers with chloroacetyl chloride. The polymers containing 8‐hydroxyquinoline moiety were prepared by reacting the chloromethyl groups containing polymers with potassium salt of 8‐hydroxy quinoline. The antimicrobial activity of the polymers obtained was examined against gram‐negative bacteria (Escherichia coli) and gram‐positive bacteria (Bacillus subtilus) as well as the fungus Trichophyton rubrum. Generally, all three polymers proved effective against the tested microorganisms, but growth inhibitory effects varied from one another. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1364–1374, 2001     

Biologically active polymers. IV. Synthesis and antimicrobial activity of tartaric acid polyamides

New bactericidal polyamides with quaternary ammonium or phosphonium salts were prepared, and their antimicrobial activities were explored. The polyamides were synthesized by the polycondensation of diethyl‐l‐tartrate or chloromethylated diethyl‐l‐tartrate with ethylenediamine in dry absolute ethanol. The polyamides were modified to yield polymers with either quaternary ammonium or phosphonium salts. The polymers were characterized with elemental microanalysis and ¹H‐NMR and IR spectra. The antimicrobial activity of the polymers bearing onium salts was studied against Gram‐negative bacteria (Escherichia coli, Pseudomones aeruginosa, Shigella sp., and Salmonella typhae), Gram‐positive bacteria (Bacillus subtilis and Bacillus cereus), and a fungus (Trichophytum rubrum) by the cut‐plug and viable‐cell‐count methods. Although all the polymers showed high antibacterial activity, some had no antifungal activity. The tributyl phosphonium salt of the polyamide was more effective against both Gram‐negative and Gram‐positive bacteria than the triethyl ammonium and triphenyl phosphonium salts of the polyamide. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4780–4790, 2006     

Thermal properties,adhesive strength,and optical transparency of cyclolinear poly(aryloxycyclotriphosphazenes)

Four cyclolinear poly(aryloxycyclotriphosphazenes) derived from poly[4,4′‐(isopropoylidene)diphenoxytetrachlorocyclotriphosphazene] and poly[4,4′‐(hexafluoroisopropylidene)diphenoxytetrachlorocyclotriphosphazene] were synthesized from the reaction of hexachlorocyclotriphosphazene (HCP) with 4,4′‐(isopropylidene)diphenol (bisphenol A) or 4,4′‐(hexafluoroisopropylidene)diphenol (bisphenol AF) in molar ratio 1 : 1 via a one‐step condensation polymerization. Subsequent reaction of the resulted chlorine‐bound polymers with adequate amount of the sodium salts of 4‐methoxycarbonylphenoxide or 4‐propoxycarbonylphenoxide yielded the corresponding chlorine‐free polymers, [poly(tetra‐4‐methoxycarbonylphenoxy)‐4,4′‐(isopropoylidene)diphenoxy cyclotriphosphazene] (MBACP), [poly(tetra‐4‐propoxycarbonylphenoxy)‐4,4′‐(isopropoylidene)diphenoxycyclotriphosphazene] (PBACP), [poly(tetra‐4‐methoxycarbonylphenoxy)‐4,4′‐(hexafluoroisopropylidene)diphenoxycyclotriphosphazene] (MBAFCP), [poly(tetra‐4‐propoxycarbonylphenoxy)‐4,4′‐(hexafluoroisopropylidene)diphenoxycyclotriphosphazene] (PBAFCP), respectively. The chemical structures were characterized by Fourier transformer infrared, ¹H, and ¹³C‐NMR. Thermal properties of polymers were investigated using DSC and TGA analysis. The obtained polymers were thermoplastic, having moderate T_g values in the range of 26–78°C and good thermal stability up to 350°C in N₂ and O₂ gases. The thermal decomposition of the isopropylidene‐containing polymers is a one‐step process, while that of hexafluoroisopropylidene‐containing polymers is a two‐step process. However, presence of the latter group in the polymers backbone showed negligible effects on the thermo‐oxidative stability. The adhesive strength was measured by lap‐shear strength test on glass–glass bonded joint and found to be in the range of 1.78–2.62 MPa, this property may be attributed to the physical interactions between glass–glass interfaces and the polar‐pendant units present at the polymers backbone. The products showed high optical transparency when they applied between two glass surfaces, the adhesive layers were colorless, with the UV cut‐off wavelength of 300–302 nm, and the maximum transparency of about 90% was observed within the wavelengths range of 400–700 nm. Because of their properties, the cyclolinear poly(aryloxycyclotriphosphazenes) synthesized in this study are recommended as potential candidates for high thermally stable, transparent adhesives required in industrial applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

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     

Synthesis,characterization, and photophysical properties of novel poly(p‐phenylene vinylene) derivatives with conjugated thiophene as side chains

Two novel poly(p‐phenylene vinylene) (PPV) derivatives with conjugated thiophene side chains, P1 and P2, were synthesized by Wittig‐Horner reaction. The resulting polymers were characterized by ¹H‐NMR, FTIR, GPC, DSC, TGA, UV–Vis absorption spectroscopy and cyclic voltammetry (CV). The polymers exhibited good thermal stability and film‐forming ability. The absorption spectra of P1 and P2 showed broader absorption band from 300 to 580 nm compared with poly[(p‐phenylene vinylene)‐alt‐(2‐methoxy‐5‐octyloxy‐p‐phenylene vinylene)] (P3) without conjugated thiophene side chains. Cyclic voltammograms displayed that the bandgap was reduced effectively by attaching conjugated thiophene side chains. This kind of polymer appears to be interesting candidates for solar‐cell applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and biological activity of medium molecular weight polymers containing 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl‐5‐fluorouracil

A new monomer, 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl‐5‐fluorouracil (ETBFU), was synthesized by reaction of 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl chloride and 5‐fluorouracil. The homopolymer of ETBFU and its copolymers with acrylic acid (AA) or vinyl acetate (VAc) were prepared by photopolymerization using 2,2‐dimethoxy‐2‐phenylacetophenone as an initiator at 25 °C. The synthesized ETBFU and its polymers were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The ETBFU content in poly(ETBFU‐co‐AA) and poly(ETBFU‐co‐VAc) was 43 and 14 mol%, respectively. The apparent number‐average molecular weight (M_n) of the polymers determined by GPC ranged from 8400 to 11 300. The in vitro cytotoxicity of the samples against mouse mammary carcinoma (FM3A), mouse leukaemia (P388), and human histiocytic lymphoma (U937) cancer cell lines decreased in the order 5‐FU ≥ ETBFU > poly(ETBFU) > poly(ETBFU‐co‐AA) > poly(ETBFU‐co‐VAc). The in vivo antitumour activity of the polymers against Balb/C mice bearing sarcoma 180 tumour cells was greater than that of 5‐fluorouracil at all doses tested. © 2000 Society of Chemical Industry     

Part 14. Synthesis and properties of new polyketoamine polymers containing cycloalkanone moieties in the main chain

A new interesting class of polyketoamine polymers based on diarylidenecycloalkanone were synthesized by suspension polycondensation. These polymers were synthesized via polymerization of 2,5‐bis(4‐chloroacetylbenzylidene)cyclopentanone and 2,6‐bis(4‐chloroacetylbenzylidene)cyclohexanone with different aliphatic and aromatic diamines including, p‐phenylenediamine, m‐phenylenediamine, o‐phenylenediamine, 4,4′‐diaminodiphenylmethane, 4,4′‐diaminodiphenylether, 4,4′‐diaminodiphenylsulfone, hydrazine hydrate, 1,2‐diaminoethane, 1,3‐diaminopropane and 1,8‐diaminooctane. Model compounds were prepared by condensation of 2,5‐bis(4‐chloroacetylbenzylidene)cyclopentanone and/or 2,6‐bis(4‐chloroacetylbenzylidene)cyclohexanone with aniline in dry benzene, and their structure was confirmed by elemental analysis and spectroscopy. The structure of the polymers obtained was also confirmed by the same methods. Moreover, the identification of the polymers was carried out by other techniques, eg crystallinity from X‐ray spectroscopy, viscosimetry, thermogravimetric analysis; the morphological properties of selected examples were tested by scanning electron microscopy. The electrical conductivity of selected examples is about 10^?12 ohm cm^?1. The results are in accord with the structure. © 2002 Society of Chemical Industry     

Synthesis and characterization of novel polyimides containing triazoles units in the main chain by click chemistry

In this study, some polyimides containing triazoles units in the main chain was prepared from the polymerization of dialkynes including imide linkages and diazides in the presence of Cu (I) catalyst in yield of 76.2–87.6%, with inherent viscosity of 0.37–0.53 dL g^?1. The obtained polymers are soluble in polar aprotic solvents such as N,N‐dimethyformamide (DMF), N,N‐dimethyacetamide (DMAc), dimethyl sulfoxide (DMSO), and N‐methyl‐2‐pyrrolidone (NMP). These polymers were characterized using FT‐IR, ¹H‐NMR, and elemental analysis techniques. Their thermal stability was evaluated with thermogravimetric (TGA) analysis and differential scanning calorimetry (DSC) techniques under a nitrogen atmosphere which is indicative of their good thermal stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis,characterization, and preliminary antimicrobial evaluation of bisphenol‐A formaldehyde resin coordinated with transition metal complexes of ethylenediamine

Coordination polymers containing bisphenol‐A, formaldehyde, and transition metal complexes of ethylenediamine [M(en)₂] were synthesized by the reaction of bisphenol‐A, formaldehyde, and M(en)₂ complex in alkaline medium, using M for Fe⁺³, Co⁺², Ni⁺², Cu⁺², and Zn⁺². The materials were characterized by elemental analysis, FTIR, UV–Vis, ¹H‐NMR spectra, TGA, and magnetic susceptibility measurement. The geometry of the central metal ions was determined by electronic spectral studies and magnetic moment measurement. The M N and C N bonds were confirmed by the IR spectra of the polychelates. The ¹H‐NMR spectra of the chelating resins confirmed polycondensation with well‐defined peaks for bridging methylene functions. Complexation studies with transition metal ions revealed effective coordination of the bisphenol‐A formaldehyde resin. The antimicrobial activities of these chelated resins were screened against E. coli, S. dysantrea (bacteria), and C. albicans, A. niger (fungi) by using agar well diffusion method. All the polymeric chelates show promising antimicrobial activities. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis,antitumour and DNA replication activities of polymers containing vinyl‐(5‐fluorouracil)‐ethanoate

A new monomer, vinyl‐(5‐fluorouracil)‐ethanoate (VFUE), was synthesized by reaction of 5‐fluorouracil (5‐FU) and vinyl iodoacetate. The homopolymer of VFUE and its copolymers with acrylic acid (A, A) and maleic anhydride (MAH) were prepared by photopolymerization. The synthesized VFUE and polymers were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The contents of VFUE unit in poly(VFUE‐co‐AA) and poly(VFUE‐co‐MAH) were 21 mol% and 16 mol%, respectively. The number average molecular weights of the polymers determined by gel permeation chromatography were in the range 9600–17900 g mol^?1. The in vitro cytotoxicities of the samples against a normal cell line decreased as follows: 5‐FU > VFUE > poly(VFUE) > poly(VFUE‐co‐AA) > poly(VFUE‐co‐MAH). The in vivo antitumour activities of the polymers against Balb/C mice bearing the sarcoma 180 tumour cells were greater than those of 5‐FU at all concentrations. The inhibition of simian virus 40 DNA replication by the samples was much greater than that of the control. © 2002 Society of Chemical Industry     

Synthesis,spectral, and thermal characterization of photosensitive poly(ether–ester)s containing α,β‐unsaturated ketone moieties in the main chain derived from 2,6‐bis[4‐(3‐hydroxypropyloxy)‐3‐methoxybenzylidene]cyclohexanone

A series of photosensitive poly(ether–ester)s containing α,β‐unsaturated ketone moieties in the main chain were synthesized from 2,6‐bis[4‐(3‐hydroxypropyloxy)‐3‐methoxybenzylidene]cyclohexanone (BHPMBCH) and aliphatic and aromatic diacid chlorides. The diol precursor, BHPMBCH, was synthesized from 2,6‐bis(4‐hydroxy‐3‐methoxybenzylidene)cyclohexanone and 3‐bromo‐1‐propanol. The solubility of the polymers was tested in various solvents. The intrinsic viscosity of the synthesized polymers, determined by an Oswald viscometer, was found to be 0.06–0.80 g/dL. The molecular structures of the monomer and polymers were confirmed by Fourier transform infrared, ultraviolet–visible, ¹H‐NMR, and ¹³C‐NMR spectral analyses. The thermal properties were studied with thermogravimetric analysis and differential scanning calorimetry. The thermogravimetric analysis data revealed that the polymers were stable up to 220°C and started degrading thereafter. The thermal stability initially increased with increasing spacer length and then decreased due to negative effects of the spacer. The self‐extinguishing properties of the synthesized polymers were studied by the determination of the limiting oxygen index values with Van Krevelen's equation. In addition, the photocrosslinking properties of the polymer chain were studied with UV spectroscopy, and we observed that the rate of photocrosslinking increased significantly with increasing methylene carbon chain length of the acid spacer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of 3,4‐dihydroxyphenylacetic acid imprinted polymers

Eight molecularly imprinted polymers (MIP1–MIP8) were synthesized with different functional monomers and porogens using 3,4‐dihydroxyphenylacetic acid (DOPAC) as a template. Thermal, radical bulk polymerization was employed in the presence of ethylene glycol dimethacrylate as a cross‐linker. A computational analysis indicated that complexes with four molecules of 4‐vinylpyridine, 1‐vinylimidazole and acrylonitrile had high positive enthalpies of formation. The polymers synthesized with these monomers showed an imprinting factor below 1. Polymer MIP8 synthesized with allylamine as the functional monomer, with the highest energy of interaction with DOPAC, was characterized by the highest imprinting factor equal to 1.91. Examination of the binding ability of DOPAC and a group of structurally related compounds showed that the strong interactions between amine groups in the polymer and carboxylic groups in the analyte governed the recognition mechanism. The Langmuir adsorption model and the pseudo‐second‐order mechanism properly evaluated the MIP8 and non‐imprinted polymer 8 adsorption characteristics. Scatchard analysis revealed that MIP8 had two classes of heterogeneous binding sites with K_d(1) = 0.12 µmol L^?1 and K_d(2) = 1.46 µmol L^?1. Finally, the potential application of MIP8 for separation of DOPAC was demonstrated. Copyright © 2011 Society of Chemical Industry     

Stimuli‐sensitive nanostructured poly(sodium 4‐styrene sulfonate): Synthesis,characterization, and study of metal ion retention properties

Stimuli‐sensitive polymers are a type of smart polymers having the capability to change their configuration or properties under adequate stimuli as heat, pH, magnetic field, mechanical strength, among other. The aim of this work was to synthesize nanostructured polymers with antibacterial properties capable to change their retention properties of divalent metal ions by external stimuli (pH and ionic strength). For that, a polymerizable nanostructured crosslinker (PNC) based on silver nanoparticles (AgNPs) and acrylic acid was synthesized. Later, NPSS was synthesized by free‐radical polymerization, characterized by different analytical techniques and its retention properties of divalent ions (Cu²⁺, Fe²⁺, Mn²⁺, and Zn²⁺) were studied at different pHs and ionic strengths (5.0, 7.0, and 9.0; and 0.0, 0.5, and 1.5% NaCl, respectively). It was evidenced that AgNPs can be synthesized using acrylic acid as stabilizing agent, and later, be used for synthesis of NPSS by free‐radical polymerization. For NPSS, metal ion retention decreases as pH is increased; in addition, results suggest that the electrostatic interaction is not the only determining factor in the retention of ions. Other possible factors which would be affecting the retention are: water flow by swelling capacity and water flow by osmotic stress resulting of high salt concentration. NPSS showed antimicrobial activity against Escherichia coli and Staphylococcus aureus which was enhanced by incorporation of PNC based on AgNPs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46001.     

Atom transfer radical polymerization of methylmethacrylate and styrene initiated by 3,5‐bis(perfluorobenzyloxy)benzyl 2‐bromopropanoate

The synthesis of polymethylmethacrylate (pMMA) and polystyrene (pSt) were realized with newly synthesized initiator, 3,5‐bis(perfluorobenzyloxy)benzyl 2‐bromopropanoate (FBr) in the presence of copper bromide (CuBr) and N,N,N′,N″,N″‐pentamethyl‐diethylenetriamine (PMDETA) by using atom transfer radical polymerization (ATRP). The perfluorinated aromatic group containing initiator was prepared by esterification of the (3,5‐bis[(perfluorobenzyl)oxy]‐phenyl alcohol. Both initiator and polymers were characterized by ¹H‐NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. The ATRP was supported by an increase in the molecular weight of the forming polymers and also by their monomodal molecular weight distribution. Contact angle measurements of water and ethylene glycol on films of synthesized polymers indicated higher degree of hydrophobicity than that of pure pMMA and pure pSt. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Micellar polymerization,characterization, and viscoelasticity of combined thermally insensitive terpolyacrylamides

Polymer chains consisting of water‐soluble polyacrylamides and N‐isopropylacrylamide (NIPAM), hydrophobically modified with low amounts of N,N‐dialkylacrylamides (N,N‐dioctylacrylamide) have been prepared via free radical micellar polymerization, using a hydrophobic initiator derived from 4,4′‐azobis(4‐cyanopentanoic acid) containing a long linear chain of 16 (C16) carbon atoms. This procedure resulted in polyacrylamides containing hydrophobic groups along the chain as well as at the chain ends. These polymers are named “combined associative polymers” and include within their structure a water‐soluble monomer (acrylamide), a thermosensitive monomer (NIPAM) and a hydrophobic monomer. The polymers were characterized by different techniques, also studying the effect of adding a surfactant anion such as sodium dodecylsulfate. The viscoelastic properties as a function of temperature of these associative polymers were investigated using steady‐flow and oscillatory experiments considering the relaxation time (T_R) and the plateau modulus (G₀). The effect of concentration of acrylamide and NIPAM on the viscosity of the associative polymer solutions was investigated. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Synthetic,spectroscopic, magnetic,thermal, and antimicrobial approach towards new biocidal coordination polymers

O‐aminophenol was reacted with glutraldehyde to obtain Schiff base, which was then reacted with formaldehyde in slight acidic medium to generate phenolic groups. Now the substituted Schiff base was reacted with the transition metal acetates of Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) to get polymeric metal complexes. Their structures have been elucidated on the basis of elemental analyses, ¹H NMR spectra, ¹³C NMR spectra, magnetic measurements, thermogravimetric analyses, electronic spectra, and infrared spectra. The results are in accordance with an octahedral environment around the central metal ion. The polychelates of Mn(II), Co(II), Ni(II), and Cu(II) are paramagnetic while Zn(II) polychelate was found to be diamagnetic. The synthesized Schiff base acted as a uninegative bidentate ligand and bonding occurs through the hydroxyl oxygen and nitrogen atoms. The thermal behavior of these coordinating polymers was studied by TGA in nitrogen atmosphere up to the temperature range of 800°C. All the synthesized polychelates were also screened for their biocidal activity against Escherichia coli, Staphylococcus aureus, Bacillus subtilis (bacteria), Candida albicans, and Muller species (yeast) by using agar well diffusion method. All the metal polychelates show promising antimicrobial activities. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 124:3971–3979, 2012     

Synthesis and biological activity of medium range molecular weight polymers containing exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidocaproic acid

A new monomer, exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidocaproic acid (ETCA), was prepared by reaction of maleimidocaproic acid and furan. The homopolymer of ETCA and its copolymers with acrylic acid (AA) or with vinyl acetate (VAc) were obtained by photopolymerizations using 2,2‐dimethoxy‐2‐phenylacetophenone as an initiator at 25 °C. The synthesized ETCA and its polymers were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The apparent average molecular weights and polydispersity indices determined by gel permeation chromatography (GPC) were as follows: M_n = 9600 g mol^?1, M_w = 9800 g mol^?1, M_w/M_n = 1.1 for poly(ETCA); M_n = 14 300 g mol^?1, M_w = 16 200 g mol^?1, M_w/M_n = 1.2 for poly(ETCA‐co‐AA); M_n = 17 900 g mol^?1, M_w = 18 300 g mol^?1, M_w/M_n = 1.1 for poly(ETCA‐co‐VAc). The in vitro cytotoxicity of the synthesized compounds against mouse mammary carcinoma and human histiocytic lymphoma cancer cell lines decreased in the following order: 5‐fluorouracil (5‐FU) ≥ ETCA > polymers. The in vivo antitumour activity of the polymers against Balb/C mice bearing sarcoma 180 tumour cells was greater than that of 5‐FU at all doses tested. © 2001 Society of Chemical Industry     

Hydrophobically modified acrylamide‐based polybetaines. I. Synthesis,characterization, and stimuli‐responsive solution behavior

Acrylamide‐based, hydrophobically modified (HM) polybetaines containing N‐butylphenylacrylamide (BPAM) and varying amounts of the sulfobetaine monomer 3‐(2‐acrylamido‐2‐methylpropanedimethylammonio)‐1‐propanesulfonate (AMPDAPS) or the carboxybetaine monomer 4‐(2‐acrylamido‐2‐methylpropyldimethylammonio)butanoate (AMPDAB) were synthesized by micellar copolymerization. The corresponding control (co)polymers lacking BPAM or betaine comonomers were also prepared. The terpolymers were characterized by ¹³C‐NMR and UV spectroscopy, classical light scattering, and potentiometric titration. Low charge density polymers contained 3.9–8.6 mol % betaine, whereas the high charge density systems contained 17–25 mol % betaine; the HM polymers contained up to 1.0 mol % BPAM as the hydrophobe. The weight‐average molecular weights of the polymers ranged from 4.19 × 10⁵ to 1.29 × 10⁶ g/mol, and most HM polymers exhibited negative second virial coefficients. The pK_a of the carboxybetaine moieties was found to increase with increasing levels of hydrophobic and betaine comonomer incorporation. The response of aqueous polymer solutions to various external stimuli, including changes in solution pH and electrolyte concentration, was investigated using rheological analysis. The solution behavior of the polymers was characteristic of HM polyacrylamides and acrylamide‐based polyzwitterions. The high charge density HM polycarboxybetaine exhibited unusual solution behavior that can be explained in terms of electrostatic, hydrophobic, and hydrogen‐bonding associations. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 647–657, 2004     

Synthesis and polymerization of the bromoacrylated plant oil triglycerides to rigid,flame‐retardant polymers

Simultaneous addition of bromine and acrylate to the double bonds of fatty acids in triglycerides was achieved. In the first part of the study, methyl oleate was bromoacrylated in the presence of acrylic acid and N‐bromosuccinimide as a model compound for the application of the reaction to the triglycerides. Next, soybean oil and high oleic sunflower oil were bromoacrylated by using the same procedure. The products were characterized by GC, IR, ¹H‐NMR, ¹³C‐NMR, and mass spectrometry. The bromoacrylation yields for soybean oil and sunflower oil were 75 and 55%, respectively. A rigid thermoset polymer was prepared from the radical copolymerization of bromoacrylated soybean oil with styrene. The bromoacrylated sunflower oil–styrene copolymer showed semirigid properties. The crosslinked network structure of the copolymers was examined by their swelling behavior in different solvents. Glass‐transition temperatures were also determined and soybean oil–based polymer and sunflower oil–based polymer showed a glass transition at 55–65 and 20–30°C, respectively. The storage moduli of the soybean‐based and sunflower‐based polymers at room temperature were approximately 1.0 × 10¹⁰ and 1.1 × 10⁸ Pa, respectively. Photopolymerization was also carried out by using 2,2‐dimethoxy‐2‐phenyl‐acetophenone as initiator. The response of the cured polymers to the thermal energy produced by a small flame was also tested by the ignition respond index method according to ASTM D 3713‐78 and was found to be 5 B at 2.00 mm. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91:2700–2710, 2004