Grafting copolymerization of styrene and maleic anhydride binary monomer systems induced by UV irradiation

Photografting copolymerization of maleic anhydride (MAH) and styrene (St) onto LDPE film was investigated by using a one-step method, and further thermally induced grafting copolymerization of them was carried out by using a two-step method. Regarding the photografting copolymerization of MAH/St binary monomer system, both conversion percentage (CP) and grafting efficiency (GE) increased with raising the content of MAH in the monomer feed. In addition, the content of MAH in the grafted copolymers also increased with increasing the fraction of MAH in the monomer feed. The formation of LDPE-g-P(MAH-co-St) grafted film was identified by FTIR and ESCA spectroscopy. In the case of grafting copolymerization of MAH/St by the two-step method, grafting copolymerization proceeded slowly compared with the non-grafting copolymerization. The apparent activation energy (E_a) for the non-grafting copolymerization in the solution and the grafting copolymerization on LDPE film was 24 and 82 kJ/mol, respectively, which were noticeably lower than those of MAH/vinyl acetate (MAH/VAC) binary monomer system under the similar grafting conditions. These data of E_a explained why the grafting copolymerization of styrene/MAH took place faster than that of MAH/VAC binary monomer system. The composition of the grafted copolymer chains was largely affected by the composition of the monomer feeds; however, the composition of the non-grafted copolymers nearly remained at 1/1 even in systems with largely different MAH/styrene ratios in monomer feeds. It is indicated that the non-grafting copolymerization proceeded predominantly following alternating copolymerization, but the grafting copolymerization performed random copolymerization.     

Copolymerization of N-vinylcaprolactam with N-vinyl(benz)imidazoles and the properties of aqueous solutions of the copolymers

The free-radical solution copolymerization of N-vinylcaprolactam with 1-vinylimidazole, 1-vinyl-2-methylimidazole, 1-vinyl-2-methyl-3-propylimidazolium iodide, or 1-vinyl-2-methylbenzimidazole was investigated and the monomer reactivity ratios in the copolymerization were calculated. It was shown that 1-vinylimidazole exhibits a relatively higher activity in the copolymerization as compared to the monomers that bear substituents on the ring. It was established that, except for the copolymers of 1-vinyl-2-methylbenzimidazole, water-soluble products could be obtained. Aqueous solutions of N-vinylcaprolactam copolymers with N-vinyl(methyl)imidazoles were found to have a higher phase separation temperature relative to poly(N-vinylcaprolactam) solutions. The thermal stability of the aqueous solutions increases with a rise in the amount of hydrophilic 1-vinyl-and 1-vinyl-2-methylimidazole units in macromolecular chains and in the presence of NaCNS or KBr. The effect of salts on the thermal stability of aqueous copolymer solutions has the same character as in the case of the N-vinylcaprolactam homopolymer.     

Immobilization and Release Studies of Triazole Derivatives from Grafted Copolymer Based on Gellan-Carrying Betaine Units

New polymer-bioactive compound systems were obtained by immobilization of triazole derivatives onto grafted copolymers and grafted copolymers carrying betaine units based on gellan and N-vinylimidazole. For preparation of bioactive compound, two new types of heterocyclic thio-derivatives with different substituents were combined in a single molecule to increase the selectivity of the biological action. The 5-aryl-amino-1,3,4 thiadiazole and 5-mercapto-1,2,4-triazole derivatives, each containing 2-mercapto-benzoxazole nucleus, were prepared by an intramolecular cyclization of thiosemicarbazides-1,4 disubstituted in acidic and basic medium. The structures of the new bioactive compounds were confirmed by elemental and spectral analysis (FT-IR and ¹H-NMR). The antimicrobial activity of 1,3,4 thiadiazoles and 1,2,4 triazoles was tested on gram-positive and gram-negative bacteria. The triazole compound was chosen to be immobilized onto polymeric particles by adsorption. The Langmuir, Freundlich, and Dubinin–Radushkevich adsorption isotherm were used to describe the adsorption equilibrium. Also, the pseudo-first and pseudo-second models were used to elucidate the adsorption mechanism of triazole onto grafted copolymer based on N-vinylimidazole and gellan (PG copolymer) and grafted copolymers carrying betaine units (PGB1 copolymer). In vitro release studies have shown that the release mechanism of triazole from PG and PGB1 copolymers is characteristic of an anomalous transport mechanism.     

Preparation and characterization of graft copolymerization of ethyl acrylate onto hydroxypropyl methylcellulose in aqueous medium

Graft copolymerization of ethyl acrylate (EA) onto water-soluble hydroxypropyl methylcellulose (HPMC) was investigated with potassium persulfate (KPS) as initiator in an aqueous medium. The effects of monomer concentration, initiator concentration, matrix concentration, reaction temperature, reaction time and pre-interacting time in terms of percentage of grafting (G) and grafting efficiency (G _E) are discussed. The graft copolymers were characterized by Fourier transform infrared spectra (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction analysis (XRD) and differential scanning calorimetry (DSC). In addition, equilibrium humidity adsorption behavior of the pure grafted copolymers was also studied.     

PP films grafted with N-isopropylacrylamide and N-(3-aminopropyl) methacrylamide by γ radiation: synthesis and characterization

Simultaneous grafting of N-isopropylacrylamide (NIPAAm) and N-(3-aminopropyl) methacrylamide hydrochloride (APMA) on polypropylene (PP) was investigated for obtaining interfaces that are stimuli-responsive under physiological conditions. A pre-irradiation method was optimized tuning the γ-irradiation dose, reaction time, temperature, and monomers concentrations. FT-IR ATR and XPS analysis of the grafted copolymers evidenced a greater content in NIPAAm than in APMA; the APMA/NIPAAm ratio increasing with the concentration of APMA in the reaction medium and when the grafting was carried out in 1 M NaNO₃. The grafted films were characterized regarding their thermal properties (DSC and TGA) swelling behavior and contact angle. Immersion of the pre-irradiated films in 1 M NIPAAm/0.5 M APMA aqueous solution rendered PP-g-(1NIPAAm-r-0.5APMA) which exhibited rapid and reversible transitions showing a LCST around the physiological temperature. By contrast, a greater content in APMA enhanced the hydrophilicity and prevented the shrinking of PP-g-(1NIPAAm-r-1APMA).     

Esterolytic activity of imidazole-containing polymers. Synthesis and characterization of copoly[1-alkyl-4- or 5-vinylimidazole/4(5)-vinylimidazole] and its catalytic activity in the hydrolysis of p-nitrophenyl acetate

The water-soluble monomers, 1-methyl-4-vinylimidazole, 1-methyl-5-vinylimidazole, 1-ethyl-5-vinylimidazole, and 1-propyl-5-vinylimidazole have been synthesized, polymerized, and copolymerized with 4(5)-vinylimidazole. The copolymers were characterized by ¹⁴C-labeling, NMR, pK_a determination and viscosity measurements. The monomer reactivity ratios determined by ¹⁴C counting are r₁ = 1.04; r₂ = 0.94 [M₁ = 4(5)-vinylimidazole, M₂ = 1-methyl-4-vinylimidazole] and r₁ = 1.01; r₂ = 0.86 [M₁ = 4(5)-vinylimidazole, M₂ = 1-methyl-5-vinylimidazole]. The esterolytic activity of the copolymers for the hydrolysis of p-nitrophenyl acetate (PNPA) at pH 7–8 in 28.5% ethanol–water was higher than that of the mixtures of homopolymers. At pH 5–6 the esterolytic activities of the copolymers and the mixtures were similar. The most efficient esterolytic activity for PNPA hydrolysis at pH 7.11 in 28.5% ethanol–water occurred for copolymers containing 75 mole % 4(5)-vinylimidazole and for copolymers containing 1-methyl-4-vinylimidazole rather than 1-methyl-5-vinylimidazole.     

Copolymerization of N,N-diallyl-N,N-dimethylammonium chloride with ethylene glycol vinyl ether in aqueous medium

The radical copolymerization of N,N-diallyl-N,N-dimethylammonium chloride (AMAC) (M₁) with ethylene glycol vinyl ether (M₂) in an aqueous medium proceeds at a high rate to afford random copolymers. The reactivity ratios equal to r ₁ = 2.18 and r ₂ = 0.01 indicate that AMAC is a more active comonomer. The overall reaction order in comonomers is 2.4, and the effective activation energy is 97.4 ± 2 kJ/mol. The monomer M₁ enters into copolymerization by both of the double bonds with the formation of pyrrolidinium structures in the chain through the cyclization stage.     

Alternating copolymerization of maleic anhydride with allyl chloroacetate

Some regularities of radical alternating copolymerization of maleic anhydride with allyl chloroacetate are studied. The formation of donor–acceptor complexes between comonomers with complexing constant K_c = 0.052 L/mol is found using ¹H NMR spectroscopy. The kinetic parameters for this copolymerization reaction are found and the quantitative contribution of monomer complexes to chain-growth radical reactions is calculated. It is shown that either a “free-monomer” mechanism (dilute solutions) or a “mixed” mechanism (concentrated solutions) prevails for chain growth during radical copolymerization depending on total monomer concentration. It is found that inhibition of degradative chain transfer in the course of the reaction studied takes place owing to the presence of α-chlorine atom in the allyl chloracetate molecule and formation of charge transfer complex.     

Graft copolymerization of methyl methacrylate onto curdlan

Graft copolymerization of methyl methacrylate onto curdlan was first investigated. In the graft copolymerization initiated by ammonium persulfate (APS) in DMSO under a homogeneous condition, the resulting graft copolymers had low molecular weights and low grafting percentages. However, the initiation by APS in water gave graft copolymers having relatively higher molecular weight ( ) and higher grafting percentage (548%) than those copolymers obtained by the homogeneous condition. When the graft copolymerization was carried out by cerium (IV) ammonium nitrate-HNO₃ initiation, the graft copolymer had the highest grafting percentage of 1620% without degradation of the curdlan backbone. The resulting graft copolymers were soluble in DMSO. The graft copolymers obtained by the cerium salt had narrow molecular weight distributions () compared with those by the APS catalyst in DMSO or water. The graft copolymers decomposed with sulfuric acid to isolate PMMAs, which molecular weights were larger than that of the corresponding homo-PMMAs. The structure of the grafted copolymers was characterized by IR, ¹³C NMR, DSC, and SEM. It was found that the graft copolymers exhibited the glass transition temperature (T_g), though curdlan had no T_g. As the grafting percentage increased, the T_g increased to reach 270°C, which was higher than the decomposition temperature of curdlan. The surface image of the grafted copolymers observed by SEM, showed smoothless compared with that of curdlan. It was also revealed that the graft copolymers having the grafting percentage of 1620% swelled in common organic solvents up to 4.5 times of the weight of the dry graft copolymer to form gels. © 1996 John Wiley & Sons, Inc.     

Single-site binding of pyrene to poly(ester-imide)s incorporating long spacer-units: prediction of NMR resonance-patterns from a fractal model

Co-polycondensation of the diimide-based diols N,N′-bis(2-hydroxyethyl)hexafluoroisopropylidene-diphthalimide, (HFDI), and N,N′-bis(2-hydroxy-ethyl)naphthalene-1,4,5,8-tetracarboxylic-diimide, (NDI), with aliphatic diacyl chlorides ClOC(CH₂)_xCOCl (x = 5 to 8) affords linear copoly(ester-imide)s. Such copolymers interact with pyrene via supramolecular binding of the polycyclic aromatic at NDI residues. This interaction results in upfield complexation shifts and sequence-related splittings of the NDI ¹H NMR resonances, but gives a very different final resonance-pattern from the copolymer where x = 2. Computational modelling of the polymer with x = 5 suggests that each pyrene molecule binds to just a single NDI residue rather than by intercalation between a pair of NDI''s at a tight chain-fold, as was found for x = 2. The new single-site binding model enables the pattern of ¹H NMR resonances for copolymers with longer spacers (x = 5 to 8) to be reproduced and assigned by simulation from sequence-specific shielding factors based on a type of fractal known as the last-fraction Cantor set. As this type of fractal also enables an understanding of pairwise binding systems, it evidently provides a general numerical framework for supramolecular sequence-analysis in binary copolymers.

Nine ¹H NMR resonances assignable to specific copoly(ester-imide) sequences identified from a fractal model result from 1 : 1 supramolecular binding of pyrene to NDI residues.     

ATRP synthesis and association properties of temperature responsive dextran copolymers grafted with poly(N-isopropylacrylamide)

Temperature responsive copolymers of dextran grafted with poly(N-isopropylacrylamide) (Dex-g-PNIPAAM) were prepared by atom transfer radical polymerization (ATRP) in homogeneous mild conditions without using protecting group chemistry. Dextran macroinitiator was synthesized by reaction of dextran with 2-chloropropionyl chloride at room temperature in DMF containing 2% LiCl. ATRP was carried out in DMF:water 50:50 (v/v) mixtures at room temperature with CuBr/Tris(2-dimethylaminoethyl)amine (Me₆TREN) as catalyst. Several grafted copolymers with well defined number and length of low polydispersity grafted chains were prepared. Temperature induced association properties in aqueous solution were studied as a function of temperature and polymer concentration by dynamic light scattering, fluorescence spectroscopy and atomic force microscopy (AFM). LCST, ranging from 35 to 41 °C, was significantly affected by number and length of grafted chains. The fine tuning of LCST around body temperature is an important characteristic not obtainable by conventional radical grafting of PNIPAAM. Well defined spherical nanoparticles were formed above the LCST of PNIPAAM. Hydrodynamic diameter was in the range 73-98 nm.     

RADICAL GRAFTING REACTIONS ONTO STARCH AND OTHER WATER-SOLUBLE COPOLYMERS IN ISOLATED GEL DROPLETS

A novel radical grafting copolymerization process has been designed for water-soluble polymers which avoids the problems of conducting grafting reactions in highly viscous polymerization media. A variety of water-soluble graft copolymers having starch or dextran as the backbone chain with grafted side chains of polyacrylamide (—AM—), poly (acrylic acid ) (—AA—), poly (acrylamide-co-acrylic acid) (—AM—NH_4AA—) or poly ( acrylamide-co-2-acryiamido-2-methyl-l-propanesulphinic acid) (—AM—AMPS—) have been synthesized in gel droplets using aceric sulphate redox initiator, and their properties compared. The reaction conditions were optimized taking into account reaction kinetic data and the observed properties of the products produced under different reaction conditions. The effects of the ratios of [backbone]/[graft monomer], [ AM]/[ AA]/[AMPS] , [Ce~(4+)]/[ S_2O_8=] and pH value on the reaction rate , conversion, grafting degree, grafted chain length and the product molecular weight have been investigated.     

Microwave-Assisted Synthesis and Characterization of Poly(2-(dimethylamino)ethyl methacrylate) Grafted Gellan Gum

Poly(2-(dimethylamino)ethylmethacrylate) was grafted on gellan gum (GG) in aqueous medium under microwave irradiation using ammonium persulfate and N,N,N′N′-tetramethylethylenediamine as the initiation system. Grafted copolymers were characterized by FT-IR, TGA, and SEM techniques. The influence of microwave power, exposure time, and composition of the reaction mixture on extent of grafting was studied. Conditions for obtaining the highest degree of grafting were optimized. The rate of grafting was determined from weight measurements. The overall activation energy for grafting is found to be 31.2 kJ/mol, indicating the occurrence of the grafting process with absorption of low thermal energy.     

NickelII-catalyzed asymmetric photoenolization/Mannich reaction of (2-alkylphenyl) ketones

A diastereo- and enantioselective photoenolization/Mannich (PEM) reaction of ortho-alkyl aromatic ketones with benzosulfonimides was established by utilizing a chiral N,N′-dioxide/Ni(OTf)₂ complex as the Lewis acid catalyst. It afforded a series of benzosulfonamides and the corresponding ring-closure products, and a reversal of diastereoselectivity was observed through epimerization of the benzosulfonamide products under continuous irradiation. On the basis of the control experiments, the role of the additive LiNTf₂ in achieving high stereoselectivity was elucidated. This PEM reaction was proposed to undergo a direct nucleophilic addition mechanism rather than a hetero-Diels–Alder/ring-opening sequence. A possible transition state model with a photoenolization process was proposed to explain the origin of the high level of stereoinduction.

A diastereo- and enantioselective photoenolization/Mannich (PEM) reaction of (2-alkylphenyl) ketones with benzosulfonimides is realized by a chiral N,N′-dioxide/Ni^II complex catalyst.     

Grafting of 1-Cyanoethanoyl-4-acryloylthiosemicabazide onto Chitosan and Biocidal Activity of the Graft Copolymers

Chitosan was grafted with a novel monomer 1-Cyanoethanoyl-4-acryloylthiosemicabazide (CEATS). The graft copolymerization was conducted using potassium persulfate (K₂S₂O₈) and sodium bisulfite (NaHSO₃) as redox initiators. The grafted samples were characterized by FTIR spectroscopy, scanning electron microscopy, X-ray diffraction, and thermogravimetric analysis. The data may indicate that grafting has occurred at the surface of chitosan. The grafted samples showed high water swelling. The antifungal behavior of chitosan and its graft copolymers was investigated in vitro and it has been found that grafting with CEATS noticeably enhances the antifungal activity.     

Esterolytic activity of imidazole-containing polymers. Hydrophobic influences in copoly[1-alkyl-4- or 5-vinylimidazole/4(5)-vinylimidazole]-catalyzed hydrolysis of 3-nitro-4-acyloxybenzoic acids

Water-soluble copolymers containing imidazole and N-alkylated imidazole pendant groups have been synthesized in order to investigate the hydrophobic interactions between polymeric catalysts and long alkyl chain ester substrates. Copoly[1-methyl-4-vinyl-imidazole/4(5)-vinylimidazole],copoly[1-methyl-5-vinylimidazole/4(5)-vinylimidazole], copoly[1-ethyl-5-vinylimidazole/4-(5)-vinyl-imidazole] and copoly[1-propyl-5-vinylimidazole/4(5)-vinylimidazole] were synthesized and their catalytic activity toward 3-nitro-4-acyloxybenzoic acid substrates (S_n^?) was determined in 28.5% ethanol–water and in water and compared with that of the mixtures of homopolymers. Hydrophobic interactions were important for rate enhancement of the hydrolysis of long-chain ester substrates compared to that of short-chain ester substrates. The copolymers catalyzed the hydrolysis of 3-nitro-4-dodecanoyloxy-benzoic acid (S₁₂^?) about two times faster than the mixtures at pH 7.11 in 28.5% ethanol–water. The hydrolysis of S₁₂^? by the copolymers was about five times faster in water than 28.5% ethanol–water.     

Reactions on polymers with amine groups. V. Addition of pyridine and imidazole groups with acetylenecarboxylic acids

Unsaturated macromolecular carboxybetaines were obtained by reaction of poly(4-vinylpyridine) and poly(N-vinylimidazole) with propiolic acid. A kinetic model was presented for 4-methylpyridine. It consists of three coupled reactions: neutralization, addition which involves two molecules of acid and leads to a cation–anion pair structure, where the cation results from the addition of the amine nitrogen to the triple bond of acid, and an equilibrium reaction between the ion-pair structure and the betaine structure. The addition rate was found to be higher for poly(4-vinylpyridine) than for poly(N-vinylimidazole); it was also higher in water than in a water–methanol mixture. The reaction with acetylenedicarboxylic acid was carried out on poly(N-vinylimidazole), but the transformed units showed the structure that results from propiolic acid. The betaine products from 4-methylpyridine did not polymerize by radical initiation. The polymeric products show characteristics of photocrosslinking polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1615–1623, 1998     

Tuning the reactivity of mononuclear nonheme manganese(iv)-oxo complexes by triflic acid

Triflic acid (HOTf)-bound nonheme Mn(iv)-oxo complexes, [(L)Mn^IV(O)]²⁺–(HOTf)₂ (L = N4Py and Bn-TPEN; N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine and Bn-TPEN = N-benzyl-N,N′,N′-tris(2-pyridylmethyl)ethane-1,2-diamine), were synthesized by adding HOTf to the solutions of the [(L)Mn^IV(O)]²⁺ complexes and were characterized by various spectroscopies. The one-electron reduction potentials of the Mn^IV(O) complexes exhibited a significant positive shift upon binding of HOTf. The driving force dependences of electron transfer (ET) from electron donors to the Mn^IV(O) and Mn^IV(O)–(HOTf)₂ complexes were examined and evaluated in light of the Marcus theory of ET to determine the reorganization energies of ET. The smaller reorganization energies and much more positive reduction potentials of the [(L)Mn^IV(O)]²⁺–(HOTf)₂ complexes resulted in greatly enhanced oxidation capacity towards one-electron reductants and para-X-substituted-thioanisoles. The reactivities of the Mn(iv)-oxo complexes were markedly enhanced by binding of HOTf, such as a 6.4 × 10⁵-fold increase in the oxygen atom transfer (OAT) reaction (i.e., sulfoxidation). Such a remarkable acceleration in the OAT reaction results from the enhancement of ET from para-X-substituted-thioanisoles to the Mn^IV(O) complexes as revealed by the unified ET driving force dependence of the rate constants of OAT and ET reactions of [(L)Mn^IV(O)]²⁺–(HOTf)₂. In contrast, deceleration was observed in the rate of H-atom transfer (HAT) reaction of [(L)Mn^IV(O)]²⁺–(HOTf)₂ complexes with 1,4-cyclohexadiene as compared with those of the [(L)Mn^IV(O)]²⁺ complexes. Thus, the binding of two HOTf molecules to the Mn^IV(O) moiety resulted in remarkable acceleration of the ET rate when the ET is thermodynamically feasible. When the ET reaction is highly endergonic, the rate of the HAT reaction is decelerated due to the steric effect of the counter anion of HOTf.     

Deep in blue with green chemistry: influence of solvent and chain length on the behaviour of N- and N,N′- alkyl indigo derivatives

Using green chemistry procedures the synthesis of N-alkyl (NC_nInd) and N,N′-dialkyl (N,N′C_nInd) indigo derivatives, with n = 1–3, 6, 8, 12 and 18, was undertaken, leading to compounds with blueish to greenish colors in solution. The effect of the alkyl chain length on the spectral (including color) and photophysical properties of the compounds was explored. This was done with solvents of different viscosities and polarities (dielectric constants). From time-resolved fluorescence and femtosecond-transient absorption (fs-TA) for the NC_nInd derivatives with n = 1 and 2, the decays are, in methylcyclohexane (MCH) and n-dodecane, single-exponential, while in 2-methyltetrahydrofuran (2MeTHF) they are bi-exponential. The excited state proton transfer (ESPT) is ultrafast (<1 ps) for NC_1,2Ind in MCH and n-dodecane, supported by time-dependent density functional theory (TDDFT) calculations, thus showing that both the chain length and solvent influence the ESPT process. For N,N′C_nInd, from time-resolved experiments, and with the exception of the shortest member of the series, N,N′C₁Ind, two conformers are found to be present in the excited state.

Using green chemistry procedures the synthesis of N- and N,N′-alkyl indigo derivatives was undertaken and the effect of the alkyl chain length on the spectral (including color) and photophysical properties of the compounds explored.     

Synthesis of ion exchange membranes from ozonized high density polyethylene

The synthesis and the characterization of graft copolymers prepared from ozonized high density polyethylene (HDPE) are described. The powder of HDPE was treated with ozone in well defined conditions and then copolymerized with monomers, such as, acrylic acid (AA), N,N-dimethylamino-2 ethylmethacrylate (MADAME) and vinyl phosphonic acid (VPA). Cationic exchange membranes were prepared from the grafted copolymers of AA and VPA and anionic exchange membrane from the grafted copolymer of MADAME. The obtained copolymers were characterized by the grafting rate, FTIR spectroscopy, scaning electronic microscopy, thickness, exchange capacity and electrical resistance.