New crosslinked N‐vinylpyrrolidone copolymers: Synthesis and sorptive properties

The crosslinked copolymers of N‐vinylpyrrolidone with 1,4‐(N,N′‐bismaleimido)benzol and with trimethoxyvinylsilane were synthesized by free radical copolymerization. The copolymers were characterized by FTIR spectroscopy and thermal analysis. The values of specific surface area and porosity of the copolymers were determined with use of low‐temperature adsorption. Sorption capacity of the copolymers toward Re (VII), Mo (VI), and W(VI) ions was investigated and was found to depend strongly on the pH. A possibility to separate Re(VII) and Mo(VI) ions with use of the copolymers under investigation in their combined presence in neutral and alkaline media was shown. Moreover, in the conjoined presence of Mo(VI) and W(VI) ions at pH 5–14, tungsten(VI) can be separated from molybdenum(VI) with the copolymer of N‐vinylpyrrolidone with trimethoxyvinylsilane. POLYM. ENG. SCI., 56:1303–1312, 2016. © 2016 Society of Plastics Engineers     

Copolymerization of N‐(4‐carboxyphenyl) itaconimide or N‐(4‐carboxyphenyl) itaconamic acid with methyl methacrylate

This paper describes the synthesis and characterization of N‐(4‐carboxyphenyl) itaconamic acid (CPA) and N‐(4‐carboxyphenyl) itaconimide (CPI) obtained by reacting itaconic anhydride with p‐aminobenzoic acid. Structural and thermal characterization of CPA and CPI was done using ¹H‐NMR, FTIR, and differential scanning calorimetry (DSC). Copolymerization of CPA or CPI with methyl methacrylate (MMA) in solution was carried out at 60 °C using azobisisobutyronitrile as an initiator and dimethyl acetamide or THF as solvent. Feed compositions having varying mole fractions of CPA or CPI ranging from 0.05–0.20 or 0.1–0.5 were taken to prepare copolymers. Copolymerizations were terminated at low percentage conversion. Structural characterization of copolymers was done by ¹H‐NMR and elemental analysis. Copolymer composition was determined using percentage nitrogen content. The reactivity ratios were r₁ (MMA) = 0.68 ± 0.06 and r₂ (CPI) = 0.46 ± 0.06. The intrinsic viscosity [η] was determined using an Ubbelohde suspension level viscometer. [η] decreased with increasing mole fraction of N‐(p‐carboxyphenyl) itaconimide or N‐(p‐carboxyphenyl) itaconamic acid in copolymers. Glass transition temperature and thermal stability of the copolymers were determined using DSC and thermogravimetric analysis, respectively. The glass transition temperature (T_g) as determined from DSC scans increased with increasing amounts of CPA or CPI in copolymers. A significant improvement in the char yield was observed upon copolymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1909–1915, 2005     

Synthesis and comparative study of thermal stabilities of the imidization of some maleic anhydride copolymers

In the present study, first, maleic anhydride‐styrene (MA‐St), maleic anhydride‐allyl phenyl ether (MA‐APhE), maleic anhydride‐heptene‐1(MA‐Hp), and maleic anhydride‐allyl propionate (MA‐AP) copolymers have been synthesized in different solvents in the presence of azobisisobutyronitrile (AIBN) at 70°C. Then, these four copolymers have been reacted with aniline at 60°C in N,N‐dimethyl formamide (DMF), and maleamidic acid derivatives of these copolymers have been synthesized. Next, they have been obtained from their maleimide derivatives by heating under vacuum at 150°C. All these polymers have been characterized by Fourier Transform infrared spectroscopy (FTIR) and investigated their thermal properties by using differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) methods. The analyses results showed that thermal properties of maleimide derivatives of maleic anhydride copolymers changed as depend on the neighbor monomers of maleic anhydride. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2250–2254, 2006     

pH and thermo‐responsive poly(N‐isopropylacrylamide) copolymer grafted to poly(ethylene glycol)

pH and thermo‐responsive graft copolymers are reported where thermo‐responsive poly(N‐isopropylacrylamide) [poly(NIPAAm), poly A ], poly(N‐isopropylacrylamide‐co‐2‐(diethylamino) ethyl methacrylate) [poly(NIPAAm‐co‐DEA), poly B ], and poly(N‐isopropylacrylamide‐co‐methacrylic acid) [poly(NIPAAm‐co‐MAA), poly C ] have been installed to benzaldehyde grafted polyethylene glycol (PEG) back bone following introducing a pH responsive benzoic‐imine bond. All the prepared graft copolymers for PEG‐g‐poly(NIPAAm) [ P‐N1 ], PEG‐g‐poly(NIPAAm‐co‐DEA) [ P‐N2 ], and PEG‐g‐poly(NIPAAm‐co‐MAA) [ P‐N3 ] were characterized by ¹H‐NMR to assure the successful synthesis of the expected polymers. Molecular weight of all synthesized polymers was evaluated following gel permeation chromatography. The lower critical solution temperature of graft copolymers varied significantly when grafted to benzaldehyde containing PEG and after further functionalization of copolymer based poly(NIPAAm). The contact angle experiment showed the changes in hydrophilic/hydrophobic behavior when the polymers were exposed to different pH and temperature. Particle size measurement investigation by dynamic light scattering was performed to rectify thermo and pH responsiveness of all prepared polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Hydrogen bonding interactions of styrene‐maleimide copolymers with diaminotriazine derivatives

Poly(styrene‐co‐N‐maleimide) precursor and poly(styrene‐co‐N‐maleimide)‐block‐polystyrene have been synthesized by quasiliving radical polymerization. Low molecular weight compounds with the sites specific for the complementary binding to the maleimide moieties via triple hydrogen bonds, 2,4‐diamino‐6‐n‐alkoxy(C‐4, C‐8, and C‐12)‐s‐triazines, have been prepared. Hydrogen bonding between diaminotriazine and maleimide units in the copolymer–diaminotriazine mixtures has been investigated by FTIR. Microphase separated structure in the block copolymer‐diaminotriazine mixtures has been confirmed by DSC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2338–2346, 2006     

Synthesis and characterization of novel organotin monomers and copolymers and their antibacterial activity

Two novel organotin monomers, (N‐tri‐n‐butyltin) maleimide and m‐acryloylamino‐(tri‐n‐butyltin benzoate), were synthesized. Copolymerization of these two monomers with styrene was carried out in the bulk at 65°C using asobisisobutyronitrile as the free radical initiator. The monomers and copolymers were characterized by elemental analysis; the molecular weights of the copolymers were determined by GPC, solubility, IR, and ¹H‐NMR spectral studies. The antibacterial activities of the synthesized organotin monomers and copolymers toward various types of bacteria were also reported. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 740–745, 2000     

Adsorption behavior and separation of vanadium(V), molybdenum(VI), and rhenium(VII) ions on crosslinked polymers containing acrylic acid derivative moieties

The radical polymerization of [2‐(acryloyloxy)ethyl]trimethylammonium methyl sulfate and [3‐(methacryloylamino)propyl]trimethylammonium chloride by using ammonium peroxydisulfate as initiator and N,N′‐methylene‐bis‐acrylamide as crosslinker agent at 70°C for 17 h was carried out. The crosslinker agent in the feed ranged between 2 and 6 mol %. The resins were completely insoluble in water and characterized by elemental analysis and FTIR spectroscopy. The metal ion binding capacity of these resins with V(V), Mo(VI), and Re(VII) were investigated using the batch equilibrium type. The pH, but not the crosslinking percentage in the feed, influenced the retention capacity of the resin, particularly for V(V) and Re(VII). Thus, at pH 1 only < 15% of V(V) was retained, but at pH 3 higher than 97% of V(V) was adsorbed. The resin–ion equilibrium was achieved between 15 min and 2 h depending on the resin, ion, and crosslinking degree. According to the pH, it is possible separate Re(VII) and Mo(VI) from V(V) at pH 1.0. To reuse the resins, the ions were stripped by using HCl, H₂SO₄, and Na₂CO₃ at different concentrations. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 369–376, 1999     

Copolymerization of N‐substituted maleimide with alkyl acrylate and its industrial applications

A series of new copolymers with desired thermal stability and mechanical properties for applications in leather industry were synthesized from various substituted maleimides and alkyl acrylates. Polymerization was carried out by a free‐radical polymerization using benzoyl peroxide (BPO) as initiator. The monomers and polymers synthesized were characterized by elemental analysis, IR, and nuclear magnetic resonance (NMR). Interestingly, these polymers were soluble in common organic solvents. Copolymer composition and reactivity ratios were determined by ¹H‐NMR spectra. The molecular weights of the polymers were determined by gel permeation chromatography. The homo‐ and copolymer of maleimide showed single‐stage decomposition (ranging from 300–580°C). The initial decomposition temperatures of poly[N‐(phenyl)maleimide] [poly(PM)], poly[N‐4‐(methylphenyl)maleimide] [poly(MPM)] and poly[N‐3‐(chlorophenyl)maleimide] [poly(CPM)] were higher compared to those of the copolymers. Heat‐resistant adhesives such as blends of epoxy resin with phenyl‐substituted maleimide‐co‐glycidyl methacrylate copolymers with improved adhesion property were developed. Different adhesive formulations of these copolymaleimides were prepared by curing with diethanolamine at two different temperatures (30°C and 60°C). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1870–1879, 2001     

Interpolymer complexes of novel linear and crosslinked acrylic acid–Schiff base copolymers

Novel linear and crosslinked copolymers of acrylic acid and Schiff base, containing the amine groups in the main chain and the carboxylic groups in the side chain, have been synthesized by the Michael addition reaction followed by radical copolymerization. The copolymers that exhibited poly(ampholyte–electrolyte) behaviour were used to prepare complexes by reaction with anionic (poly(acrylic acid), poly(styrene sodium sulfonate)), cationic (polyethyleneimine, poly(hexamethylene guanidine)) and non‐ionic (poly(N‐vinylpyrrolidone), poly(ethylene glycol), poly(vinyl alcohol)) polymers. The influence of external factors, such as solvent quality, temperature, pH and ionic strength, on phase (coil–globule) and volume (swelling–collapse) transitions has been studied. © 2003 Society of Chemical Industry     

Synthesis,characterization, and blood compatibility of copolymers of polyamidoamines and n‐vinylpyrrolidone

Two new polyamidoamines derived from piperazine (Pip)/cyclohexylamine (CHA) and N,N′‐methylene bisacrylamide (MBA) were synthesized and subsequently copolymerized with N‐vinylpyrrolidone (NVP) under suitable reaction conditions to yield the respective copolymers (Pip–MBA–NVP and CHA–MBA–NVP). The synthesized materials were characterized by spectroscopic techniques. The material surface characteristics were checked by contact angle measurement, and the data established the relative hydrophilic characteristics of the synthesized copolymers with respect to the control poly(N‐vinylpyrrolidone). A thrombus‐formation study indicated less (<1.2 mg) clot formation on the heparinized material surfaces within a 30‐min contact time with the acid citrate dextrose human blood. The percentage of hemolysis of the blood by the materials was also less than 5%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4068–4074, 2003     

Effect of the nature and degree of crosslinking on Rose Bengal binding by DVB‐, NNMBA‐, HDODA‐ and TTEGDA‐crosslinked poly(N‐vinylpyrrolidone)s

Poly(N‐vinylpyrrolidone)s with 2–20 mol% DVB, NNMBA, HDODA and TTEGDA crosslinkings were prepared by suspension polymerisation. The binding of Rose Bengal by these poly(N‐vinylpyrrolidone)s was followed by a batch equilibration method. In order to optimise the conditions of dye binding, the effect of the concentration of Rose Bengal solutions, temperature and pH were followed. Kinetic studies showed that the binding of Rose Bengal by poly(N‐vinylpyrrolidone)s is a phase boundary process followed by a three‐dimensional diffusion. Copyright © 2003 Society of Chemical Industry     

Radiation synthesis of poly(N‐vinylpyrrolidone‐co‐methacrylic acid) hydrogels and their usability in uranyl ion adsorption

In this study, N‐vinylpyrrolidone(VP)/methacrylic acid (MAA) mixtures have been prepared at three different mole percents which the methacrylic acid composition around 5, 10, and 15%. Poly(N‐vinylpyrrolidone‐co‐methacrylicacid) P(VP/MAA) hydrogels irradiated at 3.4 kGy have been used for swelling and diffusion studies in water and uranyl ion solutions. The influence of dose, pH, relative amounts of monomers in MAA/VP monomer mixtures on the swelling properties have been investigated. P(VP/MAA) hydrogels were swollen in distilled water at pH 7.0. P(VP/MAA)1 hydrogel containing 36% (mole percent) methacrylic acid showed the maximum percent swelling in water. Adsorption isotherms were constructed for uranyl ions and P(VP/MAA) hydrogel systems. It has been found that P(VP/MAA) hydrogels have very high uptake of the uranyl ions succesfully in water containing uranyl ions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,characterization and properties of functionalized styrene–maleimide copolymers

New functionalized styrene–maleimide copolymers were prepared by free radical copolymerization of styrene (St) and N‐4‐carboxybutylmaleimide (NBMI) in chloroform, using 2,2′‐azobisisobutyronitrile (AIBN) as initiator. Monomer and copolymer characterization was carried out by ¹H‐ and ¹³C‐NMR. Copolymer composition was determined by elemental analysis and Fourier‐transform infrared (FTIR) spectroscopy. The glass transition temperature (from DSC) and the thermogravimetric analysis (TGA) of the copolymers were consistent with the thermal behavior and stability observed for alternating St–maleimide copolymers. St–NBMI copolymers crosslinked with divinylbenzene (DVB) were also synthesized and their cation exchange properties evaluated in order to assess the capacity of the new copolymers to bind metallic ions. Copyright © 2005 Society of Chemical Industry     

Controlled/living RAFT polymerization of N‐phenyl maleimide and synthesis of its block copolymers

The controlled/living radical polymerization of N‐phenyl maleimide (NPMI) was achieved using 2,2′‐azobisisobutyronitrile as the initiator and 2‐cyanopropyl‐2‐yl dithiobenzoate as the reversible addition‐fragmentation chain transfer agent at 75°C in dichloroethane/ethylene carbonate (60/40, w/w) mixed solvent. The block copolymers of polystyrene‐b‐polyNPMI and poly(n‐butyl methacrylate)‐b‐polyNPMI were successfully prepared by chain extension from dithiobenzoate‐terminated polystyrene and poly (n‐butyl methacrylate) to NPMI, respectively. The obtained NPMI‐based (co)polymers were characterized by gel permeation chromatography and ¹H‐NMR spectroscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Forgotten monomers: access to α‐modified N‐vinylpyrrolidone polymers via C‐alkylation

Alkylation of N‐vinylpyrrolidone using lithium diisopropylamide and bis(2‐bromoethyl) ether was carried out to obtain 3‐(2‐(2‐bromoethoxy)ethyl)‐1‐vinyl‐2‐pyrrolidone ( 2 ). The derivative 2 represents a versatile starting molecule for further modification via nucleophilic displacement yielding, for example, the bicyclic 2‐vinyl‐8‐oxa‐2‐azaspiro[4.5]decan‐1‐one ( 4 ) or the ammonium salt 3‐diethoxy‐N,N′‐((dimethylbenzyl)ammonium bromide)‐1‐vinyl‐2‐pyrrolidone ( 10 ). Via free radical polymerization of 4 and 10 , the corresponding homopolymers were obtained. Copolymerization of 4 and 10 with N,N′‐diethylacrylamide yielded water‐soluble materials. The thermosensitive solubility of copolymers poly[(2‐vinyl‐8‐oxa‐2‐azaspiro[4.5]decan‐1‐one)‐co‐(N,N′‐diethylacrylamide)] and poly[(3‐diethoxy‐N,N′‐((dimethylbenzyl)ammonium bromide)‐1‐vinyl‐2‐pyrrolidone)‐co‐(N‐vinylpyrrolidone)] in water was investigated. © 2015 Society of Chemical Industry     

Stabilization of vinyl chloride/vinylidene chloride copolymers using N‐substituted maleimides

As a consequence of their excellent barrier properties, vinyl chloride/vinylidene chloride copolymers have long been prominent in the flexible packaging market. While these polymers possess a number of superior characteristics, they tend to undergo thermally induced degradative dehydrochlorination at process temperatures. This degradation must be controlled to permit processing of the polymers. Three series of N‐substituted maleimides (N‐alkyl‐, N‐aralkyl‐, and N‐aryl‐) have been synthesized, characterized spectroscopically, and evaluated as potential stabilizers for a standard vinyl chloride/vinylidene chloride (85 wt%) copolymer. As surface blends with the polymer, these compounds are ineffective as stabilizers. However, significant stabilization may be achieved by pretreatment of the polymer with N‐substituted maleimides. The most effective stabilization of the polymer is afforded by N‐aralkyl‐ or N‐arylmaleimides, most notably, N‐benzylmaleimide and N‐(p‐methoxyphenyl)maleimide. J. VINYL. ADDIT. TECHNOL. 12:88–97, 2006. © 2006 Society of Plastics Engineers.     

2,2′‐(Methylimino)bis(N,N‐dioctylacetamide) (MIDOA), A New Tridentate Extractant for Technetium(VII), Rhenium(VII), Palladium(II), and Plutonium(IV)

2,2′‐(Methylimino)bis(N,N‐dioctylacetamide) (MIDOA) was developed as a new extractant for technetium. MIDOA has a similar backbone to TODGA, N,N,N′,N′‐tetraoctyldiglycolamide, where the nitrogen atom bearing a methyl group replaces the ether oxygen in TODGA. MIDOA is highly lipophilic and ready to use in the HNO₃–n‐dodecane extraction system. The distribution ratio (D) for Tc(VII) is extremely high. In addition, Cr(VI), Re(VII), Mo(VI), W(VI), Pd(II), and Pu(IV) are well extracted by MIDOA. MIDOA has high selectivity toward certain oxometallates. The D(Tc) values decrease gradually with HNO₃, H⁺, and NO₃ ^? concentrations, and the log D vs log [MIDOA] dependence indicates the species extracted to be the 1:1 metal‐ligand complex. It is clear that MIDDA [2,2′‐(methylimino)bis(N,N‐didodecylacetamide)] and IDDA [2,2′‐(imino)bis(N,N‐didodecylacetamide)], which have structures analogous to MIDOA, have similar extraction behavior to that of MIDOA.     

Amphiphilic star‐shaped poly(ε‐caprolactone)‐block‐poly(l‐lysine) copolymers with porphyrin core: Synthesis,self‐assembly,and cell viability assay

Star‐shaped copolymers poly(ε‐caprolactone)‐bolck‐poly(ε‐benzyloxycarbonyl‐l ‐lysine) (SPPCL‐b‐PZLLs) with porphyrin core were synthesized by a sequential ring‐opening polymerization (ROP) of CL and Nε‐Benzyloxycarbonyl‐l ‐lysine N‐Carboxyanhydride. After the deprotection of benzyloxycarbonyl groups in polylysine blocks, the star‐shaped amphiphilic copolymers SPPCL‐b‐PLLs were obtained. These amphiphilic copolymers can self‐assemble into micelles or aggregates in aqueous solution. Investigation shows that the morphology of micelles/aggregates varied according to the change of pH values of media, indicating the pH‐responsive property of SPPCL‐b‐PLL copolymers. Furthermore, associated with conjugated porphyrin cores, the SPPCL‐b‐PLL copolymers micelles showed a certain degree of Photodynamic Therapy (PDT) effects on tumor cells, suggesting its potential application as carrier for hydrophobic drug with additional therapeutic ability of inherent porphyrin segments. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40097.     

Phase behavior of temperature‐ and pH‐sensitive poly(acrylic acid‐g‐N‐isopropylacrylamide) in dilute aqueous solution

Several different composition temperature‐ and pH‐sensitive poly(acrylic acid‐g‐N‐isopropylacrylamide) (P(AA‐g‐NIPAM)) graft copolymers were synthesized by free‐radical copolymerization utilizing macromonomer technique. The phase behavior and conformation change of P(AA‐g‐NIPAM) in aqueous solutions were investigated by UV–vis transmittance measurements, fluorescence probe, and fluorescence quenching techniques. The results demonstrate that the P(AA‐g‐NIPAM) copolymers have temperature‐ and pH‐sensitivities, and these different composition graft copolymers have different lower critical solution temperature (LCST) and critical phase transition pH values. The LCST of graft copolymer decreases with increasing PNIPAM content, and the critical phase transition pH value increases with increasing Poly(N‐isopropylacrylamide) (PNIPAM) content. At room temperature (20°C), different composition of P(AA‐g‐NIPAM) graft copolymers in dilute aqueous solutions (0.001 wt %) have a loose conformation, and there is no hydrophobic microdomain formation within researching pH range (pH 3 ～ 10). In addition, for the P(AA‐g‐NIPAM) aqueous solutions, transition from coil to globular is an incomplete reversible process in heating and cooling cycles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and Properties of Novel Surface Active Monomers Based on Derivatives of 4‐Hydroxybutyric Acid and 6‐Hydroxyhexanoic Acid

Novel surface active maleate and methacrylate monomers based on derivatives of ω‐hydroxy carboxylic acids have been synthesized. The monomers are comprised of hydrophobic alkyl chains and hydrophilic poly(ethylene glycol), quaternary ammonium, sulfonate and carboxylic fragments. Synthesized monomers sufficiently reduce surface tension at the aqueous solution‐air interface. The copolymerization of synthesized monomers with 5‐tert‐butylperoxy‐5‐methyl‐2‐hexene‐3‐yne monomer and N‐vinylpyrrolidone in solvent and emulsion copolymerization of synthesized peroxide containing surface active monomer with styrene have been carried out. The synthesized surface active monomers have been shown to be suitable emulsifiers for obtaining polystyrene colloid dispersions. It has been ascertained that the surface active copolymers obtained can form stable interpolyelectrolyte complexes with oppositely charged polymers.