New Grafted Copolymers Carrying Betaine Units Based on Gellan and N-Vinylimidazole as Precursors for Design of Drug Delivery Systems

New grafted copolymers possessing structural units of 1-vinyl-3-(1-carboxymethyl) imidazolium betaine were obtained by graft copolymerization of N-vinylimidazole onto gellan gum followed by the polymer-analogous reactions on grafted polymer with the highest grafting percentage using sodium chloroacetate as the betainization agent. The grafted copolymers were prepared using ammonium persulfate/N,N,N′,N′ tetramethylethylenediamine in a nitrogen atmosphere. The grafting reaction conditions were optimized by changing one of the following reaction parameters: initiator concentration, monomer concentration, polymer concentration, reaction time or temperature, while the other parameters remained constant. The highest grafting yield was obtained under the following reaction conditions: c_i = 0.08 mol/L, c_m = 0.8 mol/L, c_p = 8 g/L, t_r = 4 h and T = 50 °C. The kinetics of the graft copolymerization of N-vinylimidazole onto gellan was discussed and a suitable reaction mechanism was proposed. The evidence of the grafting reaction was confirmed through FTIR spectroscopy, X-ray diffraction, ¹H-NMR spectroscopy and scanning electron microscopy. The grafted copolymer with betaine structure was obtained by a nucleophilic substitution reaction where the betainization agent was sodium chloroacetate. Preliminary results prove the ability of the grafted copolymers to bind amphoteric drugs (cefotaxime) and, therefore, the possibility of developing the new sustained drug release systems.     

Characterization of N-isopropyl acrylamide/acrylic acid grafted polypropylene nonwoven fabric developed by radiation-induced graft polymerization

Radiation-induced graft copolymerization of N-isopropylacrylamide (NIPAAm) and acrylic acid (AA) mixture was carried out on polypropylene nonwoven fabric to develop a thermosensitive material and has been found to affect the thermal and physical characteristics of fabric. The grafted fabrics with different monomer ratios were characterized by thermal gravimetric analysis (TGA), fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), contact angle and atomic force microscopy (AFM). Results of FTIR clearly indicated that poly(acrylic acid) and poly(N-isopropyl acrylamide) were successfully grafted onto the membrane surface. TGA results showed that the thermal stability of PP fabric increased after grafting of NIPAAm/AA. The crystallinity values from DSC and XRD were found to decrease with increase in degree of grafting because of the addition of grafted chains within the noncrystalline region. The decrease in contact angles of the grafted fabric with an increase of the degree of grafting shows that PNIPAAm/PAA exists as the hydrophilic component. The increase in surface roughness after grafting was observed by AFM.     

Preparation of thermosensitive membranes by radiation grafting of acrylic acid/N-isopropyl acrylamide binary mixture on PET fabric

Thermosensitive membranes were prepared by radiation-induced graft copolymerization of monomers on PET fabrics. A binary mixture of N-isopropyl acrylamide (NIPAAm) and acrylic acid (AA) was grafted on polyester fabric as a base material to introduce thermosensitive poly(N-isopropyl acrylamide) pendant chains having LCST slightly higher than 37 °C in the membrane. The influence of ferrous sulfate, radiation dose and monomer composition on the degree of grafting was studied. The structure of the grafted fabric was characterized by thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy. The thermosensitive nature of the fabric was monitored by swelling at different temperatures. The graft copolymerization of AA with NIPAAm enhanced the LCST of the resultant membrane to ∼37 °C. The moisture vapor transmission rate (MVTR) and air permeability of the fabric decreased slightly, may be due to the slight blocking of the fabric pores. The immobilization of tetracycline hydrochloride as the model drug and its release characteristics at different temperatures were monitored.     

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.     

Inverse opal pH sensors with various protic monomers copolymerized with polyhydroxyethylmethacrylate hydrogel

pH sensitive inverse opal sensors were synthesized using various vinyl monomers containing acidic or basic substituents. Acrylic acid (AA), vinylphosphonic acid (VPA), vinylimidazole (VI), and dimethylaminoethylmethacrylic acid (DMAEMA) were respectively copolymerized with hydroxyethylmethacrylate (HEMA), the building block monomer of the hydrogel via UV-initiated photopolymerization. Opal templating and subsequent template removal enabled the fabrication of four inverse opal (IO) hydrogel colorimetric sensors, which responded to pH in different fashions. pH-dependent swelling of the IO hydrogel induced the red-shift of the diffracted color. The sensors containing AA or VPA, the proton donating monomers showed the color shifts from green to red with pH increase due to the increased concentration of carboxylate anions bound to the hydrogel. Diprotic VPA sensor exhibited two-step increases of diffracted wavelengths at its pK_a1 and pK_a2 respectively. The sensors containing proton acceptors, VI and DMAEMA showed the pH-dependent color changes in an opposite way to the AA sensor and the VPA sensor since their ionizations take place by lowering pH due to the protonation at the amino groups. The shapes of pH response curves of VI and DMAEMA sensors were similar but pK_bs were different from each other. Optical diffraction responses of four sensors were compared with the calculated concentration ratios of the ionized species to the total monomer with pH variation, and a deswelling effect in the vicinities of pK_as of phosphate buffer on the swelling response could be explained by shrinkage of PHEMA hydrogel under high ionic environment. In addition, copolymerization of AA, VPA and HEMA was carried out which resulted in a pH sensor exhibiting a wider range of pH for color change.     

Cellulose-g-PDMAam copolymers by controlled radical polymerization in homogeneous medium and their aqueous solution properties

Water-soluble cellulose-graft-PDMAam copolymers were prepared by single-electron-transfer living radical polymerization (SET-LRP). Cellulose based macroinitiator for SET-LRP with a degree of substitution DS ≈ 2 was synthesized from softwood dissolving pulp in a homogeneous LiCl/DMAc solution. The macroinitiator was then grafted using N,N-dimethyl acrylamide (DMAam) in DMSO. Formation of cellulose-g-DMAam copolymers were confirmed by ATR–FTIR, ¹H and ¹³C NMR spectroscopy and SEC analyses. Light scattering and steady–shear viscosity measurements revealed that the studied chain length of grafts (DP_graft) had only minor effects on the solution properties of cellulose-g-PDMAam copolymers. SLS studies suggested a loose, solvent-draining architecture of the cellulose-g-PDMAam copolymer particles in H₂O.     

Preparation of densely grafted poly(aniline‐2‐sulfonic acid‐co‐aniline)s as novel water‐soluble conducting copolymers

Various densely grafted polymers containing poly(aniline‐2‐sulfonic acid‐co‐aniline)s as side chains and polystyrene as the backbone were prepared. A styryl‐substituted aniline macromonomer, 4‐(4‐vinylbenzoxyl)(N‐tert‐butoxycarbonyl)phenylamine (4‐VBPA‐^tBOC), was first prepared by the reaction of 4‐aminophenol with the amino‐protecting moiety di‐tert‐butoxyldicarbonate, and this was followed by substitution with 4‐vinylbenzyl chloride. 4‐VBPA‐^tBOC thus obtained was homopolymerized with azobisisobutyronitrile as an initiator, and this was followed by deprotection with trifluoroacetic acid to generate poly[4‐(4‐vinylbenzoxyl)phenylamine] (PVBPA) with pendent amine moieties. Second, the copolymerization of aniline‐2‐sulfonic acid and aniline was carried out in the presence of PVBPA to generate densely grafted poly(aniline‐2‐sulfonic acid‐co‐aniline). Through the variation of the molar feed ratio of aniline‐2‐sulfonic acid to aniline, various densely grafted copolymers were generated with different aniline‐2‐sulfonic acid/aniline composition ratios along the side chains. The copolymers prepared with molar feed ratios greater than 1/2 were water‐soluble and had conductivities comparable to those of the linear copolymers. Furthermore, these copolymers could self‐dope in water through intermolecular or intramolecular interactions between the sulfonic acid moieties and imine nitrogens, and this generated large aggregates. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1090–1099, 2005     

Preparation of High‐capacity,Monodisperse Polymeric Weak Cation Exchange Packings Using Surface‐initiated Atom Transfer Radical Polymerization and Its Chromatographic Properties

A novel stationary phase for weak cation exchange (WCX) chromatography was prepared by "grafting from" strategy. Surface initiated atom transfer radical polymerization (ATRP) of acrylic acid (AA) was conducted in toluene medium, starting from the macromolecule initiators of poly(4‐vinylbenzyl chloride‐co‐divinylbenzene) (P_CMS/DVB) beads. The amounts of poly(acrylic acid) grafted chains with different ATRP formulations were calculated based on the elemental analyses. The poly(acrylic acid) grafted beads obtained with different ATRP formulations were tried as chromatographic packings in the separation of proteins by ion‐exchange chromatography. The effect of the poly(acrylic acid) grafted chain lengths on P_CMS/DVB beads for the separation of proteins was investigated in details. Simultaneously, characterization of the column was investigated as ion chromatographic stationary phase for the separation of inorganic cations. The results show that poly(acrylic acid) grafted columns had excellent performance for separation of proteins and inorganic cations. The highest of the dynamic capacity of the column was 35.55 mg/mL. The columns were provided with high column efficiency.     

Thermo‐ and pH‐induced self‐assembly of P(AA‐b‐NIPAAm‐b‐AA) triblock copolymers synthesized via RAFT polymerization

A series of environmentally sensitive ABA triblock copolymers with different block lengths were prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization from acrylic acid (AA) and N‐isopropylacrylamide (NIPAAm). The GPC and ¹H NMR analyses demonstrated the narrow molecular weight distribution and precise chemical structure of the prepared P(AA‐b‐NIPAAm‐b‐AA) triblock copolymers owing to the controlled/living characteristics of RAFT polymerization. The lower critical solution temperature (LCST) of the triblock copolymers could be tailored by adjusting the length of PAA block and controlled by the pH value. Under heating, the triblock copolymers underwent self‐assemble in dilute aqueous solution and formed nanoparticles revealed via TEM images. Physically crosslinked nanogels induced by inter‐/intra‐hydrogen bonding or core‐shell micelle particles thus could be obtained by changing environmental conditions. With a well‐defined structure and stimuli‐responsive properties, the P(AA‐b‐NIPAAm‐b‐AA) copolymer is expected to be employed as a nanocarrier for biomedical applications in controlled‐drug delivery and targeting therapy. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1109–1118     

Random copolymers of N-isopropylacrylamide and methacrylic acid monomers with hydrophobic spacers: pH-tunable temperature sensitive materials

Two series of random copolymers of N-isopropylacrylamide (NIPAAm) and comonomers derived from methacrylic acid with a different number of methylene units as hydrophobic spacers (n=4, 7 and 10) were synthesized via free radicals. The first series was prepared having the acid groups methoxy-protected while the second series have the acid groups free. The NIPAAm-copolymers of both series were prepared varying the comonomer content from 5 to 20 mol%. All the copolymers were characterized by FTIR, DSC, ¹H NMR and SLS. The aqueous solution behaviour of the copolymers having methoxy-protected acid groups shows that the comonomer increases the hydrophobicity of the copolymer chain and decreases its lower critical solution temperature (LCST). For the copolymers having free acid groups, hydrogen-bonding is responsible for a further decrease in the LCST of these copolymers in pure water. In buffer solutions, every acid comonomer have a critical ionization degree (α_crit) above which the LCST increases with increasing comonomer content while at an ionization degree lower than α_crit the LCST decreases with increasing comonomer content. In dependence of comonomer content, number of methylene units in the spacer and the pH of the buffer solution, the LCST of the copolymers can be varied widely, showing that these random copolymers have pH-tunable temperature sensitivity.     

Radiation-Induced Asymmetric Grafting of Different Monomers into Base Films to Prepare Novel Bipolar Membranes

We prepared novel bipolar membranes (BPMs) consisting of cation and anion exchange layers (CEL and AEL) using radiation-induced asymmetric graft polymerization (RIAGP). In this technique, graft polymers containing cation and anion exchange groups were introduced into a base film from each side. To create a clear CEL/AEL boundary, grafting reactions were performed from each surface side using two graft monomer solutions, which are immiscible in each other. Sodium p-styrenesulfonate (SSS) and acrylic acid (AA) in water were co-grafted from one side of the base ethylene-co-tetrafluoroethylene film, and chloromethyl styrene (CMS) in xylene was simultaneously grafted from the other side, and then the CMS units were quaternized to afford a BPM. The distinct SSS + AA- and CMS-grafted layers were formed owing to the immiscibility of hydrophilic SSS + AA and hydrophobic CMS monomer solutions. This is the first BPM with a clear CEL/AEL boundary prepared by RIAGP. However, in this BPM, the CEL was considerably thinner than the AEL, which may be a problem in practical applications. Then, by using different starting times of the first SSS+AA and second CMS grafting reactions, the CEL and AEL thicknesses was found to be controlled in RIAGP.     

Preparation and some properties of diamine-diacid type alternating copolyamides

The polycondensations of N,N′-bis-(6-aminohexyl)oxamide, N,N′-bis-(6-aminohexyl) succinimide and N,N′-bis(6-aminohexyl)-sebacamide, with p-nitrophenyl adipate in 1,2,4-trichlorobenzene solution, using relatively low temperature (100°) to avoid the amide exchange reactions, gave alternating copolyamides corresponding to (6-6) (6-2), (6-6) (6-4) and (6-6) (6–10) nylons. These copolymers have melting points between those of their corresponding homopolyamides, whereas the random copolymers melt lower than either of the homopolymers. The microstructure of the copolymers seems to be modified by heat treatment below the melting points. Amide exchange reactions occur when they are heated to melting. C¹³ spectra allowed differentiation between the CO groups of the two constituent units of the copolymers, but not between the alternating and the random copolymers.     

Polymer–Metal Complexes Obtained by Radiation‐Induced Grafting Process onto Polyester Fabrics

Abstract

This paper reports the preparation of chelating copolymers via grafting of acrylic acid, and/or acrylamide onto polyester microfiber (PETMF) fabrics using a γ‐radiation technique. The effect of monomer concentration on the grafting process at irradiation dose 20?kGy was studied. The prepared graft chains (PETMF‐g‐AA), (PETMF‐g‐AAm), and (PETMF‐g‐PAAc/PAAm) acted as chelating sites for some selected transition metal ions. The effect of grafting on mechanical properties of PETMF and its copolymer–metal complexes was investigated. The prepared chelating copolymers and their metal complexes were characterized using x‐ray (energy dispersive x‐ray, EDX), differential scanning calorimeter (DSC), color parameters, and electrical conductivity measurements. The possibility of practical uses for such prepared graft copolymer–metal complexes was discussed and determined. The observed results showed that the electrical conductivity of the grafted copolymers and their metal complexes are thermally activated. Moreover, the degree of grafting enhanced the conductivity values of the grafted and non‐complexed copolymer up to three orders of magnitude, on the other hand, the conductivity of the copolymer–metal complexes slightly increased.     

Characterisation of N-vinyl-2-pyrrolidone-based hydrogels prepared by a Diels-Alder click reaction in water

N-vinyl-2-pyrrolidone-based hydrogels were prepared by the Diels-Alder reaction in water for the first time. Copolymers of N-vinyl-2-pyrrolidone(VP) and furfuryl methacrylate(FM) were synthesised by free radical polymerisation in toluene at 70 °C by using 2,2′-azobisisobutyronltrile as an initiator. Polymeric dienophile (PEG-AMI) was prepared from N-alaninyl maleimide (AMI) and poly(ethylene glycol) (PEG) by using N,N′-dicyclohexylcarbodiimide (DCC) as a dehydrating agent. The prepared dienes and dienophile were then dissolved in water and mixed, leading to gelation via Diels-Alder reaction after some time. The gelation times of different copolymers and PEG-AMI in different solvents and at different temperatures were measured by the vial inversion method, and the swelling behaviour of dried hydrogels was studied using a general gravimetric method. The gelation time was shorter in water than in organic solvents, and the gelation time decreased with the increase of temperature and FM content in copolymers. Conversely, the swelling ratios increased with the decrease of temperature and FM content in the copolymers. Disassembly experiments suggested that N,N-dimethylformamide (DMF) could accelerate the retro-DA reaction.     

Preparation, structure and properties of PP-g-AA grafting copolymer

Polypropylene grafting with AA was prepared by reactive extrusion with pre-irradiated PP (rPP) as the homogeneous initiator. The effects of the pre-irradiated dose, the fraction of rPP and the concentration of acrylic acid on the grafting reaction were studied and the grafted PP was characterized by Fourier transition infrared spectroscopy (FTIR), differential scanning calorimeter (DSC) and polarized light microscopy (PLM). The results show that the degradation of PP was suppressed efficiently with this novel method for preparing PP-g-AA copolymers, and the grafted copolymers with good mechanical properties were obtained. It was found that the product with higher graft degree (G _d)(0.19%) and relatively excellent mechanical properties can be produced if the mass ratio of PP/rPP/AA is 90:10:0.8, where the selected pre-irradiation dose of rPP is 4 kGy. Moreover, an adhesive strength of 4.88 kN/m was reached in the PP-g-AA/aluminum laminate. __________ Translated from Chinese Journal of Applied Chemistry, 2007, 24(7): 737–741 [译自: 应用化学]     

Synthesis and water sorption studies of pH sensitive poly(acrylamide-co-itaconic acid) hydrogels

Superabsorbent copolymers of acrylamide (Am) and itaconic acid (ItA) were prepared by free radical solution polymerization using sodium persulfate and N,N,N′,N′-tetramethylenediamine (TMEDA) as initiating system at 35 °C. Two series were prepared. The first series (SA series) used varied amount of itaconic acid and fixed amount of N,N′-methylenebisacrylamide (MBAm), while in the second series (SB series) the amount of (MBAM) changed and the amount of itaconic acid was fixed. The swelling behavior was studied at room temperature and the swelling percentage, swelling kinetics parameters such as initial swelling rate, swelling rate constant, and diffusion parameters were determined. The effect of pH and saline sensitivity on swelling behavior was also studied.     

Free volume and microstructural investigation of poly(ethylene terephthalate)-g-acrylic acid (PET-g-AA) copolymer films

Acrylic acid (AA) was grafted onto PET films by preirradiation method using a ⁶⁰Co γ-radiation source. Microstructural investigation of the PET-g-AA copolymers has been carried out by wide angle X-ray diffraction (WAXD), dynamic mechanical analysis (DMA) and positron annihilation lifetime spectroscopy (PALS) techniques. The WAXD results showed only marginal variation in the crystallinity of the graft copolymers. Dynamic mechanical analysis showed an increase in the temperature of the α-relaxation and the tan δ value of subroom temperature secondary relaxations. From the PALS results, a complex variation of the free volume parameters, i.e. the o-positronium lifetime (τ₃), its intensity (I₃), fractional free volume (f_v) and the intermediate lifetime component was observed for the graft copolymers. Multiple phenomena of the effect of secondary relaxations, additive behavior of the individual polymer free volume parameters and effects from interfacial defects have been invoked to understand the fluctuational nature of the free volume properties in the graft copolymers.     

Comb copolymers of polystyrene-poly(tert-butyl (meth)acrylate) prepared by combination of nitroxide mediated polymerization and photoinduced iniferter technique

Comb copolymers consisting of polystyrene backbone and poly(tert-butyl (meth)acrylate) side chains were synthesized by combination of nitroxide (TEMPO)-mediated polymerization (NMP) and photoinduced grafting from macro-iniferters. First, poly(chloromethylstyrene), PCMS, with the degree of polymerization and two random poly(styrene-co-chloromethylstyrene) copolymers, P(S-co-CMS), with similar but different content (8 and 14 mol%) of CMS units, were synthesized by NMP. In the second step the CMS units both in the homopolymer and the copolymers were converted to N,N-diethyldithiocarbamyl groups (DC) yielding photosensitive multifunctional macro-iniferters. Finally, tert-butyl methacrylate tBuMA was grafted from the synthesized polymer backbones by iniferter technique under UV-irradiation yielding copolymers polystyrene-graft-poly(tert-butyl methacrylate) PS-g-P(tBuMA). Grafting initiated by the macro-iniferters containing ∼6-11 DC initiating sites per macromolecule proceeded by pseudo-living polymerization mechanism, i.e., the number-average molecular weight increased with conversion and the SEC traces were unimodal. In contrast, photo-polymerization initiated by highly functionalized polystyrene backbone was poorly controlled. Hydrolysis of loosely grafted copolymers PS-g-P(tBuMA) afforded amphiphilic copolymers polystyrene-graft-poly(methacrylic acid). Molecular parameters of the synthesized graft copolymers in dilute THF solutions were determined by scattering (DLS, SLS, SAXS) and viscometric measurements.     

Radiation grafting of NIPAAm and acryloxysuccinimide onto PP films and sequent crosslinking with polylysine

N-isopropylacrylamide (NIPAAm) and N-acryloxysuccinimide (NAS) were grafted from their binary mixtures in tetrahydrofurane (THF) and toluene solutions onto polypropylene (PP) films by the pre-irradiation oxidative method in air. Effects of pre-irradiation dose, dose rate, and monomer concentrations (NAS/NIPAAm) were studied. The grafted copolymers exhibited the lower critical solution temperature (LCST) at around 31 °C. Based on its thermo-reversible behavior, this system has been used for immunoassay, drug delivery, separation processes and immobilization of enzymes. N-acryloxysuccinimide (NAS) has been used as an active ester to bind proteins through amide bond formation with lysine, and because of this property, the grafted copolymer has been crosslinked with polylysine. Techniques used to characterize the films included differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), infrared (FTIR-ATR) and elemental analysis. Results on thermo-sensitivity are presented. This new system could find applications in vesicle immobilizations.     

Non-fluorinated proton-exchange membranes based on melt extruded SEBS/HDPE blends

This paper reports on functional polymer blends prepared by melt-processing technologies for proton-exchange membrane applications. Styrene–ethylene/butylene–styrene (SEBS) and high-density polyethylene (HDPE) were melt blended using twin-screw compounding, extruded into thin films by extrusion–calendering. The films were then grafted with sulfonic acid moieties to obtain ionic conductivity leading to proton-exchange membranes. The effect of blend composition and sulfonation time was investigated. The samples were characterized in terms of morphology, microstructure, thermo-mechanical properties and in terms of their conductivity, ion exchange capacity (IEC) and water uptake in an effort to relate the blend microstructure to the membrane properties. The HDPE was found to be present in the form of elongated structures which created an anisotropic structure especially at lower concentrations. The HDPE increased the membrane mechanical properties and restricted swelling, water uptake and methanol crossover. Room temperature through-plane conductivities of the investigated membranes were up to 4.5E−02 S cm⁻¹ at 100% relative humidity, with an ionic exchange capacity of 1.63 meq g⁻¹.