Poly(ethylene‐graft‐ethylene oxide) (PE‐PEO) and poly(ethylene‐co‐acrylic acid) (PEAA) as compatibilizers in blends of LDPE and polyamide‐6

In a blend of two immiscible polymers a controlled morphology can be obtained by adding a block or graft copolymer as compatibilizer. In the present work blends of low‐density polyethylene (PE) and polyamide‐6 (PA‐6) were prepared by melt mixing the polymers in a co‐rotating, intermeshing twin‐screw extruder. Poly(ethylene‐graft‐polyethylene oxide) (PE‐PEO), synthesized from poly(ethylene‐co‐acrylic acid) (PEAA) (backbone) and poly(ethylene oxide) monomethyl ether (MPEO) (grafts), was added as compatibilizer. As a comparison, the unmodified backbone polymer, PEAA, was used. The morphology of the blends was studied by scanning electron microscopy (SEM). Melting and crystallization behavior of the blends was investigated by differential scanning calorimetry (DSC) and mechanical properties by tensile testing. The compatibilizing mechanisms were different for the two copolymers, and generated two different blend morphologies. Addition of PE‐PEO gave a material with small, well‐dispersed PA‐spheres having good adhesion to the PE matrix, whereas PEAA generated a morphology characterized by small PA‐spheres agglomerated to larger structures. Both compatibilized PE/PA blends had much improved mechanical properties compared with the uncompatibilized blend, with elongation at break (ε_b) increasing up to 200%. Addition of compatibilizer to the PE/PA blends stabilized the morphology towards coalescence and significantly reduced the size of the dispersed phase domains, from an average diameter of 20 μm in the unmodified PE/PA blend to approximately 1 μm in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2416–2424, 2000     

Synergistic extraction of rare earths(III) from chloride medium with mixtures of 1‐phenyl‐3‐methyl‐4‐benzoyl‐pyrazalone‐5 and di‐(2‐ethylhexyl)‐2‐ethylhexylphosphonate

The synergistic effect of 1‐phenyl‐3‐methyl‐4‐benzoyl‐pyrazalone‐5 (HPMBP, HA) and di‐(2‐ethylhexyl)‐2‐ethylhexylphosphonate (DEHEHP, B) in the extraction of rare earths (RE) from chloride solutions has been investigated. Under the experimental conditions used, there was no detectable extraction when DEHEHP was used as a single extractant while the amount of RE(III) extracted by HPMBP alone was also low. But mixtures of the two extractants at a certain ratio had very high extractability for all the RE(III). For example, the synergistic enhancement coefficient was calculated to be 9.35 for Y³⁺, and taking Yb³⁺ and Y³⁺ as examples, RE³⁺ is extracted as RE(OH)A₂.B. The stoichiometry, extraction constants and thermodynamic functions such as Gibbs free energy change ΔG (?17.06 kJ mol^?1), enthalpy change ΔH (?35.08 kJ mol^?1) and entropy change ΔS (?60.47 J K^?1 mol^?1) for Y³⁺ at 298 K were determined. The separation factors (SF) for adjacent pairs of rare earths were calculated. Studies show that the binary extraction system not only enhances the extraction efficiency of RE(III) but also improves the selectivity, especially between La(III) and the other rare earth elements. Copyright © 2006 Society of Chemical Industry     

Carbon dioxide sorption and diffusion in poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐CO‐3‐hydroxyvalerate)

CO₂ sorption and diffusion in poly(3‐hydroxybutyrate) and three poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) copolymers were investigated gravimetrically at temperatures from 25° to 50°C and pressures up to 1 atm. The sorption behavior proved to be linear for all the copolymers studied. An additional set of measurements performed in a pressure decay apparatus at 35°C showed that the linearity could be extrapolated to pressures up to 25 atm. The sorption results obtained from both techniques were in good agreement. The poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) sorption kinetics were increasingly non‐Fickian at the higher temperatures, thus preventing the calculation of diffusion coefficients above 35°C. Interestingly, this was not the case for poly(3‐hydroxybutyrate), and diffusion coefficients and permeabilities could be calculated at all of the investigated temperatures. The 35°C permeabilities were fairly low, which is attributed to the high degree of crystallinity of this polyester family. Finally, the poly(3‐hydroxybutyrate) barrier properties against CO₂ are successfully compared with those of some selected common thermoplastics. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2391–2399, 1999     

Rheological properties of poly(ethylene glycol)/poly(N‐isopropylacrylamide‐co‐2‐acrylamido‐2‐methylpropanesulphonic acid) semi‐interpenetrating networks

For the increasing demands of multifunctional materials in applications such as drug delivery system, a pH‐ and temperature‐responsive polyelectrolyte copolymer gel system was studied using rheometry. Rheological properties, determined by plate–plate rheometry in oscillatory shear, of hydrogels formed by free radical initiated copolymerization of N‐isopropylacrylamide (NIPA) and 2‐acrylamido‐2‐methylpropanesulphonic acid (AMPS) in the presence of methylene bisacrylamide (MBAA) as crosslinker are compared with the properties of semi‐interpenetrating network (SIPN) polyelectrolyte gels made by incorporation of poly(ethylene glycol) with molar mass 6000 g mol^?1 (PEG6000). Based on our systematic studies for this PEG/SIPN system, the effects of initiator and crosslinker concentration, relative proportions of comonomer units in the main chains, PEG6000 content and temperature on viscoelastic properties, unusual high storage moduli at small strain for the SIPN were discussed. The SIPN gel with characteristics of PEG molecules as well as pH and temperature responsiveness from AMPS and NIPA units has potential application in drug delivery system design. Ice‐like rheological behavior of the PEG/AMPS‐NIPA SIPN gels at low temperature was first time reported and water remains homogeneous without phase separation in PEG/AMPS‐NIPA SIPN hydrogels at low temperature may be considered as an ideal candidate for water storage material. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermosensitive nanoparticles prepared from poly(N‐isopropylacrylamide‐acrylamide‐vinilpyrrolidone) and its blend with poly(lactide‐co‐glycolide) for efficient drug delivery system

Temperature‐responsive polymers have become increasingly attractive as carrier for the injectable drug delivery systems. In the present work, we have studied the preparation of poly(N‐isopropylacrylamide‐acrylamide‐vinilpyrrolidone) (NIPAAm‐AAm‐VP terpolymer) nanoparticulated terpolymer and its blend with poly(lactide‐co‐glycolide, PLGA; molar ratio of lactide/glycolid 1/3). Thermosensitive terpolymer, poly(NIPAAm‐AAm‐VP) was prepared by free‐radical polymerization in aqueous solution. The nanoparticles of poly(NIPAAm‐AAm‐VP) and its blend with PLGA containing naltrexone were prepared using the evaporation and w/o emulsion‐solvent evaporation methods, respectively. Nanoparticles prepared from terpolymer‐PLGA blend at low polymer concentration (5%) shows larger particle size (>300 nm) and higher drug content%. Various types of nanoparticles showed a burst release of less than 10% after 24 h . The results suggest that by regulating different variables, desired release profiles of naltrexone can be achieved using a blend of PLGA‐poly(NIPAAm‐AAm‐VP) nanoparticulate system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal and Combustion Properties of 3,4‐Bis(3‐nitrofurazan‐4‐yl)furoxan (DNTF)

Thermal decomposition of melted 3,4‐bis(3‐nitrofurazan‐4‐yl)furoxan (DNTF) in isothermal conditions was studied. The burning rates of DNTF were measured in the pressure interval of 0.1–15 MPa. The thermal stability of DNTF was found to be close to the stability of HMX, while the burning rate of DNTF was close to the burning rate of CL‐20. The thermocouple measurements in the combustion wave of DNTF showed that combustion of DNTF was controlled by the gas‐phase mechanism. The DNTF vapor pressure was determined from thermocouple measurements and agreed well with data obtained at low temperatures under isothermal conditions.     

Synthesis of 2‐Aminobenzothiazoles via Copper(I)‐Catalyzed Cross‐Coupling with Part‐Per‐Million Catalyst Loadings

An efficient protocol has been developed for the preparation of 2‐aminobenzothiazoles via a copper(I)‐catalyzed tandem reaction of 2‐iodoanilines with isothiocyanates at very low catalyst loadings [typically 50 ppm of copper(I) iodide (CuI)]. A variety of 2‐iodoanilines could be cross‐coupled with isothiocyanates, affording 2‐aminobenzothiazoles in moderate to good yields (49–93%) under the given conditions. The turnover number (TON) of this reaction reaches 67,000 and the reaction could be scaled up, at least, to the gram‐scale.     

Conducting properties of iodine‐doped low‐density polyethylene–poly(4‐vinylpyridine) blends

The conductivities of blends of low‐density polyethylene and poly(4‐vinyl pyridine) (P4VP) were studied. The blends were synthesized by in situ sorption and thermal polymerization of 4‐vinylpyridine in low‐density polyethylene. They showed, after iodine doping, conductivities of 1.7 to 5.0 × 10^?7 S cm^?1 at 298 K, depending on the P4VP mass increment into the matrix. Their conductivities were one order of magnitude higher for measurements at 338 K. The optimum ratio of iodine to pyridine (n) which gave the highest conductivity was 0.21. The thermal stability of doped blends was acceptable for their uses as electrochemical devices. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 939–944, 2003     

pH‐ and temperature‐sensitive microfiltration membranes from blends of poly(vinylidene fluoride)‐graft‐poly(4‐vinylpyridine) and poly(N‐isopropylacrylamide)

The copolymer poly(vinylidene fluoride)‐graft‐poly(4‐vinylpyridine) (PVDF‐g‐P4VP) was prepared through the graft copolymerization of poly(vinylidene fluoride) with 4‐vinylpyridine. Through the blending of the PVDF‐g‐P4VP copolymer with poly(N‐isopropylacrylamide) (PNIPAm) in an N‐methyl‐2‐pyrrolidone solution, PVDF‐g‐P4VP/PNIPAm membranes were fabricated by phase inversion in aqueous media. Elemental analyses indicated that the blend concentration of PNIPAm in the blend membranes increased with an increase in the blend ratio used in the casting solution. Scanning electron microscopy revealed that the membrane surface tended to corrugate at a low PNIPAm concentration and transformed into a smooth morphology at a high PNIPAm concentration. The surface morphology and pore size distribution of the microfiltration membranes could be regulated by the blend concentration of the casting solution, temperature, pH, and ionic strength of the coagulation bath. X‐ray photoelectron spectroscopy revealed a significant enrichment of PNIPAm on the membrane surface. The flux of aqueous solutions through the blend membranes exhibited a pH‐ and temperature‐dependent behavior. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4089–4097, 2006     

Effect of prepolyurethane on the performances of poly(acrylates‐co‐urethane) copolymer

Poly(acrylates‐co‐urethane) copolymers were synthesized by the polymerization of acrylates and 2‐hydroxyethyl acrylate terminated polyurethane (prepolyurethane) at room temperature. The polymerization was initiated by the radicals, which were produced by the oxidation of tri‐n‐butylborane (TBB) from the mixing of TBB/hexamethylene diamine complex and diisocyanate decomplexer. The effects of prepolyurethane on the performances of copolymers were discussed. The results indicated that the damping property and flexibility of copolymers were obviously higher than that of pure polyacrylates. Dynamic mechanical analysis and transmission electron microscope results showed that PU was dispersed in polyacrylates phase very well. The copolymers were found to bond well to low surface energy materials because of introduction of PU. The lap shearing strength of copolymer bonding polypropylene or polyethylene both had the trend of first increase followed by decrease with the prepolyurethane content increase. The copolymers as adhesives were also shown to have a long working life and be suitable for utilization at low temperature especially at room temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)‐diphenylsiloxane‐poly(dimethylsiloxane) block copolymers

The heterofunctional condensation of 1,3‐dichloro‐1,3‐disila‐1,3‐diphenyl‐2‐oxaindane with dihydroxydiphenylsilane at various ratios of initial compounds in the presence of amines was carried out, and α,ω‐dihydroxy(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)‐diphenylsiloxane oligomers with various degrees of condensation were obtained. Corresponding block copolymers were obtained by heterofunctional polycondensation of synthesized α,ω‐dihydroxy(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)‐diphenylsiloxane oligomers with α,ω‐dichlorodimethylsiloxanes in the presence of amines. Thermogravimetry, gel permeation chromatography, differential scanning calorimetry, and wide‐angle X‐ray analysis were carried out on the synthesized block coplymers. Differential scanning calorimetry and wide‐angle X‐ray studies of these copolymers showed that their properties were determined by the ratio of the lengths of the flexible linear poly(dimethylsiloxane) and rigid poly(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)‐diphenylsiloxane fragments in the main macromolecular chain. Two‐phase systems were obtained with specific flexible and rigid fragment length values in synthesized block copolymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3462–3467, 2006     

4‐Alkylated Silver–N‐Heterocyclic Carbene (NHC) Complexes with Cytotoxic Effects in Leukemia Cells

Computational chemistry has shown that backbone‐alkylated imidazoles ought to be efficient ligands for transition metal catalysts with improved carbene‐to‐metal donation. In this work, such alkylated imidazoles were synthesized and complexed with silver(I) by means of an eight/nine‐step synthetic pathway we devised to access a new class of biologically active silver complexes. The synthesis involves selective iodination of the imidazole backbone, followed by Sonogashira coupling to replace the backbone iodine. The installed alkyne moiety is then subjected to reductive hydrogenation with Pearlman’s catalyst. The imidazole N1 atom is arylated by the palladium‐catalyzed Buchwald N‐arylation method. The imidazole N3 position was then methylated with methyl iodine, whereupon the synthesis was terminated by complexation of the imidazolium salt with silver(I) oxide. The synthetic pathway provided an overall yield of ≈20 %. The resulting complexes were tested in vitro against HL60 and MOLM‐13 leukemic cells, two human‐derived cell lines that model acute myeloid leukemia. The most active compounds exhibiting low IC₅₀ values of 14 and 27 μM , against HL60 and MOLM‐13 cells, respectively. The imidazole side chain was found to be essential for high cytotoxicity, as the imidazole complex bearing a C₇ side chain at the 4‐position was four‐ to sixfold more potent than the corresponding imidazole elaborated with a methyl group.     

DNA adsorption on a poly‐L‐lysine‐immobilized poly(2‐hydroxyethyl methacrylate) membrane

The DNA adsorption properties of poly‐L ‐lysine‐immobilized poly(2‐hydroxyethyl methacrylate) (pHEMA) membrane were investigated. The pHEMA membrane was prepared by UV‐initiated photopolymerization and activated with epichlorohydrin. Poly‐L ‐lysine was then immobilized on the activated pHEMA membrane by covalent bonding, via a direct chemical reaction between the amino group of poly‐L ‐lysine and the epoxy group of pHEMA. The poly‐L ‐lysine content of the membrane was determined as 1537 mg m^?2. The poly‐L ‐lysine‐immobilized membrane was utilized as an adsorbent in DNA adsorption experiments. The maximum adsorption of DNA on the poly‐L ‐lysine‐immobilized pHEMA membrane was observed at 4 °C from phosphate‐buffered salt solution (pH 7.4, 0.1 M; NaCl 0.5 M) containing different amounts of DNA. The non‐specific adsorption of DNA on the plain pHEMA membrane was low (about 263 mg m^?2). Higher DNA adsorption values (up to 5849 mg m^?2) were obtained in which the poly‐L ‐lysine‐immobilized pHEMA membrane was used. Copyright © 2003 Society of Chemical Industry     

Crystal phase of poly(vinylidene fluoride‐co‐trifluoroethylene) synthesized via hydrogenation of poly(vinylidene fluoride‐co‐chlorotrifluoroethylene)

Trifluoroethylene addition and thermal treatment induced crystal phase transition in a series of poly(vinylidene fluoride‐co‐trifluoroethylene) [P(VDF‐co‐TrFE)] containing varied TrFE molar ratio (6, 9, 12, and 20 mol %) prepared from the hydrogenation of poly(vinylidene fluoride‐co‐chlorotrifluoroethylene have been investigated by means of Fourier transform infrared spectral (FTIR), X‐ray diffraction (XRD), and differential scanning calorimetry (DSC) analyses. The comprehensive applications of the three techniques could distinguish α, β and γ phase of P(VDF‐co‐TrFE) very well. The multipeak fitting technique of DSC is successfully applied to calculate the percentage of different phases in the samples, which allows us to investigate the phase transition process of P(VDF‐co‐TrFE) precisely. It is found that the crystal phase of P(VDF‐co‐TrFE) films is turned from α + γ phase (6 mol % TrFE) to α + γ + β phase (9 and 12 mol % TrFE) to β phase (20 mol % TrFE) at high temperature, and from α + γ phase (6 mol % TrFE) to γ + β phase (9 mol % TrFE) to β phase (>12 mol % TrFE) at low fabricated temperature. Both the fabrication conditions and TrFE addition are responsible for the crystal phase transition of the hydrogenised P(VDF‐co‐TrFE). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Hydrogel characteristics of a novel temperature‐sensitive polymer,poly(N‐2‐methoxyisopropylacrylamide)

In this study, a novel temperature‐sensitive polymer, poly(N‐2‐methoxyisopropylacrylamide), PNMIPA, in the crosslinked hydrogel form was obtained. The monomer, N‐2‐methoxyisopropylacrylamide (NMIPA) was synthesized by the nucleophilic substitution reactions of acryloyl chloride with 2‐methoxyisopropylamine. Hydrogel matrix of PNMIPA was obtained by the bulk polymerization method. The bulk polymerization experiments were performed at +4°C, by using N,N‐methylenebisacrylamide (MBA) as crosslinker, polyethyleneglycol (PEG) 4000 as diluent, and potassium persulfate (KPS) and tetramethylethylenediamine (TEMED) as the initiator and accelerator, respectively. The same polymerization procedures were applied by changing monomer, initiator, crosslinker and diluent concentrations in order to obtain crosslinked gel structures having different temperature–sensitivity properties. The equilibrium swelling ratio of PNIMPA gel matrices at constant temperature increased with increasing initiator concentration and decreasing monomer concentration. The use of PEG 4000 as diluent in the gel synthesis resulted in about two times increase in equilibrium swelling ratios in the low temperature region. A decrease in the equilibrium swelling ratios of gel matrices started at 30°C and the decrease became insignificant at 55°C. Temperature‐sensitivities were determined in two different media. Distilled water medium was used in order to observe the temperature‐sensitivity of the gel clearly and the phosphate buffer medium was used in order to represent the temperature‐sensitive swelling behavior of the gel when it is used in biological media. Step effect was applied on ambient temperature in two opposite directions in order to examine the dynamic swelling and shrinking behaviors of the gels. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Hydrogen‐bonding interaction between poly(ε‐caprolactone) and low‐molecular‐weight amino compounds

The specific interactions between several low‐molecular‐weight diamino compounds and poly(ε‐caprolactone) (PCL) have been investigated by FT‐IR. It was found that PCL and 3,3′‐diaminodiphenylmethane (3,3′‐DADPM) interact through strong intermolecular hydrogen bonds in the blend. Thermal and mechanical properties of PCL/3,3′‐DADPM blends were investigated by DSC and tensile measurements, respectively. The glass transition temperature of the blend increases while both the melting point and the elongation‐at‐break of the blend decrease with the increase of 3,3′‐DADPM content. Besides 3,3′‐DADPM, several other low‐molecular‐weight compounds containing two amino groups, such as o‐phenylenediamine or 1,6‐diaminohexane, were also added into PCL and the corresponding blend systems were investigated by FT‐IR and DSC. The effect of the chemical structure of the additives on the properties of PCL is discussed. © 2001 Society of Chemical Industry     

Dynamic mechanical properties in blends of poly(styrene‐b‐isoprene‐b‐styrene) with aromatic hydrocarbon resin

The damping properties in blends of poly(styrene‐b‐isoprene‐b‐styrene) (SIS) and hydrogenated aromatic hydrocarbon (C₉) resin were investigated by dynamic mechanical analysis. SIS exhibited two independent peaks of loss factor (tan δ) corresponding to the glass transition of polyisoprene (PI) and polystyrene (PS) segments, respectively. The addition of hydrogenated C₉ resin had a positive impact on the damping of SIS. With the increasing softening point and content of the resin, the main tan δ peak shifted to higher temperatures and the useful damping temperature range was broadened. Addition of mica or PS was found to widen the effective damping range evidently in the high‐temperature region, especially when PS was mixed in the solid state. It was concluded that the dispersed PS domains played a role of reinforcing fillers at low temperatures and served as a polymer component with a tan δ peak due to its glass transition at the high temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4157–4164, 2006     

Chemical Transformation of Octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) Induced by Low Energy Electron Beam Irradiation

The effects of 8.0×10⁻¹⁷ J (500 eV) and 3.2×10⁻¹⁹ J (2 eV) electrons on chemical structure of octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) were studied in situ, under ultra‐high vacuum conditions using a combination of X‐ray photoelectron spectroscopy (XPS) and quadrupole mass spectrometry. XPS data indicated that electrons impact by 8.0×10⁻¹⁷ J for 30 s caused a decrease in nitro group concentration, and a little shift in the binding energy of the nitrogen 1s peak. Such a phenomenon was found at very low kinetic energy (3.2×10⁻¹⁹ J) with time evolution. Quadrupole mass spectrometry detected gas desorption after electron irradiation included H₂O and H₂ mostly. Microscopy‐IR spectroscopic investigations also proved that the intensity of nitro groups of HMX after irradiation decreased compared with those of the pristine HMX. We attributed the structure changes obtained by XPS and IR spectroscopy result in a chemical transformation, which was associated with low‐energy dissociative electron attachment (DEA) of surface contaminants followed by deoxidization reactions to form the product molecules.     

Synthesis and characterization of star‐shaped poly(ethylene glycol)‐block‐poly(L‐lactic acid) copolymers by melt polycondensation

Compared with linear diblock or triblock poly(ethylene glycol)‐block‐poly(L ‐lactic acid) copolymer (PEG‐b‐PLLA), star‐shaped PEG‐b‐PLLA (sPEG‐b‐PLLA) copolymers exhibit smaller hydrodynamic radius and lower viscosity and are expected to display peculiar morphologies, thermal properties, and degradation profiles. Compared with the synthesis routine of PEG‐b‐PLLA form lactide and PEG, the traditional synthesis routine from LA and PEG were suffered by the low reaction efficiency, low purity, lower molecular weight, and wide molecular weight distribution. In this article, multiarm sPEG‐b‐PLLA copolymer was prepared from multiarm sPEG and L ‐lactic acid (LLA using an improved method of melt polycondensation, in which two types of sPEG, that is, sPEG₁ (four arm, Mn = 4300) and sPEG₂ (three arm, Mn = 3200) were chosen as the core. It was found the molecular weight of sPEG‐b‐PLLA could be strongly affected by the purity of LLA and sPEGs, and the purification technology of vacuum dewater and vacuum distillation could help to remove most of the impurities in commercial available LLA. The polymers, including sPEG and sPEG‐b‐PLLA with varied core (sPEG₁ and sPEG₂) and LLA/sPEG feeding ratios, were characterized and confirmed by ¹H‐NMR and ¹³C‐NMR spectroscopy, Fourier transform infrared spectroscopy (FT‐IR) and gel permeation chromatography, which showed that the terminal hydroxyl group in each arm of sPEGs had reacted with LLA to form sPEG‐b‐PLLA copolymers with fairly narrow molecular weight distribution. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of poly(tert‐butyl acrylate)‐poly(acrylic acid) amphiphilic copolymers via radiation‐induced reversible addition–fragmentation chain transfer mediated polymerization of tert‐butyl acrylate

Poly(tert‐butyl acrylate) (PtBA) is a versatile hydrophobic macromolecule usually preferred in the development of new materials for a host of applications. PtBA homopolymers with well‐defined structure and controlled molecular weight in a wide range were successfully synthesized via radiation‐induced reversible addition–fragmentation chain transfer (RAFT) polymerization in the presence of a trithiocarbonate type RAFT agent. The polymerization of tBA was performed under ⁶⁰Co γ‐irradiation in the presence of 2‐(dodecylthiocarbonothioylthio)‐2‐methylpropionic acid (DDMAT) as the RAFT agent in toluene at room temperature with three [tBA]/[DDMAT] ratios (400, 600 and 1000) and different irradiation times. Radiation‐induced polymerization of tBA displayed controlled free radical polymerization characteristics: a narrow molecular weight distribution (M_w/M_n ~ 1.1), pseudo first order kinetics and controlled molecular weights. The system followed the RAFT polymerization mechanism even at very low amounts of RAFT agent ([tBA]/[DDMAT] = 1000), and molecular weights up to 113 900 with narrow dispersity (Ð =1.06) were obtained. PtBA was further hydrolysed into different amphiphilic PtBA‐co‐poly(acrylic acid) (PAA) copolymers by low (27.5%) and high (77.3%) degrees of hydrolysis. The pH sensitivity of the two copolymers was investigated by dynamic light scattering at pH 2 and pH 9 (above and below the pK_a value of PAA) and their hydrodynamic diameters and zeta potential values were determined. © 2020 Society of Chemical Industry