Allı, Sema | Allı, Abdulkadir | Hazer, Baki

Article | 2012 | Journal of Applied Polymer Science124 ( 1 ) , pp.536 - 548

Macromonomer initiators behave as macro cross-linkers, macro initiators, and macromonomers to obtain branched and cross-linked block/graft copolymers. A series of new macromonomer initiators for atom transfer radical polymerization (MIM-ATRP) based on polyethylene glycol (M n = 495D, 2203D, and 4203D) (PEG) were synthesized by the reaction of the hydroxyl end of mono-methacryloyl polyethylene glycol with 2-bromo propanoyl chloride, leading to methacryloyl polyethylene glycol 2-bromo propanoyl ester. Poly (ethylene glycol) functionalized with methacrylate at one end was reacted with 2-bromopropionyl chloride to form a macromonomeric . . .initiator for ATRP. ATRP was found to be a more controllable polymerization method than conventional free radical polymerization in view of fewer cross-linked polymers and highly branched polymers produced from macromonomer initiators as well. In another scenario, ATRP of N-isopropylacrylamide (NIPAM) was initiated by MIM-ATRP to obtain PEG-b-PNIPAM branched block/graft copolymers. Thermal analysis, FTIR, 1H NMR, TEM, and SEM techniques were used in the characterization of the products. They had a thermo-responsive character and exhibited volume phase transition at â 36°C. A plasticizer effect of PEG in graft copolymers was also observed, indicating a lower glass transition temperature than that of pure PNIPAM. Homo and copolymerization kinetics were also evaluated. © 2011 Wiley Periodicals, Inc Daha fazlası Daha az

Allı, Abdulkadir | Allı, Sema | Becer, C. Remzi | Hazer, Baki

Article | 2016 | European Journal of Lipid Science and Technology118 ( 2 ) , pp.279 - 287

Polymeric linoleic asit graft copolymers were synthesized via a nitroxide-mediated radical polymerization (NMRP) method in the presence of 2,2-6,6-tetramethylpiperidinyl-1-oxy (TEMPO). For this purpose, PLina-ox was exposed to polymerization with styrene (Sty) or Sty and pentafluorostyrene (F5Sty) in the presence of TEMPO by NMRP method in order to obtain PLina-g-PSty and PLina-g-PF5Sty-g-PSty graft copolymers with controlled structure and low polydispersity. Chain extension study was evaluated. Principal parameters, such as monomer concentration, initiator concentration, and polymerization time, which effect the polymerization reac . . .tions, were evaluated. The products thus obtained were well characterized by 1H NMR, GPC, and 19F NMR measurements. Practical application: We report for the first time the synthesis of PLina-g-PSty and PLina-g-PSty-g-PF5Sty graft copolymers in the presence of TEMPO. NMRP reactions were performed in the presence of TEMPO in order to obtain graft copolymers with controlled molecular weight and polydispersity. Chain-extension reactions were also successfully carried out because of the activation of TEMPO terminated chain ends of graft copolymers. Pure linoleic acid was auto-oxidized under daylight and air oxygen, yielding peroxidized PLina (PLina-ox). PLina-ox has been used in the polymerization of styrene (Sty) or copolymerization of Sty and pentafluorostyrene (F5Sty). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Daha fazlası Daha az

Allı, Abdulkadir | Hazer, Baki

Article | 2011 | JAOCS, Journal of the American Oil Chemists' Society88 ( 2 ) , pp.255 - 263

To diversify edible oil thermoresponsive polymer composites, polymeric linoleic acid peroxide (PLina) and polymeric linolenic acid peroxide (PLinl) were obtained by the autoxidation of linoleic acid (Lina) and linolenic acid (Linl), respectively. The autoxidation of Lina and Linl under air at room temperature rendered waxy soluble polymeric peroxide, having a soluble fraction in chloroform of more than 91 wt% and containing up to 1.0 wt% of peroxide. The soluble polymeric oil macro-peroxide was used to initiate the free radical polymerization of N-isopropylacrylamide, NIPAM, resulting in PLina-g-PNIPAM and PLinl-g-PNIPAM graft copol . . .ymers, respectively. The PNIPAM content of the graft copolymers was calculated using the elemental nitrogen analysis of graft copolymers. Thermal analysis, FTIR, 1H NMR, and SEM techniques were used in the characterization of the products. The hydrophobic effect of the fatty acid macro peroxides on the thermal response rate of the graft copolymers was investigated by means of swelling-deswelling behaviors in response to temperature change. They have a thermoresponsive character and exhibit a volume phase transition at approximately 27-30 °C, which is 1-4 °C lower than that of pure PNIPAM. A plastizer effect of PLina and PLinl in graft copolymers was observed, indicating a lower glass transition temperature than that of pure PNIPAM. © 2010 AOCS Daha fazlası Daha az

Allı, Abdulkadir | Hazer, Baki

Article | 2009 | Hacettepe Journal of Biology and Chemistry37 ( 1 ) , pp.23 - 31

A new macromonomer initiator for atom transfer radical polymerization (ATRP-MIM) based on polyethylene glycol (Mn= 660 Da) (PEG) was synthesized by the reaction of hydroxyl end of the mono-methacryloyl polyethylene glycol with 2-bromopropanoyl chloride leading to methacryloyl polyethylene glycol 2-bromopropanoyl ester (v-PEG-Br). Poly(ethylene glycol) functionalized with methacrylate at one end was reacted with 2-bromopropionyl chloride to form a macromonomeric initiator for ATRP. Self condensing ATRP-MIM polymerization yielded branched PEG with low cross-linked fraction (3-29 wt%). In the same polymerization condition, self condens . . .ing ATRP-MIM polymerization was found faster than that of conventional free radical macromonomer initiators which behave as macro crosslinker, macro initiator and macromonomer. Besides the PEG obtained has still unreacted double bonds and halides leading to the further branching. In the second step, ATRP of methyl methacrylate was initiated by the MIM-ATRP using the copper coordination complex CuBr / N,N,N’,N’,N’’-pentamethyl diethylenetriamine (PMDETA). The ATRP-MIM and the chloroform soluble branched polymers obtained were characterized by 1H NMR spectroscopy and gel permeation chromatography (GPC). Variation of gel polymer content, molecular weight of the soluble parts and conversion of the monomers with the changing polymerization conditions were also discussed. A new macromonomer initiator for atom transfer radical polymerization (ATRP-MIM) based on polyethylene glycol (Mn= 660 Da) (PEG) was synthesized by the reaction of hydroxyl end of the mono-methacryloyl polyethylene glycol with 2-bromopropanoyl chloride leading to methacryloyl polyethylene glycol 2-bromopropanoyl ester (v-PEG-Br). Poly(ethylene glycol) functionalized with methacrylate at one end was reacted with 2-bromopropionyl chloride to form a macromonomeric initiator for ATRP. Self condensing ATRP-MIM polymerization yielded branched PEG with low cross-linked fraction (3-29 wt%). In the same polymerization condition, self condensing ATRP-MIM polymerization was found faster than that of conventional free radical macromonomer initiators which behave as macro crosslinker, macro initiator and macromonomer. Besides the PEG obtained has still unreacted double bonds and halides leading to the further branching. In the second step, ATRP of methyl methacrylate was initiated by the MIM-ATRP using the copper coordination complex CuBr / N,N,N’,N’,N’’-pentamethyl diethylenetriamine (PMDETA). The ATRP-MIM and the chloroform soluble branched polymers obtained were characterized by 1H NMR spectroscopy and gel permeation chromatography (GPC). Variation of gel polymer content, molecular weight of the soluble parts and conversion of the monomers with the changing polymerization conditions were also discussed Daha fazlası Daha az

Allı, Abdulkadir | Şanal, Timur | Hazer, Baki

Article | 2015 | Turkish Journal of Chemistry39 ( 2 ) , pp.382 - 394

Abstract: Water soluble hydroxylated soya oil polymer was used in the redox polymerization of N-isopropylacrylamide (NIPAM) in order to obtain water-based hydroxylated-soya oil polymer-g-PNIPAM graft copolymer. For this purpose, soya oil was exposed to air under sunlight to obtain autoxidized soya oil polymer (PSy-ox). PSy-ox was allowed to react with diethanol amine to obtain hydroxylated soya oil polymer (hydroxylated-PSy). An ammonium persulfate with hydroxylated-PSy redox initiating system was used in the polymerization of NIPAM in order to obtain thermo-responsive hydroxylated-PSy-g-PNIPAM water-based graft copolymers. The graf . . .t copolymers were characterized using proton nuclear magnetic resonance, Fourier transform infrared~spectroscopy, gel permeation chromatography, thermal gravimetric analysis, and differential scanning calorimetry techniques. The effects of hydroxylated-PSy on the thermal response rate of PNIPAM and the percentage of transmittance in the water of graft copolymers were studied by means of observing UV transmittance behaviors in response to changing temperature. This showed the temperature-responsive property, and exhibited a volume phase transition from 22 °C to 29 °C, while that of PNIPAM was 32 °C. Abstract: Water soluble hydroxylated soya oil polymer was used in the redox polymerization of N-isopropylacrylamide (NIPAM) in order to obtain water-based hydroxylated-soya oil polymer-g-PNIPAM graft copolymer. For this purpose, soya oil was exposed to air under sunlight to obtain autoxidized soya oil polymer (PSy-ox). PSy-ox was allowed to react with diethanol amine to obtain hydroxylated soya oil polymer (hydroxylated-PSy). An ammonium persulfate with hydroxylated-PSy redox initiating system was used in the polymerization of NIPAM in order to obtain thermo-responsive hydroxylated-PSy-g-PNIPAM water-based graft copolymers. The graft copolymers were characterized using proton nuclear magnetic resonance, Fourier transform infrared~spectroscopy, gel permeation chromatography, thermal gravimetric analysis, and differential scanning calorimetry techniques. The effects of hydroxylated-PSy on the thermal response rate of PNIPAM and the percentage of transmittance in the water of graft copolymers were studied by means of observing UV transmittance behaviors in response to changing temperature. This showed the temperature-responsive property, and exhibited a volume phase transition from 22 °C to 29 °C, while that of PNIPAM was 32 °C Daha fazlası Daha az

Balcı, Murat | Allı, Abdulkadir | Hazer, Baki | Güven, Olgun | Cavicchi, Kevin | Çakmak, Mükerrem

Article | 2010 | Polymer Bulletin64 ( 7 ) , pp.691 - 705

Allı, Abdulkadir | Allı, Sema | Becer, C. Remzi | Hazer, Baki

Article | 2014 | JOURNAL OF THE AMERICAN OIL CHEMISTS SOCIETY91 ( 5 ) , pp.849 - 858

One-pot synthesis of graft copolymers by ring-opening polymerization and free radical polymerization using polymeric linoleic acid peroxide (PLina) is reported. Graft copolymers having structures of poly(linoleic acid)-g-polystyrene-g-poly(epsilon-caprolactone) were synthesized from PLina, possessing peroxide groups on the main chain by the combination of free radical polymerization of styrene and ring-opening polymerization of epsilon-caprolactone in one-step. Principal parameters, such as monomer concentration, initiator concentration, and polymerization time, which effect the one-pot polymerization reactions were evaluated. The o . . .btained graft copolymers were characterized by H-1-NMR and DOSY-NMR spectroscopy, gel permeation chromatography, thermal gravimetric analysis and differential scanning calorimetry techniques Daha fazlası Daha az

Gökçen, Muharrem | Yıldırım, Mert | Demir, Ahmet | Allı, Abdulkadir | Allı, Sema | Hazer, Baki

Article | 2014 | Composites Part B: Engineering57 , pp.8 - 12

Au/poly(propylene glycol)-b-polystyrene/n-Si (D1) and Au/poly(propylene glycol)-b-polystyrene(HAuCl4 dispersed)/n-Si (D2) diodes were fabricated and their response to UV illumination was investigated using current-voltage measurements in dark and under various illumination intensities (50-250 mW/cm2). Scanning Electron Microscope micrographs of the diodes were provided for morphological analysis. Main electrical parameters; such as ideality factor, barrier height and reverse saturation current, are calculated using Thermionic Emission and Norde's method, and it was found that they show dependence on UV illumination. Ideality factor . . .values of D1 and D2 diodes in dark is 2.53 and 2.29 whereas they are 3.37 and 3.39 under 100 mW/cm2 UV illumination, respectively. A noticeable effect of UV illumination is the considerable increase of current in the reverse bias region compared with current in dark such that current value increases by ~10 3 times with 100 mW/cm2 UV illumination for both diodes. Furthermore, density distribution profiles of surface states in these diodes were also investigated. © 2013 Elsevier Ltd. All rights reserved Daha fazlası Daha az

Allı, Abdulkadir | Hazer, Baki | Menceloğlu, Yusuf | Süzer, Şefik

Article | 2006 | European Polymer Journal42 ( 4 ) , pp.740 - 750

The new macroazoinitiators containing poly (propylene glycol), (PPG), with molecular weight 400 and 2000, having hydrophilic character, were synthesized and polymerized with styrene to prepare PS-b-PPG block copolymers. Cast films and e-spun films were prepared and contact angles of these films with water drop were measured to examine hydrophilic/hydrophobic behavior of the copolymers. Each e-spun film with average fiber diameters from 0.25 to 2.20 µm was prepared in N,N-dimethylformamide (DMF) under controlled electrospinning process parameters such as polymer concentration, applied voltage and tip-to-collector distance. Scanning e . . .lectron microscope (SEM) images of the electrospun films were taken to determine the fiber diameters. Surface compositions of the block copolymers were also determined by using an electron spectrometer with Mg K? X-rays. NMR, and FT-IR spectroscopic, and GPC measurements were employed to characterize and determine the PPG contents (6-43%). From the results, electrospinning process increased the hydrophilic properties of the block copolymers obtained, compared their cast film forms. Our results suggest that these polymers are favorable in biological applications in cases where high ratio of the surface to volume and hydrophilicity are required simultaneously. Both chemical structure and topology of the films are important in wetting and hydrophobicity. © 2005 Elsevier Ltd. All rights reserved Daha fazlası Daha az

Allı, Abdulkadir | Hazer, Baki

Article | 2008 | European Polymer Journal44 ( 6 ) , pp.1701 - 1713

Synthesis, characterization and solution properties of a new series of the PNIPAM-soybean oil and/or polypropylene glycol, PPG, conjugates (conjugates also referred to as co-networks) have been described. For this purpose free radical polymerization of NIPAM monomer was initiated by macroinitiators based on PSB and/or PPG in order to obtain PSB-g-PNIPAM, PPG-g-PNIPAM and PSB-g-PPG-g-PNIPAM cross-linked graft copolymers. The autooxidation of soybean oil under air at room temperature rendered waxy soluble polymeric soybean oil peroxide associated with cross-linked parts. The soluble polymeric oil macro-peroxide isolated from the cross . . .-linked part was used to initiate the free radical polymerization of NIPAM to give PSB-g-PNIPAM cross-linked copolymer. To obtain PPG-macromonomeric initiator, PPG-MIM, PPG-bis amino propyl ether with Mn 400 (or 2000) Dalton was reacted with 4,4'-azo bis cyanopentanoyl chloride and methacryloyl chloride, respectively. PPG-MIM also initiated the free radical polymerization of NIPAM at 80 °C to yield PPG-g-PNIPAM cross-linked thermoresponsive product. In order to obtain PSB-g-PPG-g-PNIPAM cross-linked triblock copolymer, NIPAM was polymerized by using the mixture of two macroinitiators, PSB and PPG-MIM. PSB contents in the graft copolymers were calculated via elemental analysis of nitrogen in graft copolymers. Thermal analysis, SEM, FTIR and 1H NMR techniques were used in the characterization of the products. The effect of polymeric soybean oil, PSB, and/or PPG on the thermal response rate of poly(N-isopropylacrylamide, PNIPAM, cross-linked-graft copolymers swollen in water has been investigated by means of swelling-deswelling and drug release behaviors against to temperature change. Lower critical solution temperatures (LCST) of the cross-linked PNIPAM conjugates (conjugates also referred to as co-networks) were determined from the curves of swelling degrees versus solution temperatures. The response temperature of the hydrophobically modified PNIPAM conjugates was reduced to 27 °C, 23 °C and 27 °C for PSB-g-PNIPAM, PPG-g-PNIPAM and PSB-g-PPG-g-PNIPAM, respectively. We have found that the graft copolymers were not pH-responsive. In addition, higher pH ranges cause the hydrolysis of the PSB ester linkages, quickly and makes the cross-linked graft copolymers soluble. The fastest shrinking of the gels was observed by loosing water between 65% and 98% at 50 °C. Methyl orange (MO), was used as a model drug, loaded into cross-linked graft copolymers to examine and compare the effects of controlled release at lower and higher temperatures of lower critical solution temperature (LCST). © 2008 Elsevier Ltd. All rights reserved Daha fazlası Daha az

Allı, Abdulkadir | Hazer, Baki

Proceedings | 2009 | ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY237 , pp.1701 - 1713

WOS: 000207857807440

Allı, Abdulkadir | Hazer, Baki | Adamus, Grażyna | Kowalczuk, Marek

Book Part | 2017 | Handbook of Telechelic Polyesters, Polycarbonates, and Polyethers , pp.65 - 114

Poly(3-hydroxyalkanoate)s, PHAs, are natural polyesters collected as intracellular granules as a result of a metabolic stress upon unbalanced growth, owing to a limited supply of a necessary nutrient and to the presence of an excess of a carbon source [1,2,3,4,5,6,7-8]. PHAs have material properties ranging from rigid and highly crystalline to elastic, rather amorphous, and flexible. Many studies have been reported on the modification reactions of PHAs to enhance their mechanical and thermal properties [9,10,11,12,13,14,15,16-17]. © 2017 by Pan Stanford Publishing Pte. Ltd.