Synthesis and characterization of stereoregular poly(N-ethylacrylamide) hydrogel by using Y(OTf)(3) Lewis acid

Biswas, Chandra Sekhar | Hazer, Baki

Article | 2015 | COLLOID AND POLYMER SCIENCE293 ( 1 ) , pp.143 - 152

Macroporous poly(N-ethylacrylamide) (PNEAM) hydrogels have been prepared in a methanol-water (1:1, v/v) mixture in the presence of 0, 0.05, 0.1, 0.15, and 0.2 M yttrium trifluoromethanesulfonate [Y(OTf)(3)] Lewis acid (LA) concentrations. SEM micrographs show that the resulted hydrogels are highly porous. Swelling ratios of all the hydrogels in water decrease with the increase in the temperature, and the hydrogels show lower critical solution temperature (LCST) volume phase transition at around 75 A degrees C. LCST of PNEAM homopolymers gradually increases with the increase in the isotacticity of the polymers. Moreover, the hydrogel . . .s show cononsolvency in different methanol-water mixtures at 50 A degrees C. Deswelling rate of the hydrogels prepared in the presence of LA is higher than the gel prepared in the absence of LA and this rate increases with increase in the LA concentration. The reswelling rate of the hydrogels also follows the same order, that is reswelling rate also increases with the increase in the LA loading in the gels. All these results are explained on the basis of the formation of the highly porous hydrogels with a higher isotactic PNEAM chain segment in a methanol-water mixture in the presence of LA Daha fazlası Daha az

Poly(N-isopropylacrylamide) thermoresponsive cross-linked conjugates containing polymeric soybean oil and/or polypropylene glycol

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

Synthesis of PNIPAM-PEG Double hydrophilic polymers using oleic acid macro peroxide initiator

Hazer, Baki | Ayyıldız, Elif | Bahadır, Faruk

Article | 2017 | JOURNAL OF THE AMERICAN OIL CHEMISTS SOCIETY94 ( 9 ) , pp.1141 - 1151

This work refers to the synthesis of a new double hydrophilic thermo-responsive polymer using fatty acid macroperoxide initiator, N-isopropyl acryl amide (NIPAM) and polyethylene glycol with two primary amine ends (PEGNH2). For this purpose, oleic acid was spread out onto a petri dish and exposed to air oxygen at room temperature for 2 months. The obtained fatty acid macro-peroxide initiator was used in the free radical polymerization of NIPAM in the presence of PEGNH2. Poly oleic acid-g-PNIPAM-g-PEG graft copolymers were successfully obtained. Lower critical solution temperature (LCST) of the graft copolymer was determined by using . . . UV-Vis spectrometry with a sensible heating unit. Morphology of the fractured surface of the double hydrophilic polymers was visualized by using SEM micrographs. Graft copolymers with LCST close to body temperature were obtained by changing PEG inclusion. Structural characterization, thermal analysis and size exclusion chromatography measurements of the obtained products were done Daha fazlası Daha az

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