Poly(<i>N</i>-isopropylacrylamide) thermoresponsive cross-linked conjugates containing polymeric soybean oil and/or polypropylene glycol
A Alli, B Hazer
article (Uluslararası, Hakemli) | Yazar(lar): A Alli, B Hazer | Yıl: 2008 | Dergi/Kurum: EUROPEAN POLYMER JOURNAL | İndeks: WOS.SCI | DOI: 10.1016/j.eurpolymj.2008.04.004 | Anahtar Kelimeler: thermoresponsive polymer, polymeric soybean oil peroxide, macromonomeric initiator, poly(N-isopropylacrylamide), polypropylene g
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 autooxiclation 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 degrees 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 H-1 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 degrees C, 23 degrees C and 27 degrees 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 degrees 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). (C) 2008 Elsevier Ltd. All rights reserved.