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

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.

Eser Adı
[dc.title]
Poly(N-isopropylacrylamide) thermoresponsive cross-linked conjugates containing polymeric soybean oil and/or polypropylene glycol
Yazar
[dc.contributor.author]
Allı, Abdulkadir
Yazar
[dc.contributor.author]
Hazer, Baki
Yayın Yılı
[dc.date.issued]
2008
Yayın Türü
[dc.type]
article
Özet
[dc.description.abstract]
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.
Kayıt Giriş Tarihi
[dc.date.accessioned]
2019-12-23
Açık Erişim Tarihi
[dc.date.available]
2019-12-23
Yayın Dili
[dc.language.iso]
eng
Konu Başlıkları
[dc.subject]
Cross-linked graft copolymer
Konu Başlıkları
[dc.subject]
Macromonomeric initiator
Konu Başlıkları
[dc.subject]
Poly(N-isopropylacrylamide)
Konu Başlıkları
[dc.subject]
Polymeric soybean oil peroxide
Konu Başlıkları
[dc.subject]
Polypropylene glycol
Konu Başlıkları
[dc.subject]
Thermoresponsive polymer
Künye
[dc.identifier.citation]
Allı, A. ve Hazer, B. (2008). Poly(N-isopropylacrylamide) thermoresponsive cross-linked conjugates containing polymeric soybean oil and/or polypropylene glycol. European Polymer Journal, 44(6), 1701-1713. doi:10.1016/j.eurpolymj.2008.04.004
Haklar
[dc.rights]
info:eu-repo/semantics/closedAccess
ISSN
[dc.identifier.issn]
0014-3057
Sponsor YAYINCI
[dc.description.sponsorship]
104M128
Sponsor YAYINCI
[dc.description.sponsorship]
This work was financially supported by Zonguldak Karaelmas University Research Fund and TUBITAK Grant No. 104M128.
İlk Sayfa Sayısı
[dc.identifier.startpage]
1701
Son Sayfa Sayısı
[dc.identifier.endpage]
1713
Dergi Adı
[dc.relation.journal]
European Polymer Journal
Dergi Sayısı
[dc.identifier.issue]
6
Dergi Cilt Bilgisi
[dc.identifier.volume]
44
Tek Biçim Adres
[dc.identifier.uri]
https://dx.doi.org/10.1016/j.eurpolymj.2008.04.004
Tek Biçim Adres
[dc.identifier.uri]
https://hdl.handle.net/20.500.12628/7052
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cross-linked copolymers temperature solution temperatures soybean soluble polymeric PSB-g-PPG-g-PNIPAM PPG-g-PNIPAM PSB-g-PNIPAM PPG-MIM PNIPAM obtain polymerization conjugates radical and/or response characterization respectively (LCST) analysis critical (conjugates chloride initiated higher macroinitiators referred release co-networks) copolymer reduced determined
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