Thermally Responsive Amphiphilic Conetworks and Gels Based on Poly(N-isopropylacrylamide) and Polyisobutylene

被引:77
作者
Kali, Gergely [1 ]
Vavra, Szilvia [2 ]
Laszlo, Krisztina [2 ]
Ivan, Bela [1 ]
机构
[1] Hungarian Acad Sci, Dept Polymer Chem, Inst Mat & Environm Chem, Res Ctr Nat Sci, H-1525 Budapest, Hungary
[2] Budapest Univ Technol & Econ, Dept Phys Chem & Mat Sci, H-1521 Budapest, Hungary
基金
匈牙利科学研究基金会;
关键词
SOLID-STATE NMR; N-ISOPROPYLACRYLAMIDE; COPOLYMER MICELLES; POLYMER CONETWORKS; MODEL CONETWORKS; METHACRYLIC-ACID; CELL-CULTURE; HYDROGELS; NETWORKS; TEMPERATURE;
D O I
10.1021/ma400535r
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Novel amphiphilic conetworks (APCN) consisting of thermoresponsive poly(N-isoproplyacrylamide) (PNiPAAm) cross-linked by hydrophobic methacrylate-telechelic polyisobutylene (MA-PIB-MA) were successfully synthesized in a broad composition range. The resulting PNiPAAm-l-PIB conetworks (l stands for linked by) were obtained by radical copolymerization of NiPAAm with MA-PIB-MA in tetrahydrofuran, a cosolvent for all the components. Low amounts of extractables substantiated efficient network formation. The composition dependent two glass transition temperatures (T-g) by DSC analysis indicate microphase separation of the cross-linked components without mixed phases. It was found that the PNiPAAm-l-PIB conetworks are uniformly swellable in both water and n-hexane; i.e., these new materials behave either as hydrogels or as hydrophobic gels in aqueous or nonpolar media, respectively. The uniform swelling in both polar and nonpolar solutes indicates cocontinuous (bicontinuous) phase morphology. The equilibrium swelling degrees (R) depend on composition, that is, the higher the PIB content, the lower the R in water and the higher in n-hexane. The PNiPAAm phase keeps its thermoresponsive behavior in the conetworks as shown by significant decrease of the swelling degree in water between 20 and 35 degrees C. The lower critical solubility temperature (LCST) values determined by DSC are found to decrease from 34.1 degrees C (for the pure PNiPAAm homopolymer) to the range of 25-28 degrees C in the conetworks, and the extent of the LCST decrease is proportional with the PIB content. Deswelling-swelling, i.e., heating-cooling, cycle indicates insignificant hysteresis in these new thermoresponsive materials. This indicates that PNiPAAm-l-PIB conetworks with predetermined and thermoresponsive swelling behavior can be designed and utilized in several advanced applications on the basis of results obtained in the course of this study.
引用
收藏
页码:5337 / 5344
页数:8
相关论文
共 92 条
[1]   Stimuli responsive polymers for biomedical applications [J].
Alarcón, CDH ;
Pennadam, S ;
Alexander, C .
CHEMICAL SOCIETY REVIEWS, 2005, 34 (03) :276-285
[2]  
[Anonymous], 1992, HANSER MUNICH
[3]   Singular thermosensitivity of polymethyl methacrylate/poly-N-isopropylacrylamide conetworks prepared by a facile synthetic route [J].
Aranaz, Inmaculada ;
Carrasco, Sergio ;
Tardajos, Myriam G. ;
Elvira, Carlos ;
Reinecke, Helmut ;
Lopez, Daniel ;
Gallardo, Alberto .
POLYMER CHEMISTRY, 2011, 2 (03) :709-713
[4]   Antibiofouling Hybrid Dendritic Boltorn/Star PEG Thiol-ene Cross-Linked Networks [J].
Bartels, Jeremy W. ;
Imbesi, Philip M. ;
Finlay, John A. ;
Fidge, Christopher ;
Ma, Jun ;
Seppala, Jonathan E. ;
Nystrom, Andreas M. ;
Mackay, Michael E. ;
Callow, James A. ;
Callow, Maureen E. ;
Wooley, Karen L. .
ACS APPLIED MATERIALS & INTERFACES, 2011, 3 (06) :2118-2129
[5]   Prediction of glass transition temperatures: Binary blends and copolymers [J].
Brostow, Witold ;
Chiu, Rachel ;
Kalogeras, Ioannis M. ;
Vassilikou-Dova, Aglaia .
MATERIALS LETTERS, 2008, 62 (17-18) :3152-3155
[6]   Thermoresponsive surfaces for cell culture and enzyme-free cell detachment [J].
Brun-Graeppi, Amanda K. Andriola Silva ;
Richard, Cyrille ;
Bessodes, Michel ;
Scherman, Daniel ;
Merten, Otto-Wilhelm .
PROGRESS IN POLYMER SCIENCE, 2010, 35 (11) :1311-1324
[7]   Nanophase separated amphiphilic conetwork coatings and membranes [J].
Bruns, N ;
Scherble, J ;
Hartmann, L ;
Thomann, R ;
Iván, B ;
Mülhaupt, R ;
Tiller, JC .
MACROMOLECULES, 2005, 38 (06) :2431-2438
[8]   Amphiphilic network as nanoreactor for enzymes in organic solvents [J].
Bruns, N ;
Tiller, JC .
NANO LETTERS, 2005, 5 (01) :45-48
[9]   Amphiphilic conetworks as activating carriers for the enhancement of enzymatic activity in supercritical CO2 [J].
Bruns, Nico ;
Bannwarth, Willi ;
Tiller, Joerg C. .
BIOTECHNOLOGY AND BIOENGINEERING, 2008, 101 (01) :19-26
[10]   Amphiphilic Polymer Conetworks as Matrices for Phase Transfer Reactions [J].
Bruns, Nico ;
Hanko, Michael ;
Dech, Stephan ;
Ladisch, Reinhild ;
Tobis, Jan ;
Tiller, Joerg C. .
POLYMER NETWORKS: SYNTHESIS, PROPERTIES, THEORY AND APPLICATIONS, 2010, 291-292 :293-+