Top

Polymer Bulletin

Published in:

25-06-2018 | Original Paper

Study of phase separation behavior of poly(N,N-diethylacrylamide) in aqueous solution prepared by RAFT polymerization

Authors: Mei Wu, Haibing Zhang, Hongliang Liu

Published in: Polymer Bulletin | Issue 2/2019

Activate our intelligent search to find suitable subject content or patents.

search-config

AI-assisted search

Off

Abstract

A series of poly(N,N-diethylacrylamide) samples with low molecular weights (1.9 × 10³–5.3 × 10⁴) and narrow polydispersities (below 1.5 and usually lower than 1.25) was synthesized by reversible addition-fragmentation chain transfer polymerization. The phase separation behavior of poly(N,N-diethylacrylamide) in aqueous solution was investigated by turbidimetry, fluorescent probe technology and DSC. It is interesting to find that the lower critical solution temperature (LCST) of the samples increases with increasing molecular weight and remains more or less a constant above a critical molecular weight of 1.2 × 10⁴. At the same time, an inverse dependence of LCST on the concentration was found and this effect was more pronounced for lower molecular weight. To further investigate the novel molecular weight dependence of the LCST, the fluorescent probe study was conducted and the experimental results demonstrated that there was an increase in hydrophobicity when decreasing the molecular weight and increasing the concentration and flower-like micelles were probably formed which can further be proved by TEM.

previous article Controlled drug release behavior of 5-aminosalicylic acid using polyacrylamide grafted oatmeal (OAT-g-PAM): a pH-sensitive drug carrier

next article Compounding sequence as a critical factor in the dispersion of OMMT/hydrocarbon resin/PP-g-MA/PP nanocomposites

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Online-Abonnement

Mit Springer Professional "Wirtschaft+Technik" erhalten Sie Zugriff auf:

über 102.000 Bücher
über 537 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Finance + Banking
Management + Führung
Marketing + Vertrieb
Maschinenbau + Werkstoffe
Versicherung + Risiko

Jetzt Wissensvorsprung sichern!

inform now

Springer Professional "Technik"

Online-Abonnement

Mit Springer Professional "Technik" erhalten Sie Zugriff auf:

über 67.000 Bücher
über 390 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Maschinenbau + Werkstoffe

Jetzt Wissensvorsprung sichern!

inform now

Available only for authorised users

Privalov PL (1979) Stability of proteins small globular proteins. Adv Protein Chem 33:167–241. https://doi.org/10.1016/S0065-3233(08)60460-X CrossRefPubMed

Privalov PL, Creighton TE (eds) (1992) In protein folding. W. H. Freeman & Co, New York, p 83

Privalov PL (1982) Stability of proteins: proteins which do not present a single cooperative system. Adv Protein Chem 35:1–104. https://doi.org/10.1016/S0065-3233(08)60468-4 CrossRefPubMed

Freire E, Murphy KP (1991) Molecular basis of co-operativity in protein folding. J Mol Biol 222:687–698. https://doi.org/10.1016/0022-2836(91)90505-Z CrossRefPubMed

Bychkova VE, Berni R, Rossi GL, Kutyshenko VP, Ptitsyn OB (1992) Retinol-binding protein is in the molten globule state at low pH. Biochemistry 31:7566–7571. https://doi.org/10.1021/bi00148a018 CrossRefPubMed

Schild HG, Tirrell DA (1990) Microcalorimetric detection of lower critical solution temperatures in aqueous polymer solutions. J Phys Chem 94:4352–4356. https://doi.org/10.1021/j100373a088 CrossRef

Shunsuke K, Sokei S, Takahiro O, Tomohiro H, Koichi U, Cheng H, Tetsuo A (2017) NMR studies of water dynamics during sol-to-gel transition of poly(N-isopropylacrylamide) in concentrated aqueous solution. Polymer 109:287–296. https://doi.org/10.1016/j.polymer.2016.12.063 CrossRef

Takanori T, Tomohiro H, Koichi U, Yukiteru K, Taka-Aki A, Tatsuya S, Noboru K, Yasuyuki T (2016) Effects of syndiotacticity on the dynamic and static phase separation properties of poly(N-isopropylacrylamide) in aqueous solution. J Phys Chem B 120:7724–7730. https://doi.org/10.1021/acs.jpcb.6b03200 CrossRef

Fujishige S, Kubota K, Ando I (1989) Phase transition of aqueous solutions of poly(N-isopropylacrylamide) and poly(N-isopropylmethacrylamide). J Phys Chem 93:3311–3313. https://doi.org/10.1021/j100345a085 CrossRef

10.

Kenji M, Tomonari S, Kenichiro K (2016) Liquid–liquid phase separation of N-isopropylpropionamide aqueous solutions above the lower critical solution temperature. Sci Rep 6:24657. https://doi.org/10.1038/srep24657 CrossRef

11.

Wu C, Zhou SQ (1995) Laser light scattering study of the phase transition of poly(N-isopropylacrylamide) in water. 1. Single Chain. Macromolecules 28:8381–8387. https://doi.org/10.1021/ma00128a056 CrossRef

12.

Zeng F, Zheng X, Tong Z (1998) Network formation in poly(N-isopropyl acrylamide)/water solutions during phase separation. Polymer 39:1249–1251. https://doi.org/10.1016/s0032-3861(97)00471-0 CrossRef

13.

Lessard DG, Ousalem M, Zhu XX (2001) Effect of the molecular weight on the lower critical solution temperature of poly(N,N-diethylacrylamide) in aqueous solutions. Can J Chem 79:1870–1874. https://doi.org/10.1139/cjc-79-12-1870 CrossRef

14.

Idziak I, Acoce D, Lessard D, Gravel D, Zhu XX (1999) Thermosensitivity of aqueous solutions of poly(N,N-diethylacrylamide). Macromolecules 32:1260–1263. https://doi.org/10.1021/ma981171f CrossRef

15.

Mitsuhiro M, Ryo W, Takanori T, Taka-Aki A, Tatsuya S, Noboru K, Yasuyuki T (2016) Rapid phase separation in aqueous solution of temperature-sensitive poly(N,N-diethylacrylamide). Macromol Chem Phys 217:2576–2583. https://doi.org/10.1002/macp.201600239 CrossRef

16.

Plate NA, Lebedeva LI, Valuev LI (1999) Lower critical solution temperature in aqueous solutions of N-alkyl-substituted polyacrylamides. Polym J 31:21–27. https://doi.org/10.1295/polymj.31.21 CrossRef

17.

Okano T (1993) Molecular design of temperature-responsive polymers as intelligent materials. Adv Polym Sci 110:179–197. https://doi.org/10.1007/BFb0021133 CrossRef

18.

Miyajima M, Yoshida M, Sato H, Omichi H, Katakai R, Higuchi WI (1994) In vitro release of 9-β-d-arabinofuranosyladenine from thermo-responsive copoly(acryloyl-l-proline methyl ester/styrene) gels. Eur Polym J 30:827–831. https://doi.org/10.1016/0014-3057(94)90011-6 CrossRef

19.

Chen JP, Hsu (1997) Preparations and properties of temperature-sensitive poly(N-isopropylacrylamide)-chymotrypsin conjugates. J Mol Catal B Enzym 2:233–241. https://doi.org/10.1016/s1381-1177(96)00032-x CrossRef

20.

Xue W, Champ S, Huglin MB (2001) New superabsorbent thermoreversible hydrogels. Polymer 42:2247–2250. https://doi.org/10.1016/S0032-3861(00)00550-4 CrossRef

21.

Snowden MJ, Thomas D, Vincent B (1993) Use of colloidal microgels for the absorption of heavy metal and other ions from aqueous solution. Analyst 118:1367–1369. https://doi.org/10.1039/AN9931801367 CrossRef

22.

Heskins M, Guillet JE (1968) Solution properties of poly(N-isopropylacrylamide). J Macromol Sci A2:1441–1455. https://doi.org/10.1080/10601326808051910 CrossRef

23.

Taylor LD, Cerankowski LD (1975) Preparation of films exhibiting a balanced temperature dependence to permeation by aqueous solutions—a study of lower consolute behavior. J Polym Sci 11:2551–2570. https://doi.org/10.1002/pol.1975.170131113 CrossRef

24.

Eliassaf J (1978) Aqueous solutions of poly(N-isopropylacrylamide). J Appl Polym Sci 22:873–874. https://doi.org/10.1002/app.1978.070220328 CrossRef

25.

Lee LT, Cabane B (1997) Effects of surfactants on thermally collapsed poly(N-isopropylacrylamide) macromolecules. Macromolecules 30:6559–6566. https://doi.org/10.1021/ma9704469 CrossRef

26.

Staikos G (1995) Viscometric study of the coil-globule transition of poly(N-isopropylacrylamide) in solutions of surfactant. Macromol Rapid Commun 16:913–917. https://doi.org/10.1002/marc.1995.030161206 CrossRef

27.

Schild HG, Muthukumar M, Tirrell DA (1991) Cononsolvency in mixed aqueous solutions of poly(N-isopropylacrylamide). Macromolecules 24:948–952. https://doi.org/10.1021/ma00004a022 CrossRef

28.

Tong Z, Zeng F, Zheng X (1999) Inverse molecular weight dependence of cloud points for aqueous poly(N-isopropylacrylamide) solutions. Macromolecules 32:4488–4490. https://doi.org/10.1021/ma990062d CrossRef

29.

Otake K, Karaki R, Ebina T, Yokoyama C, Takahashi S (1993) Pressure effects on the aggregation of poly(N-isopropylacrylamide) and poly(N-isopropylacrylamide-co-acrylic acid) in aqueous solutions. Macromolecules 26:2194–2197. https://doi.org/10.1021/ma00061a008 CrossRef

30.

Xue W, Huglin MB, Jones TGJ (2003) Parameters affecting the lower critical solution temperature of linear and crosslinked poly(N-ethylacrylamide) in aqueous media. Macromol Chem Phys 204:1956–1965. https://doi.org/10.1002/macp.200300008 CrossRef

31.

Zheng X, Tong Z, Xie XL, Zeng F (1998) Phase separation in poly(N-isopropyl acrylamide)/water solutions I. cloud point curves and microgelation. Polym J (Tokyo) 30:284–288. https://doi.org/10.1295/polymj.30.284 CrossRef

32.

Elizaveta IT, Vladimir NU, Vanda BL, Stanislav IK, Valentina EB, Oleg BP (1995) ”Domain” coil-globule transition in homopolymers. Macromolecules 28:7519–7524. https://doi.org/10.1021/ma00126a032 CrossRef

33.

Ru GY, Feng JW (2001) Effect of end groups on phase transition and segmental mobility of poly(N-isopropylacrylamide) chains in D₂O. J Polym Sci B Polym Phys 49:749–755. https://doi.org/10.1002/polb.22237 CrossRef

34.

Lazzari M, Liu GJ, Lecommandoux S (2006) Block copolymers in nanoscience. Wiley-VCH, WeinheimCrossRef

35.

Malmsten M (2002) Surfactants and polymers in drug delivery. Marcel Dekker, New YorkCrossRef

36.

Vasilieva YA, Thomas DB, Scales CW, McCormick CL (2004) Direct controlled polymerization of a cationic methacrylamido monomer in aqueous media via the RAFT process. Macromolecules 37:2728–2737. https://doi.org/10.1021/ma035574d CrossRef

37.

McCormick CL, Lowe AB (2004) Aqueous RAFT polymerization: recent developments in synthesis of functional water-soluble (co)polymers with controlled structures. Acc Chem Res 37:312–325. https://doi.org/10.1021/ar0302484 CrossRefPubMed

38.

Thomas DB, Convertine AJ, Myrick LJ, Scales CW, Smith AE, Lowe AB, Vasilieva YA, Ayres N, McCormick CL (2004) Kinetics and molecular weight control of the polymerization of acrylamide via RAFT. Macromolecules 37:8941–8950. https://doi.org/10.1021/ma048199d CrossRef

39.

Donovan MS, Sumerlin BS, Lowe AB, McCormick CL (2002) Controlled/“living” polymerization of sulfobetaine monomers directly in aqueous media via RAFT. Macromolecules 35:8663–8666. https://doi.org/10.1021/ma0209996 CrossRef

40.

Thomas DB, Sumerlin BS, Lowe AB, McCormick CL (2003) Conditions for facile, controlled RAFT polymerization of acrylamide in water. Macromolecules 36:1436–1439. https://doi.org/10.1021/ma025960f CrossRef

41.

Ganachaud F, Monteiro MJ, Gilbert RG (2000) Molecular weight characterization of poly(N-isopropylacrylamide) prepared by living free-radical polymerization. Macromolecules 33:6738–6745. https://doi.org/10.1021/ma0003102 CrossRef

42.

Yang HJ, Cole CA, Monji N, Hoffman AS (1990) Preparation of a thermally phase-separating copolymer, poly(N-isopropylacrylamide-co-N-acryloxysuccinimide), with a controlled number of active esters per polymer chain. J Polym Sci Part A Polym Chem 28:219–226. https://doi.org/10.1002/pola.1990.080280116 CrossRef

43.

Ganachaud F, Monteiro MJ, Gilber RG, Dourges MA, Thang SH, Rizzardo E (2000) Molecular weight characterization of poly(N-isopropylacrylamide) prepared by living free-radical polymerization. Macromolecules 33:6738–6745. https://doi.org/10.1021/ma0003102 CrossRef

44.

Moad G, Rizzardo E, Thang SH (2008) Radical addition–fragmentation chemistry in polymer synthesis. Polymer 49:1079–1131. https://doi.org/10.1016/j.polymer.2007.11.020 CrossRef

45.

Le TP, Moad G, Rizzardo E, Thang SH (1998) PCT Int Appl 9(801):478

46.

Arotcaréna M, Heise B, Ishaya S, Laschewsky A (2002) Switching the Inside and the outside of aggregates of water-soluble block copolymers with double thermoresponsivity. J Am Chem Soc 124:3787–3793. https://doi.org/10.1021/ja012167d CrossRefPubMed

47.

Patterson D (1969) Free volume and polymer solubility. A qualitative view. Macromolecules 2:672–677. https://doi.org/10.1021/ma60012a021 CrossRef

48.

Wang F, Saeki S, Yamaguchi T (1999) Absolute prediction of upper and lower critical solution temperatures in polymer/solvent systems based on corresponding state theory. Polymer 40:2779–2785. https://doi.org/10.1016/S0032-3861(98)00480-7 CrossRef

49.

Liu Y, He JP, Xu JT, Fan DQ, Tang W, Yang YL (2005) Thermal decomposition of cumyl dithiobenzoate. Macromolecules 38:10332–10335. https://doi.org/10.1021/ma0513970 CrossRef

50.

Pamies R, Zhu KZ, Nyström B (2009) Thermal response of low molecular weight poly-(N-isopropylacrylamide) polymers in aqueous solution. Polym Bull 62:487–502. https://doi.org/10.1007/s00289-008-0029-4 CrossRef

51.

Malcolm GN, Rowlinson JS (1957) The thermodynamic properties of aqueous solutions of polyethylene glycol, polypropylene glycol and dioxane. Trans Faraday Soc 53:921–931. https://doi.org/10.1039/TF9575300921 CrossRef

52.

Baulin VA, Halperin A (2002) Concentration dependence of the flory χ parameter within two-state models. Macromolecules 35:6432–6438. https://doi.org/10.1021/ma020296o CrossRef

53.

Matsuyama A, Tanaka F (1990) Theory of solvation-induced reentrant phase separation in polymer solutions. Phys Rev Lett 65:341–344. https://doi.org/10.1103/PhysRevLett.65.341 CrossRefPubMed

54.

De Gennes PG (1991) A model for the tack of molten polymers. CR Acad Sci Paris Ser II 313:1415–1418

55.

Painter PC, Berg LP, Veytsman B, Coleman MM (1997) Intramolecular screening in nondilute polymer solutions. Macromolecules 30:7529–7535. https://doi.org/10.1021/ma970792q CrossRef

56.

Kalyanasundaram K, Thomos JK (1997) Environmental effects on vibronic band intensities in pyrene monomer fluorescence and their application in studies of micellar systems. J Am Chem Soc 99:2039–2044. https://doi.org/10.1021/ja00449a004 CrossRef

57.

Wilhelm M, Zhao CL, Wang YC, Xu RL, Winnik MA (1991) Poly(styrene-ethylene oxide) block copolymer micelle formation in water: a fluorescence probe study. Macromolecules 24:1033–1040. https://doi.org/10.1021/ma00005a010 CrossRef

58.

Turro NJ, Grätzel M, Braun A (1980) Photophysical and photochemical processes in micellar systems. Angew Chem Int Ed Eng 19:675–696. https://doi.org/10.1002/anie.198006751 CrossRef

59.

Tang WT, Hadziioannou G, Smith BA, Frank C (1988) Facile method for labelling polystyrene with various fluorescent dyes. Polymer 29:1313–1317. https://doi.org/10.1016/0032-3861(88)90062-6 CrossRef

60.

Major MD, Torkelson JM, Brearly AM (1990) Fluorescence energy transfer studies of styrene-isoprene diblock copolymer solutions. Macromolecules 23:1700–1710. https://doi.org/10.1021/ma00208a025 CrossRef

61.

Nagasaki Y, Okada T, Scholz C, Lijima M, Kato M, Kataoka K (1998) The reactive polymeric micelle based on an aldehyde-ended poly(ethylene glycol)/poly(lactide) block copolymer. Macromolecules 31:1473–1479. https://doi.org/10.1021/ma971294k CrossRef

62.

Astafieva I, Zhong XF, Eisenberg A (1993) Critical micellization phenomena in block polyelectrolyte solutions. Macromolecules 26:7339–7352. https://doi.org/10.1021/ma00078a034 CrossRef

63.

Itakura M, Inomata K, Nose T (2000) Aggregation behavior of poly(N,N-diethylacrylamide) in aqueous solution. Polymer 41:8681–8687. https://doi.org/10.1016/S0032-3861(00)00267-6 CrossRef

64.

Freitag R, Baltes T, Eggert M (1994) A comparison of thermoreactive water-soluble poly-N,N-diethylacrylamide prepared by anionic and by group transfer polymerization. J Polym Sci Part A Polym Chem 32:3019–3030. https://doi.org/10.1002/pola.1994.080321603 CrossRef

Title: Study of phase separation behavior of poly(N,N-diethylacrylamide) in aqueous solution prepared by RAFT polymerization
Authors: Mei Wu
Haibing Zhang
Hongliang Liu
Publication date: 25-06-2018
Publisher: Springer Berlin Heidelberg
Published in: Polymer Bulletin / Issue 2/2019
Print ISSN: 0170-0839
Electronic ISSN: 1436-2449
DOI: https://doi.org/10.1007/s00289-018-2411-1

Springer Professional

Abstract

Please log in to get access to your license.

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Springer Professional "Technik"

Other articles of this Issue 2/2019

The study of factors affecting the swelling of ultrasound-prepared hydrogel

Preparation of nanocomposites based on styrene/(p-methylstyrene) and SiO2 nanoparticles, through a metallocene–MAO initiating system

Novel nanogels based on hydroxypropyl cellulose–poly(itaconic acid) for adsorption of methylene blue from aqueous solution: process modeling and optimization using response surface methodology

Synthesis, characterization and biocompatible properties of novel silk fibroin/graphene oxide nanocomposite scaffolds for bone tissue engineering application

GHz permittivity of carbon black and polyaniline with styrene–butadiene–styrene composites

A new dual hydrophilic–hydrophobic acrylic resin containing pyridine and 1,3,4-oxadiaxole moieties for removal of Co(II)ions

Premium Partners