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Linear poly(ethylene imine)s by acidic hydrolysis of poly(2-oxazoline)s: kinetic screening, thermal properties, and temperature-induced solubility transitions

Hanneke ML Lambermont-Thijs, Friso S van der Woerdt, Anja Baumgaertel, Lies Bonami UGent, Filip Du Prez UGent, Ulrich S Schubert and Richard Hoogenboom UGent (2010) MACROMOLECULES. 43(2). p.927-933
abstract
The kinetics for the acidic hydrolysis of two water-soluble poly(2-oxazoline)s with methyl and ethyl substituents were investigated. It could be observed that poly(2-ethyl-2-oxazoline) (PEtOx) and poly(2-methyl-2-oxazoline) (PMeOx) are hydrolyzed following a linear relation with time. Various polymer lengths and concentrations were investigated, revealing that both parameters had 110 influence on the hydrolysis kinetics. Comparison between PEtOx and PMeOx revealed that the smaller PMeOx side group could be removed faster. Furthermore, a series of linear poly(ethylene imine) (PEI) were synthesized with varying M/I ratio from 5 to 200 to elucidate structure-property relations. Thermal measurements indicated that the T-g of PMeOx was increasing up to a M/I ratio of 100. PEI on the other hand, is crystalline and exhibits a melting temperature which shows it similar increase with M/I ratio as observed for the T-g of PMeOx. Solubility measurements in water and water/ethanol mixtures indicated a solubility transition to a soluble state at elevated temperatures. The solubility transition was observed to fit with the melting temperature, indicating that the PEI crystals need to melt in solution before solubilizing. Moreover, when adding ethanol to the water solution, the formed crystals are less stable due to the improved solubility of PEI in ethanol, causing a decrease in cloud point temperature. Upon cooling, PEI crystallizes at much lower temperatures compared to dissolution, causing a large hysteresis presumably due to extensive intermolecular hydrogen bonding, which also plays a role in the formation of the hydrate crystals.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
SYSTEM, POLY(2-ETHYL-2-OXAZOLINE), WATER, POLYMERS, 2-METHYL-2-OXAZOLINE, KeyWords Plus: POLYMERIZATION, COPOLYMERS, POLYETHYLENIMINE, VECTOR, 2-ETHYL-2-OXAZOLINE
journal title
MACROMOLECULES
Macromolecules
volume
43
issue
2
pages
927 - 933
Web of Science type
Article
Web of Science id
000273618100045
JCR category
POLYMER SCIENCE
JCR impact factor
4.837 (2010)
JCR rank
5/78 (2010)
JCR quartile
1 (2010)
ISSN
0024-9297
DOI
10.1021/ma9020455
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
941903
handle
http://hdl.handle.net/1854/LU-941903
date created
2010-05-04 12:20:51
date last changed
2010-09-02 09:46:23
@article{941903,
  abstract     = {The kinetics for the acidic hydrolysis of two water-soluble poly(2-oxazoline)s with methyl and ethyl substituents were investigated. It could be observed that poly(2-ethyl-2-oxazoline) (PEtOx) and poly(2-methyl-2-oxazoline) (PMeOx) are hydrolyzed following a linear relation with time. Various polymer lengths and concentrations were investigated, revealing that both parameters had 110 influence on the hydrolysis kinetics. Comparison between PEtOx and PMeOx revealed that the smaller PMeOx side group could be removed faster. Furthermore, a series of linear poly(ethylene imine) (PEI) were synthesized with varying M/I ratio from 5 to 200 to elucidate structure-property relations. Thermal measurements indicated that the T-g of PMeOx was increasing up to a M/I ratio of 100. PEI on the other hand, is crystalline and exhibits a melting temperature which shows it similar increase with M/I ratio as observed for the T-g of PMeOx. Solubility measurements in water and water/ethanol mixtures indicated a solubility transition to a soluble state at elevated temperatures. The solubility transition was observed to fit with the melting temperature, indicating that the PEI crystals need to melt in solution before solubilizing. Moreover, when adding ethanol to the water solution, the formed crystals are less stable due to the improved solubility of PEI in ethanol, causing a decrease in cloud point temperature. Upon cooling, PEI crystallizes at much lower temperatures compared to dissolution, causing a large hysteresis presumably due to extensive intermolecular hydrogen bonding, which also plays a role in the formation of the hydrate crystals.},
  author       = {Lambermont-Thijs, Hanneke ML and van der Woerdt, Friso S and Baumgaertel, Anja and Bonami, Lies and Du Prez, Filip and Schubert, Ulrich S and Hoogenboom, Richard},
  issn         = {0024-9297},
  journal      = {MACROMOLECULES},
  keyword      = {SYSTEM,POLY(2-ETHYL-2-OXAZOLINE),WATER,POLYMERS,2-METHYL-2-OXAZOLINE,KeyWords Plus: POLYMERIZATION,COPOLYMERS,POLYETHYLENIMINE,VECTOR,2-ETHYL-2-OXAZOLINE},
  language     = {eng},
  number       = {2},
  pages        = {927--933},
  title        = {Linear poly(ethylene imine)s by acidic hydrolysis of poly(2-oxazoline)s: kinetic screening, thermal properties, and temperature-induced solubility transitions},
  url          = {http://dx.doi.org/10.1021/ma9020455},
  volume       = {43},
  year         = {2010},
}

Chicago
Lambermont-Thijs, Hanneke ML, Friso S van der Woerdt, Anja Baumgaertel, Lies Bonami, Filip Du Prez, Ulrich S Schubert, and Richard Hoogenboom. 2010. “Linear Poly(ethylene Imine)s by Acidic Hydrolysis of Poly(2-oxazoline)s: Kinetic Screening, Thermal Properties, and Temperature-induced Solubility Transitions.” Macromolecules 43 (2): 927–933.
APA
Lambermont-Thijs, H. M., van der Woerdt, F. S., Baumgaertel, A., Bonami, L., Du Prez, F., Schubert, U. S., & Hoogenboom, R. (2010). Linear poly(ethylene imine)s by acidic hydrolysis of poly(2-oxazoline)s: kinetic screening, thermal properties, and temperature-induced solubility transitions. MACROMOLECULES, 43(2), 927–933.
Vancouver
1.
Lambermont-Thijs HM, van der Woerdt FS, Baumgaertel A, Bonami L, Du Prez F, Schubert US, et al. Linear poly(ethylene imine)s by acidic hydrolysis of poly(2-oxazoline)s: kinetic screening, thermal properties, and temperature-induced solubility transitions. MACROMOLECULES. 2010;43(2):927–33.
MLA
Lambermont-Thijs, Hanneke ML, Friso S van der Woerdt, Anja Baumgaertel, et al. “Linear Poly(ethylene Imine)s by Acidic Hydrolysis of Poly(2-oxazoline)s: Kinetic Screening, Thermal Properties, and Temperature-induced Solubility Transitions.” MACROMOLECULES 43.2 (2010): 927–933. Print.