English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  New bio-based polymers : synthesis and polymerization of cystine-based macrocycles

Behrendt, F. (2018). New bio-based polymers: synthesis and polymerization of cystine-based macrocycles. PhD Thesis, Universität, Potsdam.

Item is

Files

show Files
hide Files
:
Thesis.pdf (Any fulltext), 7MB
 
File Permalink:
-
Name:
Thesis.pdf
Description:
-
OA-Status:
Visibility:
Restricted (Max Planck Institute of Colloids and Interfaces, MTKG; )
MIME-Type / Checksum:
application/pdf
Technical Metadata:
Copyright Date:
-
Copyright Info:
-
License:
-

Locators

show

Creators

show
hide
 Creators:
Behrendt, Felix1, Author           
Affiliations:
1Helmut Schlaad, Kolloidchemie, Max Planck Institute of Colloids and Interfaces, Max Planck Society, ou_1863316              

Content

show
hide
Free keywords: polymers; ADMET; ROMP; disulfide; macrocycles; ring-opening polymerization; amino acids
 Abstract: Redox-responsive polymers, such as poly(disulfide)s, are a versatile class of polymers with potential applications including gene- and drug-carrier systems. Their degradability under reductive conditions allows for a controlled response to the different redox states that are present throughout the body. Poly(disulfide)s are typically synthesized by step growth polymerizations. Step growth polymerizations, however, may suffer from low conversions and therefore low molar masses, limiting potential applications. The purpose of this thesis was therefore to find and investigate new synthetic routes towards the synthesis of amino acid-based poly(disulfide)s. The different routes in this thesis include entropy-driven ring opening polymerizations of novel macrocyclic monomers, derived from cystine derivatives. These monomers were obtained with overall yields of up to 77% and were analyzed by mass spectrometry as well as by 1D and 2D NMR spectroscopy. The kinetics of the entropy-driven ring-opening metathesis polymerization (ED-ROMP) were thoroughly investigated in dependence of temperature, monomer concentration, and catalyst concentration. The polymerization was optimized to yield poly(disulfide)s with weight average molar masses of up to 80 kDa and conversions of ~80%, at the thermodynamic equilibrium. Additionally, an alternative metal free polymerization, namely the entropy-driven ring-opening disulfide metathesis polymerization (ED-RODiMP) was established for the polymerization of the macrocyclic monomers. The effect of different solvents, concentrations and catalyst loadings on the polymerization process and its kinetics were studied. Polymers with very high weight average molar masses of up to 177 kDa were obtained. Moreover, various post-polymerization reactions were successfully performed. This work provides the first example of the homopolymerization of endo-cyclic disulfides by ED-ROMP and the first substantial study into the kinetics of the ED-RODiMP process.

Details

show
hide
Language(s): eng - English
 Dates: 2018
 Publication Status: Accepted / In Press
 Pages: vii, 153 S.
 Publishing info: Potsdam : Universität
 Table of Contents: -
 Rev. Type: -
 Identifiers: URN: https://nbn-resolving.org/urn:nbn:de:kobv:517-opus4-418316
 Degree: PhD

Event

show

Legal Case

show

Project information

show

Source

show