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Functional Degradable Polymers: from the monomeric point of view
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Degradable polymers is key, within the future vison, of creating a sustainable society were all aspects, cradle to grave, can be realized in a sustainable way. It is imperative to consider, how the monomer is formed, its polymerization, the material properties created and the final degradation behavior. In this thesis, the major focus will be placed on the three former aspects from the vantage point of the monomer. The immense variety of different monomers available within the realm of polymer chemistry necessitates a logical division among them. Herein, we make such a division according to their respective inherent thermodynamic properties and how these translate into the synthetic behavior of the corresponding polymers. These divisions are as follows: stable monomers (monomers that resist becoming polymers), meta-stable monomers (monomers for which temperature is of immense importance during polymer formation), and unstable monomers (monomers that desire to be in the polymeric state). From this viewpoint, three different investigations were conducted, thereby demonstrating the inherent advantages and disadvantages of each type together with the importance of using the “right” catalyst for the “right” monomer.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. , 75 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:26
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-166872ISBN: 978-91-7595-585-8 (print)OAI: oai:DiVA.org:kth-166872DiVA: diva2:812909
Public defence
2015-06-12, D2, Lindstedtsvägen 5, KTH, Stockholm, 09:00 (English)
Opponent
Supervisors
Note

QS C 20150222

Available from: 2015-05-22 Created: 2015-05-20 Last updated: 2015-05-22Bibliographically approved
List of papers
1. Establishing α-bromo-γ-butyrolactone as a platform for synthesis of functional aliphatic polyesters-bridging the gap between ROP and SET-LRP
Open this publication in new window or tab >>Establishing α-bromo-γ-butyrolactone as a platform for synthesis of functional aliphatic polyesters-bridging the gap between ROP and SET-LRP
2014 (English)In: Polymer Chemistry, ISSN 1759-9954, E-ISSN 1759-9962, Vol. 5, no 12, 3847-3854 p.Article in journal (Refereed) Published
Abstract [en]

Utilizing a-bromo-g-butyrolactone (aBrgBL) as a comonomer with 3-caprolactone (3CL) or L-lactide (LLA)produces copolymers with active and available grafting sites, e.g., for SET-LRP, where the choice of thegrafting monomers is limited only by one's imagination. This was deduced by utilizing a wide range ofdifferent acrylates of varying polarities and was realized with the aid of a fluorinated alcohol, 2,2,2-trifluoroethanol, which acts as a universal solvent for both the hydrophobic macroinitiators and thegrafting monomers. Using aBrgBL successfully provides a simple route to merge the two polymerizationmethodologies, ROP and SET-LRP. aBrgBL inherently meets all of the prerequisites to act as a platformmonomer for the synthesis of functional aliphatic polyesters, i.e., it is inexpensive, available, and able toform isolated grafting sites along the polymer chain. The copolymerization of aBrgBL together with twoof the most commonly used cyclic ester monomers, 3-CL and LLA, proceeds with a high degree ofcontrol and a linear relationship between the feed ratio of aBrgBL and its composition in the copolymer.The formation of isolated units of aBrgBL in the copolymer is visualized by the reactivity ratios of thecopolymerization reactions and confirmed by 13C-NMR spectroscopy. The incorporation of isolatedaBrgBL is the feature that makes this class of copolymers unique, and it can be considered to provide aroute to the “perfect graft copolymer” with a degradable backbone.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2014
National Category
Polymer Technologies
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-145189 (URN)10.1039/C4PY00148F (DOI)000336804800015 ()2-s2.0-84901352273 (Scopus ID)
Note

QC 20140627

Available from: 2014-05-14 Created: 2014-05-14 Last updated: 2017-12-05Bibliographically approved
2. epsilon-Decalactone: A Thermoresilient and Toughening Comonomer to Poly(L-lactide)
Open this publication in new window or tab >>epsilon-Decalactone: A Thermoresilient and Toughening Comonomer to Poly(L-lactide)
2013 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 14, no 8, 2883-2890 p.Article in journal (Refereed) Published
Abstract [en]

The renewable monomer epsilon-decalactone is an excellent partner to L-lactide, where their copolymers overcome inherent drawbacks of polylactide, such as low thermal stability and brittleness. epsilon-Decalactone is a seven-membered lactone that was successfully polymerized with Sn(Oct)(2) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene into both an amorphous homopolymer and copolymers with high molecular weight, low dispersity, and predicted macromolecular architecture. The thermoresilient nature of epsilon-decalactone is reflected in a high polymerization ceiling temperature and increased thermal stability for the prepared copolymers. The high ceiling temperature enables easy modulation of the polymerization rate via temperature while maintaining architectural control. The apparent rate constant was increased 15-fold when the temperature was increased from 110 to 150 degrees C. Copolymers of L-lactide and epsilon-decalactone, either with the latter as a central block in triblock polymers or with randomly positioned monomers, exhibited exceptionally tough material characteristics. The triblock copolymer had an elongation-at-break 250 times greater than that of pure poly(L-lactide). The toughness of the copolymers is attributed to the flexible nature of the polymer derived from the monomer epsilon-decalactone and to the segment immiscibility. These properties result in phase separation to soft and hard domains, which provides the basis for the elastomeric behavior.

National Category
Biochemistry and Molecular Biology
Identifiers
urn:nbn:se:kth:diva-128481 (URN)10.1021/bm400733e (DOI)000323143700049 ()2-s2.0-84881596775 (Scopus ID)
Funder
EU, European Research Council, 246776
Note

QC 20130912

Available from: 2013-09-12 Created: 2013-09-12 Last updated: 2017-12-06Bibliographically approved
3. Ring-Closing Depolymerization: A Powerful Tool for Synthesizing the Allyloxy-Functionalized Six-Membered Aliphatic Carbonate Monomer 2-Allyloxymethyl-2-ethyltrimethylene Carbonate
Open this publication in new window or tab >>Ring-Closing Depolymerization: A Powerful Tool for Synthesizing the Allyloxy-Functionalized Six-Membered Aliphatic Carbonate Monomer 2-Allyloxymethyl-2-ethyltrimethylene Carbonate
2014 (English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 47, no 18, 6189-6195 p.Article in journal (Refereed) Published
Abstract [en]

Ring-dosing depolymerization is demonstrated to be a powerful synthetic methodology for the formation of six-membered functional aliphatic carbonate monomers, providing a rapid, straightforward, inexpensive, and green route for obtaining six-membered functional aliphatic carbonate monomers at a scale greater than 100g. The utility of this technique was observed via the synthesis of the allyloxy-functionalized six-membered cyclic carbonate monomer 2-allyloxymethyl-2-ethyltrimethylene carbonate (AOMEC). The synthesis was performed in a one-pot bulk reaction, starting from trimethylolpropane allyl ether, diethyl carbonate, and NaH, resulting in a final AOMEC yield of 63%. The synthetic methodology is based upon the reversible nature of this class of polymers. The anionic environment produced by NaH was observed to mediate the monomer equilibrium concentration; thus, an additional catalyst is not required to induce depolymerization. 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) was demonstrated to be a very active catalyst for the ring-opening polymerization (ROP) of AOMEC, resulting in a rapid (k(p)(aPP) =28.2 s(-1)) and controlled polymerization with a low dispersity D = 1.2). The availability and activity of the functionality of poly(AOMEC)s were established through subsequent postpolymerization functionalization via the UV-initiated thiol-ene chemistry of poly(AOMEC) with 1-dodecanethiol and benzophenone as a radical initiator. The functionalization proceeded with high control and with a linear relation between the molecular weight and conversion of the unsaturation, revealing the high orthogonality of the reaction and the stability of the carbonate backbone. Hence, as a synthetic methodology, depolymerization provides a straightforward and simple approach for the synthesis of the highly versatile functional carbonate AOMEC. In addition, formation of the monomer does not require any solvents, reactive ring-dosing reagents, or transition-metal-based depolymerization catalysts, thereby providing a "greener" route for obtaining functional carbonate monomers and polymers.

Keyword
Opening Polymerization, Cyclic Carbonates, 2, 2-Dimethyltrimethylene Carbonate, Efficient Synthesis, Organic Carbonates, Copolymers, Esters, Polycarbonates, Mechanism, Polymers
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-154373 (URN)10.1021/ma5012304 (DOI)000342184700006 ()2-s2.0-84918537979 (Scopus ID)
Funder
EU, European Research Council, 246776
Note

QC 20141021

Available from: 2014-10-21 Created: 2014-10-20 Last updated: 2017-12-05Bibliographically approved
4. Macromolecular Design via an Organocatalytic, Monomer-Specific and Temperature-Dependent "On/Off Switch": High Precision Synthesis of Polyester/Polycarbonate Multiblock Copolymers
Open this publication in new window or tab >>Macromolecular Design via an Organocatalytic, Monomer-Specific and Temperature-Dependent "On/Off Switch": High Precision Synthesis of Polyester/Polycarbonate Multiblock Copolymers
2015 (English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 48, no 6, 1703-1710 p.Article in journal (Refereed) Published
Abstract [en]

The employment of a monomer-specific on/off switch was used to synthesize a nine-block copolymer with a predetermined molecular weight and narrow distribution (D = 1.26) in only 2.5 h. The monomers consisted of a six-membered cyclic carbonate (i.e., 2-allyloxymethyl-2-ethyl-trimethylene carbonate (AOMEC)) and epsilon-caprolactone (epsilon CL), which were catalyzed by 1,5,7-triazabicyclo[4.4.0]-dec-5-ene (TBD). The dependence of polymerization rate with temperature was different for the two monomers. Under similar reaction conditions, the ratio of the apparent rate constant of AOMEC and epsilon CL [k(p)(app)(AOMEC)/k(p)(app)(epsilon CL)] changes from 400 at T = -40 degrees C to 50 at T = 30 degrees C and 10 at T = 100 degrees C. Therefore, by decreasing the copolymerization temperature from 30 degrees C to -40 degrees C, the conversion of epsilon CL can be switched off, and by increasing the temperature to 30 degrees C, the conversion of epsilon CL can be switched on again. The addition of AOMEC at T = -40 degrees C results in the formation of a pure carbonate block. The cyclic addition of AOMEC to a solution of epsilon CL along with a simultaneous temperature change leads to the formation of multiblock copolymers. This result provides a new straightforward synthetic route to degradable multiblock copolymers, yielding new interesting materials with endless structural possibilities.

National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-165214 (URN)10.1021/acs.macromol.5b00254 (DOI)000351792200011 ()2-s2.0-84925424349 (Scopus ID)
Note

QC 20150506

Available from: 2015-05-06 Created: 2015-04-24 Last updated: 2017-12-04Bibliographically approved

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