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Ring-opening polymerization from cellulose for biocomposite applications
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

There is an emerging interest in the development of sustainable materials with high performance. Cellulose is promising in this regard as it is a renewablere source with high specific properties, which can be utilized as strong reinforcements in novel biocomposites. However, to fully exploit the potential ofcellulose, its inherent hydrophilic character has to be modified in order toimprove the compatibility and interfacial adhesion with the more hydrophobicpolymer matrices commonly used in composites.In this study, the grafting of poly(ε-caprolactone) (PCL) and poly(L-lactide)(PLLA) from cellulose surfaces, via ring-opening polymerization (ROP) of ε-caprolactone and L-lactide, was investigated. Both macroscopic and nano-sizedcellulose were explored, such as filter paper, microfibrillated cellulose (MFC),MFC-films, and regenerated cellulose spheres. It was found that thehydrophobicity of the cellulose surfaces increased with longer graft lengths, andthat polymer grafting rendered a smoother surface morphology.To improve the grafting efficiency in the ROP from filter paper, both covalent(bis(methylol)propionic acid, bis-MPA) and physical pretreatment (xyloglucanbisMPA)were explored. The highest grafting efficiency was obtained with ROPfrom the bis-MPA modified filter papers, which significantly increased amountof polymer on the surface, i.e. the thickness of the grafted polymer layer.MFC was grafted with PCL to different molecular weights. The dispersability innon-polar solvent was obviously improved for the PCL grafted MFC, incomparison to neat MFC, and the stability of the MFC suspensions was better maintained with longer grafts. PCL based biocomposites were prepared from neat MFC and PCL grafted MFCwith different graft lengths. The polymer grafting improved the mechanical properties of the composites, and the best reinforcing effect was obtained when PCL grafted MFC with the longest grafts were used as reinforcement.A bilayer laminate consisting of PCL and MFC-films grafted with different PCL graft lengths displayed a gradual increase in the interfacial adhesion with increasing graft length.The effect of grafting on the adhesion was also investigated via colloidal probeatomic force microscopy at different temperatures and time in contact. A significant improvement in the adhesion was observed after polymer grafting.

Place, publisher, year, edition, pages
Stockholm: KTH , 2009. , 68 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2009:24
Keyword [en]
cellulose, ring-opening polymerization, polycaprolactone, grafting from
National Category
Other Basic Medicine
Identifiers
URN: urn:nbn:se:kth:diva-10455ISBN: 978-91-7415-338-5 (print)OAI: oai:DiVA.org:kth-10455DiVA: diva2:217744
Public defence
2009-06-05, F3, KTH, Lindstedsvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20100730Available from: 2009-05-18 Created: 2009-05-15 Last updated: 2010-07-30Bibliographically approved
List of papers
1. Grafting of cellulose fibers with polycaprolactone and poly(lactide) via ring-opening polymerization
Open this publication in new window or tab >>Grafting of cellulose fibers with polycaprolactone and poly(lactide) via ring-opening polymerization
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2006 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, no 7, 2178-2185 p.Article in journal (Refereed) Published
Abstract [en]

In this study, ring-opening polymerization (ROP) of epsilon-caprolactone (epsilon-CL) and L-lactide (L-LA) has been performed from cellulose fibers. The hydroxyl groups on cellulose act as initiators in the polymerization, and the polymers are covalently bonded to the cellulose fiber. As an attempt to introduce more available hydroxyl groups on the surface, and thereby obtain higher grafting efficiency in the ROP of epsilon-CL and L-LA, unmodified paper was modified with xyloglucan-bis(methylol)-2-methylpropanamide (XG-bis-MPA) and 2,2-bis(methylol)propionic acid (bis-MPA), respectively. The grafted substrates were characterized via Fourier transform infrared spectroscopy (FTIR), contact angle measurement, atomic force microscopy, and enzymatic degradation. The results showed a successful grafting of poly(epsilon-caprolactone) (PCL) and poly(L-lactic acid) (PLLA) from the cellulose fiber surfaces. Furthermore, the results showed an improved grafting efficiency after activation of the cellulose surface with bis-MPA, and showed that the amount of grafted polymer could be controlled by the ratio of added free initiator to monomer.

National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-10452 (URN)10.1021/bm060178z (DOI)000238848800014 ()16827585 (PubMedID)2-s2.0-33746319530 (Scopus ID)
Note
QC 20100730Available from: 2009-05-15 Created: 2009-05-15 Last updated: 2017-12-13Bibliographically approved
2. Surface grafting of microfibrillated cellulose with poly(epsilon-caprolactone) - Synthesis and characterization
Open this publication in new window or tab >>Surface grafting of microfibrillated cellulose with poly(epsilon-caprolactone) - Synthesis and characterization
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2008 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 44, no 9, 2991-2997 p.Article in journal (Refereed) Published
Abstract [en]

In cellulose nanocomposites, the surface of the nanocellulosic phase is critical with respect to nanocellulose dispersion, network formation and nanocomposite properties. Microfibrillated cellulose (MFC) has been grafted with poly(epsilon-caprolactone) (PCL), via ring-opening polymerization (ROP). This changes the surface characteristics of MFC and makes it possible to obtain a stable dispersion of MFC in a nonpolar solvent; it also improves MFC's compatibility with PCL. The thermal behavior of MFC grafted with different amount of PCL has been investigated using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). From TGA measurements, the fraction of PCL in MFC-PCL samples was estimated to 16%, 19%, and 21%. The crystallization and melting behavior of free PCL and MFC-PCL were studied with DSC, and a significant difference was observed regarding melting points, crystallization temperature, degree of crystallinity, as well as the time required for crystallization.

Keyword
Microfibrillated cellulose, Grafting of poly(epsilon-caprolactone), Ring-opening polymerization, Thermal gravimetric analysis, Differential scanning calorimetry, Dispersion, NONISOTHERMAL CRYSTALLIZATION, NANOCOMPOSITE MATERIALS, WHISKERS, FIBERS, BEHAVIOR, POLYCAPROLACTONE, BIOPOLYMERS, SUSPENSIONS, COPOLYMERS
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-13468 (URN)10.1016/j.eurpolymj.2008.06.023 (DOI)000260274400031 ()2-s2.0-51149086166 (Scopus ID)
Note
QC20100618Available from: 2010-06-18 Created: 2010-06-18 Last updated: 2017-12-12Bibliographically approved
3. Grafting of polycaprolactone from microfibrillated cellulose and the investigation of graft lengths impact on the mechanical properties innano-biocomposites
Open this publication in new window or tab >>Grafting of polycaprolactone from microfibrillated cellulose and the investigation of graft lengths impact on the mechanical properties innano-biocomposites
(English)Manuscript (Other academic)
Keyword
biocomposites, microfibrillated cellulose, polycaprolactone, grafting from, graft length
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-10481 (URN)
Note
QC 20100729Available from: 2009-05-18 Created: 2009-05-18 Last updated: 2010-07-30Bibliographically approved
4. Towards molecular design of the cellulose/polycaprolactoneinterphase: engineering of debonding toughness
Open this publication in new window or tab >>Towards molecular design of the cellulose/polycaprolactoneinterphase: engineering of debonding toughness
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(English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126Article in journal (Refereed) Submitted
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-10484 (URN)
Note
QS 20120328Available from: 2009-05-18 Created: 2009-05-18 Last updated: 2017-12-13Bibliographically approved
5. Adhesion Dynamics for Cellulose Nano-Composites
Open this publication in new window or tab >>Adhesion Dynamics for Cellulose Nano-Composites
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2009 (English)In: ACS applied Materials & Interfaces, ISSN 1944-8252, 2098-2103 p.Article in journal (Refereed) Published
Abstract [en]

The efficiency of poly(ε-caprolactone) (PCL) as a matrix polymer for cellulose nano-composites has been investigated at the macromolecular contact level using atomic force microscopy (AFM) in colloidal probe configuration.  Model cellulose micro-spheres grafted with PCL were prepared via ring-opening polymerization (ROP).  Force measurements between the functionalized particles revealed the adhesion to be highly dependent on contact time due to a diffusion controlled mechanism.  Moreover, an increase of the temperature to 60 °C (close to Tm for the PCL-graft) greatly enhanced the adhesion at the polymer-polymer interface demonstrating the importance of entanglements in the annealing of composite materials.

Keyword
atomic force microscopy, cellulose, surface forces, adhesion, colloidal probe, nano-composites, ring-opening polymerization, surface grafting, poly(ε-caprolactone)
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-11001 (URN)10.1021/am900381t (DOI)000271105000002 ()2-s2.0-79955835800 (Scopus ID)
Note
QC 20100730Available from: 2009-09-03 Created: 2009-09-03 Last updated: 2010-12-06Bibliographically approved

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