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  • 1.
    Antoni, Per
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Nyström, Daniel
    KTH, School of Chemical Science and Engineering (CHE).
    Ropponen, Jarmo
    KTH, School of Chemical Science and Engineering (CHE).
    Lundberg, Pontus
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hult, Anders
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malkoch, Michael
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Click chemistry as a tool for accelerated and one-pot synthesis of dendrimers: thermal study and application2007Manuscript (preprint) (Other academic)
    Abstract [en]

    Dendrons, dendrimers and linear polymers have been synthesized using click chemistry in combination with anhydride chemistry and atom transfer radical polymerization, ATRP. Functional materials were obtained in multigram scale using these orthogonal chemistries simultaneous.

  • 2.
    Antoni, Per
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Robb, Maxwell J.
    Campos, Luis
    Montanez, Maria
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hult, Anders
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malkoch, Michael
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hawker, Craig J.
    Pushing the Limits for Thiol-Ene and CuAAC Reactions: Synthesis of a 6th Generation Dendrimer in a Single Day2010In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 43, no 16, p. 6625-6631Article in journal (Refereed)
    Abstract [en]

    Dendrimer synthesis should not be tedious and time-consuming. By utilizing an AB(2)-CD2 approach and having orthogonal, "clickable" groups on each monomer, the time for dendrimer assembly can be drastically reduced. This was shown by preparation of a sixth generation dendrimer from starting monomer units in a single day.

  • 3.
    Aulin, Christian
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Lindqvist, Josefina
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Shchukarev, Andrei
    Umeå Universitet.
    Lindström, Tom
    Wetting kinetics of oil mixtures on fluorinated model cellulose surfaces2008In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 317, p. 556-567Article in journal (Refereed)
    Abstract [en]

    The wetting of two different model cellulose surfaces has been studied; a regenerated cellulose (RG) surface prepared by spin-coating, and a novel multilayer film of poly(ethyleneimine) and a carboxymethylated microtibrillated cellulose (MFC). The cellulose films were characterized in detail using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). AFM indicates smooth and continuous films on a nanometer scale and the RMS roughness of the RG cellulose and MFC surfaces was determined to be 3 and 6 nm, respectively. The cellulose films were modified by coating with various amounts of an anionic fluorosurfactant, perfluorooctadecanoic acid, or covalently modified with pentadecafluorooctanyl chloride. The fluorinated cellulose films were used to follow the spreading mechanisms of three different oil mixtures. The viscosity and surface tension of the oils were found to be essential parameters governing the spreading kinetics on these surfaces. XPS and dispersive surface energy measurements were made on the cellulose films coated with perfluorooctadecanoic acid. A strong correlation was found between the surface concentration of fluorine, the dispersive surface energy and the contact angle of castor oil on the surface. A dispersive surface energy less than 18 mN/m was required in order for the cellulose surface to be non-wetting (theta(e) > 90 degrees) by castor oil.

  • 4. Bellier, Q.
    et al.
    Bouit, P. -A
    Kamada, K.
    Feneyrou, P.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Maury, O.
    Andraud, C.
    Design of near-infrared dyes for nonlinear optics: Towards optical limiting applications at telecommunication wavelengths2009In: Optical Materials in Defence Systems Technology VI, SPIE - International Society for Optical Engineering, 2009, p. 74870G-Conference paper (Refereed)
    Abstract [en]

    The rapid development of frequency-tunable pulsed lasers up to telecommunication wavelengths (1400-1600 nm) led to the design of new materials for nonlinear absorption in this spectral range. In this context, two families of near infra-red (NIR) chromophores, namely heptamethine cyanine and aza-borondipyrromethene (aza-bodipy) dyes were studied. In both cases, they show significant two-photon absorption (TPA) cross-sections in the 1400-1600 nm spectral range and display good optical power limiting (OPL) properties. OPL curves were interpreted on the basis of TPA followed by excited state absorption (ESA) phenomena. Finally these systems have several relevant properties like nonlinear absorption properties, gram scale synthesis and high solubility. In addition, they could be functionalized on several sites which open the way to numerous practical applications in biology, solid-state optical limiting and signal processing.

  • 5.
    Bergenudd, Helena
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Coullerez, Geraldine
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Malmström, Eva E.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Solvent Effects on ATRP of Oligo(ethylene glycol) Methacrylate. Exploring the Limits of Control2009In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 42, no 9, p. 3302-3308Article in journal (Refereed)
    Abstract [en]

    Five copper complexes in combination with six monomer-solvent mixtures have been used to investigate the solvent effects oil ATRP of oligo(ethylene glycol) methacrylate (OEGMA). The redox properties of the copper complexes in OEGMA-solvent mixtures and the apparent rate constants (k(p)(app)) for ATRP of OEGMA were correlated to the degree of control over the polymerizations. Based on this correlation, a general discussion of the limits of control in ATRIP is carried out. One of the key parameters for control in ATRP is the propagation rate constant, making the choice of monomer essential for the design of ail ATRP system. Also, the solvent effects oil the ATRP equilibrium constant (K-ATRP) affect the limit of control (i.e., the apparent rate constant above which control is lost). The choice of copper complex is also more important than the choice of solvent for the design of a well-controlled ATRP system.

  • 6.
    Bergenudd, Helena
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry (closed 20110630).
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry (closed 20110630).
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Investigation of iron complexes in ATRP: Indications of different iron species in normal and reverse ATRP2011In: Journal of Molecular Catalysis A: Chemical, ISSN 1381-1169, E-ISSN 1873-314X, Vol. 346, no 1-2, p. 20-28Article in journal (Refereed)
    Abstract [en]

    In an attempt to correlate the ATRP kinetics and the redox properties of the mediator, eight iron complexes with nitrogen, phosphorous and carboxylic acid containing ligands were investigated by electrochemical measurements and by using them as mediators in normal and reverse ATRP of MMA in DMF. The redox properties of the iron complexes in DMF, measured by cyclic voltammetry, did not differ significantly, which was reflected in the ATRP kinetics as the apparent rate constants were practically the same with all the complexing ligands. The degree of control over the polymerization was, however, much improved in reverse ATRP as compared to normal ATRP. In this ATRP system, the ligand type is not crucial for the redox or polymerization properties. Several observations indicate that the iron species in the two systems were not the same, the Fe(III) species resulting from oxidation of Fe(II) in normal ATRP is different from the starting Fe(III) species in reverse ATRP.

  • 7.
    Bergenudd, Helena
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Predicting the Limit of Control in the ATRP Process: Results from Kinetic Simulations2011In: Macromolecular Theory and Simulations, ISSN 1022-1344, E-ISSN 1521-3919, Vol. 20, no 9, p. 814-825Article in journal (Refereed)
    Abstract [en]

    Kinetic simulations are reported, where the ATRP equilibrium constant K(ATRP) is varied and the rates and degree of control in different ATRP systems are evaluated. The apparent rate constant k(app) increases with increasing K(ATRP), but a maximum is reached. The limit of control is passed before the maximum, i.e. when K(ATRP) is increased further, apparent first-order kinetics and well-controlled molecular weights will no longer be obtained. The equilibrium constant at which the limit of control is reached varies linearly with the propagation rate constant. This enables the design of well controlled ATRP systems. The influence of the conversion and chain length dependence of the termination rate constant on the simulation results is discussed.

  • 8.
    Bergenudd, Helena
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Nyström, Daniel
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Heterogeneous iron(II)-chloride mediated radical polymerization of styrene2009In: Journal of Molecular Catalysis A: Chemical, ISSN 1381-1169, E-ISSN 1873-314X, Vol. 306, no 1-2, p. 69-76Article in journal (Refereed)
    Abstract [en]

    In an attempt to perform atom transfer radical polymerization (ATRP) with a more environmentally friendly mediator, polymerization of styrene in the presence of iron(II)-chloride and EDTA was explored from a mechanistic point of view. The presence of EDTA, which normally can form a complex with FeCl2, had no influence on the polymerization results as both the mediator and EDTA were insoluble in the polymerization medium. A mechanism is suggested for the heterogeneous polymerization of styrene mediated by iron (II)-chloride in p-xylene at 50 °C. Varying the mediator amount more than 10-fold revealed that the rate limiting step at low mediator amounts was the adsorption of the initiator or dormant polymer to the mediator surface, whereas at higher mediator amounts, the rate limiting step was instead the activation step in the ATRP equilibrium. The mechanism changed to free radical polymerization in solution at a certain conversion, resulting in lower apparent rate constant and an increased amount of transfer and termination reactions. Chain extension with MMA showed that a significant proportion of the polymer chain ends were active also at high conversions.

  • 9. Bouit, Pierre-Antoine
    et al.
    Westlund, Robert
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Feneyrou, Patrick
    Maury, Olivier
    Malkoch, Michael
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Andraud, Chantal
    Dendron-decorated cyanine dyes for optical limiting applications in the range of telecommunication wavelengths2009In: New Journal of Chemistry, ISSN 1144-0546, E-ISSN 1369-9261, Vol. 33, no 5, p. 964-968Article in journal (Refereed)
    Abstract [en]

    Cyanine dyes decorated with 2,2-bis(methylol) propionic acid (bis-MPA) based dendrons up to third generation were synthesized. Dendrons were attached to the chromophore using a "click chemistry'' reaction. Photophysical characterizations of these dyes show intense absorption and emission in the near-infrared (NIR), while nonlinear transmission experiments of the dendron-decorated chromophores indicate that properties in the IR of the parent dyes are conserved. This synthetic approach is a crucial preliminary step towards the preparation of solid functional materials for optical limiting (OL) applications in the IR.

  • 10.
    Boujemaoui, Assya
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Carlsson, Linn
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Lahcini, Mohammed
    Berglund, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Sehaqui, Houssine
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Facile Preparation Route for Nanostructured Composites: Surface-Initiated Ring-Opening Polymerization of epsilon-Caprolactone from High-Surface-Area Nanopaper2012In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 4, no 6, p. 3191-3198Article in journal (Refereed)
    Abstract [en]

    In this work, highly porous nanopaper, i.e., sheets of papers made from non-aggregated nanofibrillated cellulose (NFC), have been surface-grafted with poly(epsilon-caprolactone) (PCL) by surface-initiated ring-opening polymerization (SI-ROP). The nanopaper has exceptionally high surface area (similar to 300 m(2)/g). The "grafting from" of the nanopapers was compared to "grafting from" of cellulose in the form of filter paper, and in both cases either titanium n-butoxide (Ti(On-Bu)(4)) or tin octoate (Sn(Oct)(2)) was utilized as a catalyst. It was found that a high surface area leads to significantly higher amount of grafted PCL in the substrates when Sn(Oct)2 was utilized as a catalyst. Up to 79 wt % PCL was successfully grafted onto the nanopapers as compared to filter paper where only 2-3 wt % PCL was grafted. However, utilizing Ti(On-Bu)4 this effect was not seen and the grafted amount was essentially similar, irrespectively of surface area. The mechanical properties of the grafted nanopaper proved to be superior to those of pure PCL films, especially at elevated temperatures. The present bottom-up preparation route of NFC-based composites allows high NFC content and provides excellent nanostructural control. This is an important advantage compared with some existing preparation routes where dispersion of the filler in the matrix is challenging.

  • 11.
    Boujemaoui, Assya
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Mazieres, Stephane
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Destarac, Mathias
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    SI-RAFT/MADIX polymerization of vinyl acetate on cellulose nanocrystals for nanocomposite applications2016In: Polymer, ISSN 0032-3861, E-ISSN 1873-2291, Vol. 99, p. 240-249Article in journal (Refereed)
    Abstract [en]

    In the present work, poly(vinyl acetate) grafted cellulose nanocrystals (CNC-g-PVAc) were prepared via surface initiated reversible addition-fragmentation chain transfer and macromolecular design via the interchange of xanthates (SI-RAFT/MADIX) polymerization. Successful grafting of PVAc from CNC was confirmed by FT-IR and TGA analysis. PVAc nanocomposites reinforced with CNC-g-PVAc, as well as pristine CNC for comparison, of different weight percentages (0.5, 1, 3 and 5 wt%) of CNC were prepared via solvent casting. The PVAc reinforced with CNC-g-PVAc resulted in higher transparency and improved mechanical properties compared with unmodified CNC nanocomposites. The addition of 5 wt% CNC-g-PVAc increased the modulus of neat PVAc with as much as 154%. The proposed SI-RAFT/MADIX on CNC could be applied to wide range of monomers, and it is believed to be an efficient and robust method for CNC functionalization, thus expanding the potential applicability of CNC.

  • 12.
    Boujemaoui, Assya
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Mongkhontreerat, Surinthra
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Preparation and characterization of functionalized cellulose nanocrystals2015In: Carbohydrate Polymers, ISSN 0144-8617, E-ISSN 1879-1344, Vol. 115, p. 457-464Article in journal (Refereed)
    Abstract [en]

    In this work, a series of functional nanocrystals (F-CNCs) was successfully produced by an efficient preparation method, combining acid hydrolysis and Fischer esterification with various organic acids. Functionalities such as ATRP initiators, double bonds, triple bonds, and thiols could be incorporated on CNCs. Surface modification was confirmed by FT-IR, XPS, and elemental analysis. Physical properties of FC-NCs were assessed by AFM, XRD and TGA. Moreover, ATRP initiator functionalized CNCs were utilized to graft poly(methyl methacrylate) via ATRP, thiol functionalized CNCs were reacted with Ellman's reagent to determine the thiol content and dye disperse red 13 was attached to alkyne functionalized CNCs to estimate the propiolate content. The herein presented method is a highly versatile and straightforward procedure for the preparation of F-CNCs which is believed to be a better alternative for the commonly utilized, extensive, multistep, and time consuming post functionalization methods.

  • 13.
    Bruce, Carl
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Fogelström, Linda
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Johansson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Bionanocomposites reinforcedwith cellulose nanofibrils compatibilized through covalent grafting or physisorption of PCL –a comparative studyManuscript (preprint) (Other academic)
  • 14.
    Bruce, Carl
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Javakhishvili, Irakli
    Technical University of Denmark.
    Fogelström, Linda
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Hvilsted, Søren
    Technical University of Denmark.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Preparation and evaluation of triblock copolymers based on poly(2-(dimethylamino)ethyl methacrylate) and poly(epsilon-caprolactone)2013In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 245, p. 613-POLY-Article in journal (Other academic)
    Abstract [en]

    In this work, the preparation of two block copolymers based on poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(ε-caprolactone) (PCL) has been conducted, creating the triblock copolymers PDMAEMA-b-PCL-b-PDMAEMA and PCL-b-PDMAEMA-b-PCL. The PDMAEMA-part was then quaternized, to give polyelectrolytes with either one or two charged block(s). Subsequently, differences in properties were studied in the solid state, in solution and in water dispersion with techniques including differential scanning calorimetry, size exclusion chromatography and dynamic light scattering.

  • 15.
    Bruce, Carl
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Javakhishvili, Irakli
    Fogelström, Linda
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Hvilsted, Søren
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Well-defined ABA- and BAB-type block copolymers of PDMAEMA and PCL2014In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 4, no 49, p. 25809-25818Article in journal (Refereed)
    Abstract [en]

    Triblock copolymers of ABA- and BAB-type consisting of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA, A) and poly(epsilon-caprolactone) (PCL, B) have successfully been prepared. PDMAEMA-b-PCL-b-PDMAEMA (ABA) and PCL-b-PDMAEMA-b-PCL (BAB) were synthesised by a combination of ring-opening polymerisation of epsilon-CL, atom transfer radical polymerisation of DMAEMA and end-group conversion, performed through either acylation or azide-alkyne "click" chemistry. All samples were analysed by size exclusion chromatography where it was found that the evaluation of PDMAEMA-containing polymers was difficult due to the thermoresponsivity of PDMAEMA, affecting the solubility of the polymer in the temperature range at which the SEC was operated. From differential scanning calorimetry measurements it was shown that the crystallinity could be altered by changing the order of the blocks; with PDMAEMA as the outer block (ABA), the inherent crystallinity of PCL was destroyed while with PCL as the outer block (BAB), the degree of crystallinity was in the same proximity as for a PCL homopolymer.

  • 16.
    Bruce, Carl
    et al.
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Nilsson, Camilla
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Fogelström, Linda
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Malmström, Eva
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Paper sheets and laminates based on PCL- and PLLA-grafted fibers2011Conference paper (Refereed)
  • 17.
    Bruce, Carl
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Nilsson, Camilla
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Fogelström, Linda
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Paper-sheet biocomposites based on wood pulp grafted with poly(ε-caprolactone)Manuscript (preprint) (Other academic)
  • 18.
    Bruce, Carl
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Nilsson, Camilla
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Fogelström, Linda
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Paper-sheet biocomposites based on wood pulp grafted with poly(epsilon-caprolactone)2015In: Journal of Applied Polymer Science, ISSN 0021-8995, E-ISSN 1097-4628, Vol. 132, no 23, article id 42039Article in journal (Refereed)
    Abstract [en]

    Kraft pulp fibers were used as substrates for the grafting of poly(epsilon-caprolactone) (PCL) from available hydroxyl groups through ring-opening polymerization, targeting three different chain lengths (degree of polymerization): 120, 240, and 480. In a paper-making process, paper-sheet biocomposites composed of grafted fibers and neat pulp fibers were prepared. The paper sheets possessed both the appearance and the tactility of ordinary paper sheets. Additionally, the sheets were homogenous, suggesting that PCL-grafted fibers and neat fibers were compatible, as demonstrated by both Fourier transform infrared spectroscopy microscopy and through dye-labeling of the PCL-grafted fibers. Finally, it was shown that the paper-sheet biocomposites could be hot-pressed into laminate structures without the addition of any matrix polymer; the adhesive joint produced could even be stronger than the papers themselves. This apparent and sufficient adhesion between the layers was thought to be due to chain entanglements and/or co-crystallization of adjacent grafted PCL chains within the different paper sheets. (c) 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42039.

  • 19.
    Bruce, Carl
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Utsel, Simon
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Javakhishvili, Irakli
    Technical University of Denmark.
    Pettersson, Torbjörn
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Fogelström, Linda
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Hvilsted, Søren
    Technical University of Denmark.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Preparation and evaluation of well-defined di- and triblock copolymers based on poly[2-(dimethylamino)ethyl methacrylate] and poly(ε-caprolactone)2014In: ACS National Meeting, 2014Conference paper (Refereed)
    Abstract [en]

    In this work, di- and triblock copolymers based on poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(ε-caprolactone) (PCL) have been prepared. The PDMAEMA length was kept constant for both di- and triblock copolymers, while in the diblock copolymers the PCL length was varied in three different lengths, yielding three separate block copolymers. For the triblock blockcopolymers, on the other hand, also the PCL blocks were of the same length yielding one ABA- and one BAB-type block copolymer. In the next step, the PDMAEMA-part was quaternized to yield polyelectrolytes with either one or two charged block(s). In the final step, difference in adsorption behavior onto a negatively charged cellulose surface and subsequent alteration of surface properties was investigated. Overall, the polymers were evaluated in solid state, in solution, in water dispersion, and on cellulose surfaces with techniques including differential scanning calorimetry, size exclusion chromatography, dynamic light scattering and quartz crystal microbalance.

  • 20.
    Bruce, Carl
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Utsel, Simon
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Larsson, Emma
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Carlmark, Anna
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Fogelström, Linda
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Malmström, Eva
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    A comparative study of covalent grafting and physical adsorption of PCL onto cellulose2012Conference paper (Refereed)
    Abstract [en]

    A growing concern for the environment has, in the past years, directed the research towards a bigger focus on new “greener” materials, such as cellulose-reinforced options. Cellulose is the most abundant organic raw material in the world and it is a versatile material. However, to be able to use it in applications where it is not inherently compatible, a modification is often necessary.1-3 One common method to achieve this modification is to graft polymers onto/from the cellulose chain. This can change the inherent properties of cellulose to attain new properties, such as dimensional stability and water repellency.3 In addition to this, it has been shown that polyectrolytes can be physiosorbed onto charged surfaces.4 Due to this, it is possible to physically modify cellulose by adsorbing a polymer through electrostatic interactions instead of attaching it with a covalent bond.5

    However, a more detailed investigation concerning differences of covalent and physical attachment of poly(ε-caprolactone) (PCL) onto cellulose, has to the author’s best knowledge not been performed. Therefore, this project aims to compare these two techniques. Covalently bonded PCL was grafted by surface-initiated ring opening polymerization (SI-ROP) from the cellulose. For the adsorption approach, a block copolymer consisting of PCL and a shorter segment of poly(di(methylamino)ethyl methacrylate) (PDMAEMA) was made combining ROP and atom transfer radical polymerization (ATRP). The PDMAEMA-part was then quaternized, which resulted in a cationically charged chain – a polyelectrolyte. This can then be used as an electrostatic linker allowing the PDMAEMA-PCL copolymer to be adsorbed onto the negatively charged cellulose model surface. Finally, differences between the two approaches are evaluated regarding for example surface coverage and grafting/physiosorption efficiency investigated with techniques such as atomic force microscopy (AFM).

  • 21.
    Bruce, Carl
    et al.
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Utsel, Simon
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Larsson, Emma
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Carlmark, Anna
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Fogelström, Linda
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Wågberg, Lars
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Malmström, Eva
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Preparation and evaluation of a block copolymer compatibilizer for biocomposite applications2012Conference paper (Refereed)
    Abstract [en]

    In this study, a comparison between covalent grafting and physical adsorption of PCL onto a nanocellulose model surface was conducted. For the covalent attachment, surface-initiated ring-opening polymerization (SI-ROP) was performed. For the physical attachment, a charged block copolymer consisting of PCL and quaternized PDMAEMA was synthesized by ROP and ATRP, and adsorbed to the cellulose. Finally, differences in between the two substrates were investigated with techniques such as AFM.

  • 22.
    Bruce, Carl
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Utsel, Simon
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Larsson, Emma
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Fogelström, Linda
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    A comparative study of covalent grafting and physical adsorption of PCL onto cellulose2011Conference paper (Refereed)
    Abstract [en]

    In the past years, a growing concern for the environment has forced the research to focus more on new “greener” materials. The most abundant organic raw material in the world is cellulose. This, in combination with the versatility of the material, makes it interesting as a green option in various applications. However, to be able to take advantage of all characteristics possessed by cellulose, i.e., use it in applications where it is not inherently compatible, modification is often necessary.1-3 One common method used for modifying cellulose is grafting of polymers onto/from the cellulose chain. This offers a way of changing the inherent properties of cellulose to attain new properties, such as dimensional stability and water repellency.3

    Additionally, it has been shown that polyectrolytes can be physiosorbed onto charged surfaces.4 This has made it possible to physically modify cellulose by adsorbing a polymer through electrostatic interactions instead of attaching it with a covalent bond.5 However, a more detailed investigation concerning the differences, such as surface coverage and grafting/physiosorption efficiency, between a covalent and physical attachment of a polymer has to the author’s best knowledge earlier not been performed. Therefore, this project aims to compare these two techniques. A block copolymer consisting of poly(ε-caprolactone) (PCL) and poly(di(methylamino)ethyl methacrylate) (PDMAEMA) is made, see figure 1 for 1H-NMR-spectrum.

    Figure 1. The 1H-NMR-spectrum of PCL-block-PDMAEMA (in CDCl3).

    The PDMAEMA-part is then quaternized (figure 2), which results in a charged chain – a polyelectrolyte.

    Figure 2.The quaternization of the PDMAEMA block to obtain cationic charges.

    The charges allow for the PDMAEMA-PCL copolymer to be adsorbed onto a cellulose surface. Finally, to evaluate and compare the differences between the covalent and the physical surface modification, regarding for example surface coverage, grafting/physiosorption efficiency, adhesion and matrix compatibility, various characterization methods are employed: fourier transform infrared spectroscopy (FTIR), contact angle measurements (CA), micro adhesion measurement apparatus (MAMA), force measurements using atomic force microscopy (AFM) and macroscopic peel tests using dynamical mechanical analysis (DMA) or Instron.

    Figure 3. A schematic drawing of covalent attachment and physical adsorption of PCL onto cellulose.

    Further work after preparation of fibres may include such steps as making of fiber-reinforced composites, out of both chemically and physically modified fibres, where for example differences concerning mechanical properties would be investigated.

    References

    (1) Lönnberg, H.; Fogelström, L.; Berglund, L.; Malmström, E.; Hult, A. European Polymer Journal 2008, 44, 2991.

    (2) Lönnberg, H.; Zhou, Q.; Brumer, H., 3rd; Teeri Tuula, T.; Malmström, E.; Hult, A. Biomacromolecules 2006, 7, 2178.

    (3) Roy, D.; Semsarilar, M.; Guthrie, J. T.; Perrier, S. Chemical Society Reviews 2009, 38, 2046.

    (4) Decher, G.; Hong, J. D. Berichte der Bunsen-Gesellschaft 1991, 95, 1430.

    (5) Utsel, S.; Carlmark, A.; Pettersson, T.; Bergström, M.; Malmström, E.; Wågberg, L. Abstracts of Papers, 241st ACS National Meeting & Exposition, Anaheim, CA, United States, March 27-31, 2011 2011, CELL.

  • 23.
    Bruce, Carl
    et al.
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Utsel, Simon
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Larsson, Emma
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Fogelström, Linda
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Wågberg, Lars
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Malmström, Eva
    KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Comparative study of covalent grafting and physical adsorption of PCL onto cellulose2012Conference paper (Refereed)
    Abstract [en]

    In this work, an investigation concerning differences between covalent and physical attachment of poly(ε-caprolactone) (PCL) to a nanocellulose modell surface was conducted. For the covalent attachment, ring-opening polymerization (ROP) was performed using the “grafting-from” approach, building the polymer from the surface. For the physical attachment, a block copolymer consisting of PCL and poly(di(methylamino)ethyl methacrylate) (PDMAEMA) was made combining ROP and atom transfer radical polymerization (ATRP). The PDMAEMA-part was then quaternized, which resulted in a charged chain – a polyelectrolyte. The charges allow for the PDMAEMA-PCL copolymer to be adsorbed onto the nanocellulose modell surface. The length of the PDMAEMA-part was kept constant (DP=20), and the length of PCL was varied (DP=150, 300, 600) for both the covalently attached polymer and for the copolymer. Finally, differences between the two approaches were evaluated regarding for example surface coverage and grafting/physiosorption efficiency investigated with techniques such as atomic force microscopy.

  • 24.
    Bruce, Carl
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Utsel, Simon
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Larsson, Emma
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Fogelström, Linda
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Malmström Jonsson, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Comparative study of covalent grafting and physical adsorption of PCL onto cellulose2012In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 243Article in journal (Other academic)
  • 25.
    Bruce, Carl
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Utsel, Simon
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Pettersson, Torbjörn
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Fogelström, Linda
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Physical Tuning of Cellulose-Polymer Interactions Utilizing Cationic Block Copolymers Based on PCL and Quaternized PDMAEMA2013Conference paper (Refereed)
    Abstract [en]

    In this study, the aim was to prepare and evaluate a block copolymer that can be used as a compatibilizer in cellulose fiber-reinforced biocomposites. It is an amphiphilic block copolymer consisting of poly(ε-caprolactone) (PCL), prepared with  ring-opening polymerization (ROP)1, and a shorter segment of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) synthesized with atom transfer radical polymerization (ATRP)2. The PDMAEMA-part was prepared in one single length, while the PCL-part was varied in three different lengths. In the last synthesis step the PDMAEMA-part was quaternized, turning it into a cationically charged chain – a polyelectrolyte. The block copolymers were then able to form cationic micelles in water, from where they can adsorb, under mild conditions, to anionic surfaces such as silicon oxide and cellulose-model surfaces. A similar concept has been investigated earlier in a system fully prepared with ATRP3. Additionally, physical adsorption of micelles is a milder approach of attaching a polymer to a cellulose surface compared to more traditional covalent attachment4, making it an interesting option to use in industry. After adsorption, the surface had a more hydrophobic character shown with contact angle measurements, and with AFM force measurements, it was demonstrated that there is a clear entanglement behavior obtained between the block copolymers and a PCL surface at about 60 °C, which is of importance for the information regarding the adhesive interface in a future biocomposite.

  • 26.
    Bruce, Carl
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Utsel, Simon
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Pettersson, Torbjörn
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Fogelström, Linda
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Physical Tuning of Cellulose-Polymer Interactions Utilizing Cationic Block Copolymers Based on PCL and Quaternized PDMAEMA2013Conference paper (Refereed)
    Abstract [en]

    In this study, the aim was to prepare and evaluate a block copolymer that can be used as a compatabilizer in cellulose fiber-reinforced biocomposites. It as an amphiphilic block copolymer consisting of poly(ε-caprolactone) (PCL), made with  ring-opening polymerization (ROP), and a shorter segment of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) that was synthesized with atom transfer radical polymerization (ATRP). The PDMAEMA-part was made in one single length, while the PCL-part was varied in three different lengths; in total were three block copolymers prepared. In the last step of the synthesis, the PDMAEMA-part was quaternized that turns it into a cationically charged chain – a polyelectrolyte. The block copolymers were then able to form cationic micelles in water, from where they can adsorb, under mild conditions, to anionic surfaces such as silicon oxide and cellulose-model surfaces. This provides the surface with a more hydrophobic character shown with contact angle measurements. Finally, with atomic force microscopy (AFM) force measurements, it was demonstrated that there is a clear entanglement behavior obtained between the block copolymers and a PCL surface at about 60 °C, which is of importance for the information regarding the adhesive interface in a future biocomposite.

  • 27.
    Bruce, Carl
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Utsel, Simon
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Pettersson, Torbjörn
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Larsson, Emma
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Fogelström, Linda
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Preparation and evaluation of a block copolymer compatibilizer for biocomposite applications2012Conference paper (Refereed)
    Abstract [en]

    In this study, the concept of using a free polymer as a compatibilzer in biocomposite applications has been evaluated with focus on the polymer poly(ɛ-caprolactone) (PCL), commonly used in conventional grafting onto/from cellulose. A block copolymer consisting of PCL and a shorter segment of poly(di(methylamino)ethyl methacrylate) (PDMAEMA) was made combining ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). The length of the PDMAEMA-part was kept constant, and the PCL-part was varied in three different lengths, yielding three separate block copolymers. As a final step, the PDMAEMA-part was quaternized, which resulted in cationically charged chains –polyelectrolytes. The charged part could then be used as an electrostatic linker allowing the PDMAEMA-PCL copolymer to be adsorbed onto negatively charged cellulose model surfaces. Finally, these cellulose model surfaces were evaluated regarding for example amount of polymer adsorbed and hydrophobic character, investigated with techniques such as quartz crystal microbalance (QCM) and contact angle measurements.

  • 28.
    Brännström, Sara
    et al.
    KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology.
    Finnveden, Maja
    KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Industrial Biotechnology.
    Johansson, Mats
    KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology.
    Martinelle, Mats
    KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Industrial Biotechnology.
    Malmström, Eva
    KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology.
    Itaconate based polyesters: Selectivity and performance of esterification catalysts2018In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 103, p. 370-377Article in journal (Refereed)
    Abstract [en]

    The performance of different esterification catalysts was studied for the use in synthesis of renewable polyesters from dimethyl itaconate (DMI), dimethyl succinate (DMS) and 1,4-butanediol (BD). Itaconic acid and derivatives such as DMI are interesting monomers because of their multiple functionalities and previous work has shown great potential. However, the multiple functionalities also pose challenges to avoid side reactions such as thermally initiated, premature, radical crosslinking and/or isomerization of the 1,1-disubstituted unsaturation. Additionally, the two carboxylic acids have inherently different reactivity. One key factor to control reactions with IA is to understand the performance of different catalysts. In this study, six esterification catalysts were investigated; immobilized Candida antarctica lipase B (CalB), titanium(IV)butoxide (Ti(OBu)4), p-toluenesulfonic acid (pTSA), sulfuric acid (H2SO4), 1,8-diazabicycloundec-7-ene (DBU), and 1,5,7-triazabicyclodec-5-ene (TBD). CalB and Ti(OBu)4 were selected for further characterization with appreciable differences in catalytic activity and selectivity towards DMI. CalB was the most effective catalysts and was applied at 60 °C while Ti(OBu)4 required 160 °C for a reasonable reaction rate. CalB was selective towards DMS and the non-conjugated side of DMI, resulting in polyesters with itaconate-residues mainly located at the chain ends, while Ti(OBu)4 showed low selectivity, resulting in polyesters with more randomly incorporated itaconate units. Thermal analysis of the polyesters showed that the CalB-catalyzed polyesters were semi-crystalline, whereas the Ti(OBu)4-catalyzed polyesters were amorphous, affirming the difference in monomer sequence. The polyester resins were crosslinked by UV-initiated free radical polymerization and the material properties were evaluated and showed that the crosslinked materials had similar material properties. The films from the polyester resins catalyzed by CalB were furthermore completely free from discoloration whereas the film made from the polyester resins catalyzed with Ti(OBu)4 had a yellow color, caused by the catalyst. Thus, it has been shown that CalB can be used to attain sustainable unsaturated polyesters resins for coating applications, exhibiting equally good properties as resins obtained from traditional metal-catalysis.

  • 29.
    Carlmark, Anna E.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Carlsson, Linn
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Malmström, Eva E.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Surface-initiated ring-opening metathesis polymerization from cellulose fibers2011In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 242, p. 432-POLY-Article in journal (Refereed)
  • 30.
    Carlmark, Anna E
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Vestberg, Robert
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström Jonsson, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Atom transfer radical polymerization of methyl acrylate from a multifunctional initiator at ambient temperature2002In: Polymer, ISSN 0032-3861, E-ISSN 1873-2291, Vol. 43, no 15, p. 4237-4242Article in journal (Refereed)
    Abstract [en]

    A multifunctional initiator for ATRP has been synthesized by reacting a hyperbranched polyether, based on 3-ethyl-3-(hydroxymethyl)oxetane, with 2-bromo-isobutyrylbromide. The macroinitiator contained approximately 25 initiating sites per molecule. It was used for the atom transfer radical polymerization of methyl acrylate mediated by Cu(I)Br and tris(2-(dimethylamino)ethyl)amine (Me-6-TREN) in ethyl acetate at room temperature. This yielded a co-polymer with a dendritic-linear architecture. The large number of growing chains from each macromolecule increases the probability of inter-and intramolecular reactions. In order to control these kinds of polymerizing systems and prevent them from forming a gel, the concentration of propagating radicals must be kept low. The polymerizations under these conditions were well controlled. When a ratio of initiating sites-to-catalyst of 1:0.05 was used, the polymers from all of the reactions had a low polydispersity, ranging from 1.1 to 1.4. None of the polymerizations under these conditions gave gelation. Monomer conversions as high as 65% were reached while maintaining control over the polymerization. (C) 2002 Elsevier Science Ltd. All rights reserved.

  • 31.
    Carlmark, Anna
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Larsson, Emma
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Grafting of cellulose by ring-opening polymerisation - A review2012In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 48, no 10, p. 1646-1659Article, review/survey (Refereed)
    Abstract [en]

    In this review, homogeneous and heterogeneous grafting from cellulose and cellulose derivatives by ring-opening polymerisation (ROP) are reported. Cellulose is biorenewable and biodegradable as well as a stiff material with a relatively low specific weight, foreseen to be an excellent replacement for synthetic materials. By utilising ROP of monomers such as -caprolactone or l-lactide from cellulose, composite materials with new and/or improved properties can be obtained. Grafting of solid cellulose substrates, such as cotton, microfibrillated cellulose (MFC) or cellulose nanocrystals, renders cellulose that can easily be dispersed into polymer matrices and may be used as reinforcing elements to improve mechanical and/or barrier properties of biocomposites. A surface grafted polymer can also tailor the interfacial properties between a matrix and the fibrillar structure of cellulose. When derivatives of cellulose are grafted with polymers in homogenous media, amphiphilic materials with interesting properties can be achieved, anticipated to be utilised for applications such as encapsulation and release.

  • 32.
    Carlmark, Anna
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Atom transfer radical polymerization from cellulose fibers at ambient temperature2002In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 124, no 6, p. 900-901Article in journal (Refereed)
    Abstract [en]

    Cellulose fibers have been successfully grafted with poly(methyl acrylate) using atom transfer radical polymerization, mediated by Me6-TREN and Cu(I)Br at ambient temperature. The initially hydrophilic cellulose was first modified by reacting the hydrozyl groups with 2-bromoisobutyryl bromide whereupon methyl acrylate was grafted from the surface. The resulting polymer-grafted papers were extremely hydrophobic, θa = 133°. FT-IR analysis indicates that the amount of grafted polymer can be controlled by adding sacrificial initiator to the polymerizing system. Size exclusion chromatography of the bulk polymer revealed narrow polydispersities and a molecular weight corresponding to the ratio [M]:[I].

  • 33.
    Carlmark, Anna
    et al.
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Malmström, Eva
    KTH, Superseded Departments, Fibre and Polymer Technology.
    ATRP grafting from cellulose fibers to create block-copolymer grafts2003In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 4, no 6, p. 1740-1745Article in journal (Refereed)
    Abstract [en]

    Cellulose fibers, in the form of a conventional filter paper, have been modified by reacting the hydroxyl groups on the fiber surface with 2-bromoisobutyryl bromide, followed by grafting using ATRP conditions. The papers were first grafted with methyl acrylate (MA), rendering the paper very hydrophobic as reported in an earlier work. The papers were analyzed by gravimetry, FT-IR, ESCA, and AFM. To verify that the polymerization from the surface was living, a second layer of another, hydrophilic, polymer, 2-hydroxyethyl methacrylate (HEMA), was grafted upon the PMA layer, creating a block-copolymer graft from the fibers. After the layer of PHEMA had been attached, contact angle measurements were no longer possible, because of the absorbing nature of PHEMA-grafted layer. This indicates that a copolymer had indeed been formed on the surface. FT-IR showed a large increase in carbonyl content after the PHEMA-grafting, which further proves that a layer of PHEMA was attached to the PMA layer. This goes to show that the hydrophilic/ hydrophobic behavior of a cellulose surface can be tailored by the use of living/controlled radical polymerization methods such as ATRP.

  • 34.
    Carlmark, Anna
    et al.
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Malmström, Eva E
    KTH, Superseded Departments, Fibre and Polymer Technology.
    ATRP of dendronized aliphatic macromonomers of generation one, two, and three2004In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 37, no 20, p. 7491-7496Article in journal (Refereed)
    Abstract [en]

    Atom transfer radical polymerization (ATRP) of dendritic, aliphatic macromonomers has been investigated. The macromonomers were based on acrylate functionalized 2,2-bis(methylol)propionic acid (bis-MPA) dendrons, with a flexible spacer of 10 carbons incorporated in the structure in between the polymerizable group and the dendritic wedge. Dendronized polymers of generation one, two, and three were successfully synthesized by ATRP. The polymerizations proceeded until over 80% conversion was reached, while maintaining control over polydispersity index (PDI). Plots of ln([M](0)/[M]) vs time for the polymerization of all three macromonomers showed a linear dependence, indicating that the number of propagating radicals in the reaction solution was constant throughout the reaction, when ethyl 2-bromopropionate (EBrP) was used as an initiator (i.e., radical termination was negligible). All of the resulting polymers had low PDI values and molecular weight close to the theoretical ones. The products were analyzed by H-1 and C-13 NMR spectroscopies, size exclusion chromatography (SEC), differential scanning calorimetry (DSC), and matrix-assisted laser desorption-ionization time-of-flight (MALDI-TOF).

  • 35.
    Carlmark, Anna
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malkoch, Michael
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Dendritic architectures based on bis-MPA: functional polymeric scaffolds for application-driven research2013In: Chemical Society Reviews, ISSN 0306-0012, E-ISSN 1460-4744, Vol. 42, no 13, p. 5858-5879Article, review/survey (Refereed)
    Abstract [en]

    Dendritic polymers are highly branched, globular architectures with multiple representations of functional groups. These nanoscale organic frameworks continue to fascinate researchers worldwide and are today under intensive investigation in application-driven research. A large number of potential application areas have been suggested for dendritic polymers, including theranostics, biosensors, optics, adhesives and coatings. The transition from potential to real applications is strongly dictated by their commercial accessibility, scaffolding ability as well as biocompatibility. A dendritic family that fulfills these requirements is based on the 2,2-bismethylolpropionic acid (bis-MPA) monomer. This critical review is the first of its kind to cover most of the research activities generated on aliphatic polyester dendritic architectures based on bis-MPA. It is apparent that these scaffolds will continue to be in the forefront of cutting-edge research as their structural variations are endless including dendrons, dendrimers, hyperbranched polymers, dendritic-linear hybrids and their hybridization with inorganic surfaces.

  • 36.
    Carlsson, Linn
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Fall, Andreas
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Chaduc, Isabelle
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Charleux, Bernadette
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    D'Agosto, Franck
    Lansalot, Muriel
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Modification of cellulose model surfaces by cationic polymer latexes prepared by RAFT-mediated surfactant-free emulsion polymerization2014In: Polymer Chemistry, ISSN 1759-9954, E-ISSN 1759-9962, Vol. 5, no 20, p. 6076-6086Article in journal (Refereed)
    Abstract [en]

    This paper presents the successful surface modification of a model cellulose substrate by the preparation and subsequent physical adsorption of cationic polymer latexes. The first part of the work introduces novel charged polymer nanoparticles constituted of amphiphilic block copolymers based on cationic poly(N,N-dimethylaminoethyl methacrylate-co-methacrylic acid) (P(DMAEMA-co-MAA)) as the hydrophilic segment, and poly(methyl methacrylate) (PMMA) as the hydrophobic segment. First, RAFT polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA) in water was performed at pH 7, below its pK(a). The simultaneous hydrolysis of DMAEMA led to the formation of a statistical copolymer incorporating mainly protonated DMAEMA units and some deprotonated methacrylic acid units at pH 7. The following step was the RAFT-mediated surfactant-free emulsion polymerization of methyl methacrylate (MMA) using P(DMAEMA-co-MAA) as a hydrophilic macromolecular RAFT agent. During the synthesis, the formed amphiphilic block copolymers self-assembled into cationic latex nanoparticles by polymerization-induced self-assembly (PISA). The nanoparticles were found to increase in size with increasing molar mass of the hydrophobic block. The cationic latexes were subsequently adsorbed to cellulose model surfaces in a quartz crystal microbalance equipment with dissipation (QCM-D). The adsorbed amount, in mg m(-2), increased with increasing size of the nanoparticles. This approach allows for physical surface modification of cellulose, utilizing a water suspension of particles for which both the surface chemistry and the surface structure can be altered in a well-defined way.

  • 37.
    Carlsson, Linn
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Fall, Andreas
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Chaduc, Isabelle
    Charleux, Bernadette
    D'Agosto, Franck
    Lansalot, Muriel
    Modification of cellulose surfaces by cationic latex prepared by RAFT-mediated surfactant-free emulsion polymerizationManuscript (preprint) (Other academic)
  • 38.
    Carlsson, Linn
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Ingverud, Tobias
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Blomberg, Hanna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Larsson, Per Tomas
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. Innventia AB, Sweden.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Surface characteristics of cellulose nanoparticles grafted by surface-initiated ring-opening polymerization of epsilon-caprolactone2015In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 22, no 2, p. 1063-1074Article in journal (Refereed)
    Abstract [en]

    In this study, surface-initiated ring-opening polymerization has been employed for the grafting of epsilon-caprolactone from cellulose nanoparticles, made by partial hydrolysis of cellulose cotton linters. A sacrificial initiator was employed during the grafting reactions, to form free polymer in parallel to the grafting reaction. The degree of polymerization of the polymer grafts, and of the free polymer, was varied by varying the reaction time. The aim of this study was to estimate the cellulose nanoparticle degree of surface substitution at different reaction times. This was accomplished by combining measurement results from spectroscopy and chromatography. The prepared cellulose nanoparticles were shown to have 3.1 (+/- 0.3) % of the total anhydroglucose unit content present at the cellulose nanoparticle surfaces. This effectively limits the amount of cellulose that can be targeted by the SI-ROP reactions. For a certain SI-ROP reaction time, it was assumed that the resulting degree of polymerization (DP) of the grafts and the DP of the free polymer were equal. Based on this assumption it was shown that the cellulose nanoparticle surface degree of substitution remained approximately constant (3-7 %) and seemingly independent of SI-ROP reaction time. We believe this work to be an important step towards a deeper understanding of the processes and properties controlling SI-ROP reactions occurring at cellulose surfaces.

  • 39.
    Carlsson, Linn K.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Boujemaoui, Assya
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Sehaqui, Houssine
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Lachini, Mohammad
    Malmström Jonsson, Eva E.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Carlmark, Anna E.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Synthesis and characterization of biocomposites from cellulose nano- and filter papers prepared by ring-opening polymerization of epsilon-caprolactone with titanium based catalyst2012In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 243Article in journal (Other academic)
  • 40.
    Carlsson, Linn
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Larsson, Per Tomas
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Ingverud, Tobias
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Blomberg, Hanna
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Solid State CP/MAS 13C-NMR investigation of hydrolyzed cotton linters grafted by surface‐initiated ring‐opening polymerization of ε‐caprolactoneManuscript (preprint) (Other academic)
  • 41.
    Carlsson, Linn
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Surface-initiated ring-opening metathesis polymerisation from cellulose fibres2012In: POLYM CHEM-UK, ISSN 1759-9954, Vol. 3, no 3, p. 727-733Article in journal (Refereed)
    Abstract [en]

    In this study, cellulose fibres have been grafted utilizing surface-initiated ring-opening metathesis polymerisation (SI-ROMP). Initially, a Grubbs' type catalyst was immobilized onto filter paper whereafter SI-ROMP of norbornene was performed from the surface of the fibres at three different reaction temperatures, room temperature (RT), 0 degrees C and -18 degrees C, and for different reaction times. The evaluation of the grafted cellulose was performed by contact angle measurements, FT-Raman spectroscopy, FE-SEM and TGA. After the grafting, all samples were clearly hydrophobic with weight increases up to over 100%. The FT-Raman spectroscopy analysis showed significant structural changes after polymerization for cellulose substrates polymerized at 0 degrees C and RT, confirming that a polymer was grafted from the surface. FE-SEM images verified that these samples are covered by polynorbornene and that the fibrillar structure of the native cellulose disappeared. For the samples grafted at -18 degrees C, no significant changes were seen with these analysis methods. However, SI-ROMP appears to be a versatile method to modify cellulose fibres.

  • 42.
    Carlsson, Linn
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Utsel, Simon
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Surface-initiated ring-opening polymerization from cellulose model surfaces monitored by a Quartz Crystal Microbalance2012In: Soft Matter, ISSN 1744-683X, E-ISSN 1744-6848, Vol. 8, no 2, p. 512-517Article in journal (Refereed)
    Abstract [en]

    Polymer surface-grafting is an excellent method to modify the properties of a surface. However, surface-initiated polymerization is still relatively poorly understood due to the lack of appropriate characterization methods and tools to monitor the polymerizations. Herein, we report the in situ, surface-initiated ring-opening polymerization (SI-ROP) investigated in real time by the Quartz Crystal Microbalance (QCM) technique. The polymerization was performed from a cellulose model surface and the polymerization was initiated directly from the available hydroxyl groups on the cellulose. The cyclic monomer 3-caprolactone and an organic catalyst, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), were used, and the reaction was performed in bulk at room temperature. Since a free polymer was formed in bulk in parallel to the grafting from the surface, the reaction was performed in three cycles with rinsing steps in between to measure only the effect of the surface grafting. The change in frequency showed that the grafted amount of polymer increased after each cycle indicating that most of the chain ends remained active. After polymer grafting, the cellulose model surface showed a more hydrophobic character, and the surface roughness of the cellulose model surface was reduced. This study clearly shows that QCM is a viable method to monitor SI-ROP in situ from cellulose surfaces. We believe this is an important step towards a deeper understanding of how to tailor the interface between polymer-modified cellulose and a polymer matrix in biocomposites.

  • 43.
    Claesson, Hans
    et al.
    KTH, Superseded Departments, Polymer Technology.
    Malmström, Eva
    KTH, Superseded Departments, Polymer Technology.
    Johansson, Mats K. G.
    KTH, Superseded Departments, Polymer Technology.
    Hult, Anders
    KTH, Superseded Departments, Polymer Technology.
    Synthesis and characterisation of star branched polyesters with dendritic cores and the effect of structural variations on zero shear rate viscosity2002In: Polymer, ISSN 0032-3861, E-ISSN 1873-2291, Vol. 43, no 12, p. 3511-3518Article in journal (Refereed)
    Abstract [en]

    A series of branched polyesters consisting of poly(epsilon-caprolactone) (PCL) (degree of polymerisation: 5-200) initiated from hydroxy-functional cores and end-capped with methylmethacrylate have been prepared. The cores were third-generation hyperbranched polyester, Boltorn, with approximately 32 hydroxyl groups, a third-generation dendrimer with 24 hydroxyl groups and a third-generation dendron with eight hydroxyl groups. Finally, a linear PCL was synthesised as a reference material. All initiators were based on 2,2-bis(methylol) propionic acid (bis-MPA). C-13 NMR spectra of the polymers showed that those with shorter arms contained unreacted hydroxyl groups on the core. Rheological measurements of zero shear rate viscosity, eta(0), showed that the branched polyesters had a considerably lower eta(0) than linear polyester with similar molecular weight. The low melt viscosity and the crystallity produced a theological behaviour suitable for the film formation process for powder coatings. Measurements of mechanical properties of cured films showed that those with low arm molecular weight, M-a, were amorphous while those of high M-a were crystalline.

  • 44.
    Claesson, Hans
    et al.
    KTH, Superseded Departments, Polymer Technology.
    Malmström, Eva
    KTH, Superseded Departments, Polymer Technology.
    Johansson, Mats K. G.
    KTH, Superseded Departments, Polymer Technology.
    Hult, Anders
    KTH, Superseded Departments, Polymer Technology.
    Doyle, M.
    Manson, J. A. E.
    Rheological behaviour during UV-curing of a star-branched polyester2002In: Progress in organic coatings, ISSN 0300-9440, E-ISSN 1873-331X, Vol. 44, no 1, p. 63-67Article in journal (Refereed)
    Abstract [en]

    Using a rheometer coupled with an UV-light generator, the viscoelastic behaviour during the fast cure of star-branched polyester is investigated. The 32 arm star polymers consist of a hyperbranched polyester core, Boltorn(TM) and linear grafts of poly(E-caprolactone) (degree of polymerisation: 20-52) with methacrylate end groups. The resins are crystalline and the melting points range from 34 to 50degreesC; films can be formed and cured below 80degreesC. The crossover of G' and G was used as the gel point. The time to reach the gel point, a few seconds, increases linearly with molecular weight.

  • 45.
    Claesson, Hans
    et al.
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Scheurer, Curzio
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Malmström, Eva
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Johansson, Mats K. G.
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Hult, Anders
    KTH, Superseded Departments, Polymer Technology.
    Paulus, W.
    Schwalm, R.
    Semi-crystalline thermoset resins: tailoring rheological properties in melt using comb structures with crystalline grafts2004In: Progress in organic coatings, ISSN 0300-9440, E-ISSN 1873-331X, Vol. 49, no 1, p. 13-22Article in journal (Refereed)
    Abstract [en]

    Thermosetting resins with semi-crystalline grafts have been synthesized. An amorphous resin with epoxide groups was first functionalized with hydroxyl groups using 2,2-bis(methylol) propionic acid, bis-MPA in bulk at 155 degreesC. Functionalization with bis-MPA was monitored using FT-IR, FT-Raman and SEC. The reaction was complete in 30 min. Grafts of poly(epsilon-caprolactone) were then grown from the hydroxyl functional resin and end capped with methacrylate groups. The polymerization Of epsilon-caprolactone, performed in bulk at 110 degreesC using Sn(Oct)(2), was characterized using H-1 NMR and SEC. The obtained molecular weights agreed well with theoretical values. The final end capping was performed using methacrylic anhydride, and monitored with SEC and H-1 NMR, which indicated full substitution. Two combs were synthesized with different arm lengths, DP 10 and 20, and the obtained M-W were close to calculated values. The complex viscosity was measured from low to high temperature for the crystalline resins, the amorphous resin and blends thereof. Rheological data show a rapid decrease in viscosity within a temperature change of 10-15 degreesC for the crystalline resins while the amorphous resin exhibited a slow softening. The blends exhibited a behavior in-between that of the crystalline and the amorphous resin. Films were prepared from the pure resins and the blends. The films were cured using UV irradiation. The comb architecture of these resins has advantages such as crystallinity, high molecular weight and low viscosity, facilitating leveling and resulting in smooth films. The final film properties varied with the ratio of crystalline to amorphous resin, where increase in the amount of crystalline resin correlated with increased the flexibility.

  • 46. Coullerez, G.
    et al.
    Lundmark, S.
    Malkoch, Michael
    KTH, Superseded Departments, Polymer Technology.
    Magnusson, H.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hult, Anders
    KTH, Superseded Departments, Polymer Technology.
    Mathieu, H. J.
    Insights into ToF-SIMS analysis of dendritic macromolecules: cationization and PCA to probe their molecular weight on surfaces2003In: Applied Surface Science, ISSN 0169-4332, E-ISSN 1873-5584, Vol. 203, p. 620-624Article in journal (Refereed)
    Abstract [en]

    Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is utilized to study dendrons, dendrimers and hyperbranched derivatives prepared from the 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) or the 3-ethyl-3-(hydroxymethyl)oxetane (TMPO). We show that the cationization experiments of the intact molecules with alkali or metal ions such as Na+, Cu+ or Ag+ allow to detect whole molecular species up to 3000 Da (low generation). It allows to probe directly their molecular TM weight and end-functionality. However, when the molecule lift-off fails for series of hyperbranched polyesters Boltorn(TM), the fingerprint part of the SIMS spectra (m/z < 300 Da) is instead used. The low-mass fragments are mainly assigned to the bis-MP repeating unit. Ions due to the core molecule are also distinguished. Data treatment is combined with the principal component analysis (PCA) multivariate statistical method to highlight the main differences between the spectra. Only one principal component (PC1) is needed to describe most of the variance between the samples taking into account the generation effect. PC1 plotted as a function of the molecular weight gives a calibration curve. Normalization of the data set by ion intensities from the core molecule allows the linearization of the SIMS intensities vs. the molecular weight.

  • 47. Coullerez, G.
    et al.
    Lundmark, S.
    Malmström, Eva
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Hult, Anders
    KTH, Superseded Departments, Polymer Technology.
    Mathieu, H. J.
    ToF-SIMS for the characterization of hyperbranched aliphatic polyesters: probing their molecular weight on surfaces based on principal component analysis (PCA)2003In: Surface and Interface Analysis, ISSN 0142-2421, E-ISSN 1096-9918, Vol. 35, no 8, p. 693-708Article in journal (Refereed)
    Abstract [en]

    A series of 2,2-bis(hydroxymethyl)propionic acid (Bis-MPA) hyperbranched aliphatic polyesters with different molecular weights (generations) is analysed for the first time by time-of-flight secondary ion mass spectrometry (ToF-SIMS). The main negative and positive low-mass fragments are identified in the fingerprint part of the spectra (m/z < 400) and are principally assigned to fragmentation of the Bis-MPA repeating units. In addition, it is shown that the fragmentation pattern is highly affected by the functional end-groups. This is illustrated for a phthalic acid end-capped hyperbranched polymer and for an acetonide-terminated dendrimer analog. Also, typical fragments assigned to the ethoxylated pentaerythritol core molecule are detected. These ions show decreasing intensities with increasing molecular weight. This intensity dependency on the generation is used to calibrate the molecular weight of hyperbranched polyesters on the surface. To obtain quantitative information, a principal component analysis WCA) multivariate statistical method is applied to the ToF-SIMS data. The influence of different normalization procedures prior to PCA calculation is tested, e.g. normalization to the total intensity, to the intensities of ions assigned to the Bis-MPA repeating unit or to intensities of fragments due to the core molecule. It is shown that only one principal component (PC1) is needed to describe most of the variance between the samples. In addition, PC1 takes into account the generation effect. However, different relationships between the PC1 scores and the hyperbranched mass average molecular weights are observed depending on the normalization procedure used. Normalization of data set ion intensities by ion intensities from the core molecule allows linearization of the SIMS intensities versus the molecular weight and allows the hyperbranched polymers to be discriminated up to the highest generations. In addition, PCA applied to ToF-SIMS data provides an extended interpretation of the spectra leading to further identification of the correlated mass peaks, such as those of the Bis-MPA repeating unit (terminal, dendritic and linear) and those of the core molecule. Finally, the work presented demonstrates the extreme potential of the static ToF-SIMS and PCA techniques in the analysis of dendritic molecules on solid surfaces.

  • 48.
    Coullerez, Geraldine
    et al.
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Carlmark, Anna
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Malmström, Eva
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Jonsson, Mats
    KTH, Superseded Departments, Chemistry.
    Understanding copper-based atom-transfer radical polymerization in aqueous media2004In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 108, no 35, p. 7129-7131Article in journal (Refereed)
    Abstract [en]

    This study investigates the mechanism of copper(I)-mediated living atom-transfer radical polymerization (ATRP) in aqueous media. It is shown that the ATRP apparent rate constant for polymerization of methoxycapped oligo(ethylene glycol) methacrylate (OEGMA) in water (k(P)(app)) at room temperature correlates with the redox potential (E-1/2) of the copper complexes. The results are discussed along with previously published results on the kinetics for bulk polymerization of methyl acrylate at 60 degreesC with the redox potentials measured in MeCN. The faster ATRP kinetics in water can mainly be attributed to a higher equilibrium concentration of propagating radicals [W] and to solvent effects on the rate of propagation k(p). It is shown that [R*] can be calculated from the redox properties of the alkyl halide and the copper complex. The values of [R*] in MeCN/bulk and in H2O were determined to be 8.2 x 10(-8) and 6.3 x 10(-5) M, respectively. The respective kp values are in good agreement with the literature values (3.6 x 10(3) M-1 s(-1) for OEGMA in water and 2.5 x 10(3) M-1 s(-1) for methyl acrylate in bulk).

  • 49.
    Coullerez, Geraldine
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Solvent effects on the redox properties of Cu complexes used as mediators in atom transfer radical polymerization2006In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 110, no 34, p. 10355-10360Article in journal (Refereed)
    Abstract [en]

    Solvent effects on the redox properties of six Cu(I) complexes used as mediators in atom transfer radical polymerization (ATRP) have been studied using cyclic voltammetry. The six ligands used were tris[2(dimethylamino) ethyl] amine, N-(n-propyl)-2-pyridylmethanimine, N, N, N', N', N'-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyl-triethylenetetramine, 2,2'-bipyridine, and 1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecan. The solvents used were DMSO, DMF, MeCN, MeOH, IP, and BuOH. Significant solvent effects were observed and quantitatively analyzed in terms of Kamlet-Taft relationships. The resulting Kamlet-Taft equations were found to successfully describe the solvent effects and could thus be used as tools for the design of ATRP in new solvents. The solvent sensitivity of the different ligands and the nature of the solvent effects are also discussed to some extent.

  • 50.
    Ek, Monica
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Chirat, Christine
    Fogelstrom, Linda
    Iversen, Tommy
    Li, Dongfang
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Norström, Emelie
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Sixta, Herbert
    Testova, Lidia
    Toivari, Terhi
    Wawro, Dariusz
    WOBAMA: wood based materials and fuels2014In: Cellulose Chemistry and Technology, ISSN 0576-9787, Vol. 48, no 9-10, p. 773-779Article in journal (Refereed)
    Abstract [en]

    WOBAMA - Wood Based Materials and Fuels is a biorefinery oriented scientific research project supported by Wood Wisdom-Net Research Programme and ERA-NET Bioenergy. In this project, the wood based raw materials were converted to a range of value added products through unconventional techniques. So far, many demonstrators have been prepared, such as the dissolving pulps with high cellulose content, the regenerated cellulose films with high tenacity, the hydrophobic materials based on cellulose and birch bark suberin, as well as the adhesives based on polysaccharides.

12345 1 - 50 of 227
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