Lignin esters for use in unsaturated thermosets: lignin modification and solubility modeling.

Department of Chemical Engineering and Center for Composite Materials, University of Delaware, Newark, Delaware 19716, USA.
Biomacromolecules (Impact Factor: 5.37). 01/2005; 6(4):1895-905. DOI: 10.1021/bm0500345
Source: PubMed

ABSTRACT Kraft lignins from hardwood and softwood were esterified with several anhydrides to alter their solubility behavior in nonpolar solvents, such as styrene-containing thermoset resins. The esterification reaction was facile, it reduced the amount of waste products, and can be readily scaled up. Increasing the carbon chain length on the ester group improved the solubility of kraft lignin in nonpolar solvents, with butyrated lignin being completely soluble in styrene. Esterification with unsaturated groups such as methacrylic anhydride, improved the solubility to a lesser extent than the saturated analogues. The solubility behavior of the modified lignin was described using the Flory-Huggins solubility theory, combined with the predictive method of Hoy. The main goal to obtain a styrene soluble kraft lignin that could be used in unsaturated polyesters and vinyl esters was achieved with fully butyrated kraft lignin and a butyrated/methacrylated kraft lignin. The solubility of the latter is governed by the butyrate/methacrylate ratio. The reaction rate constants for the butyration and methacrylation reactions were also determined and the aromatic hydroxyl groups were found to be consistently three times more reactive than the aliphatic ones.

  • [Show abstract] [Hide abstract]
    ABSTRACT: AbstractPolymerizable amphiphilic organophosphorous compounds were synthesized and their self-aggregation behavior was investigated. The studied molecules contain a hydrophilic phosphorus end group, an alkyl chain spacer with a variable length from 3 to 11 CH2 groups and a polymerizable methacrylic group at the other chain end. Thus, the molecules represent a class of polymerizable surfactants. Two different reaction methods were used; either unsaturated alcohols or bromine-containing alcohols were applied as starting compounds for the preparation of the organophosphorous surfactants. The self-aggregation and micelle formation of the prepared compounds were investigated in aqueous solution by dynamic light scattering measurements. The critical micelle concentration of the P-containing amphiphiles was in all cases smaller than 0.040mol/l and strongly dependent on the polarity of the phorphorous head group and the chain length of the spacer. Graphical abstract The synthesis of organophosphorous amphiphiles as surface active monomers for the modification of metal oxide surfaces is presented. The spacer between the phosphorous head group and the methacrylate group was varied with regard to their length and composition. The self-aggregation behavior of these methacrylate-functionalized phosphates and phosphonates surfactants was investigated.
    Monatshefte fuer Chemie/Chemical Monthly 04/2012; 140(4):413-422. · 1.63 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Three kinds of acrylic monomers (2,2,3,4,4,4-Hexafluorobutyl methacrylate (HFBMA), methyl methacrylate (MMA) and butyl acrylate (BA)) were utilized to modify the lignin (BBL) by "grafting from" Free Radical Polymerization (FRP) respectively. Calcium chloride/Hydrogen peroxide (CaCl2/H2O2) was used as initiator. Effects of monomer type and concentration, initiator concentration and polymerization time on grafting from BBL were studied. Grafting of poly (acrylic monomers) onto BBL was verified by the following characterizations and this synthesis method was found to be high efficient and selective for grafting polymerization of BBL. The presence of the BBL moiety in the backbone also resulted in higher glass transition temperature compared with the homopolymer of each monomer, and some modified copolymers also improved its thermal stability. All modifications made BBL more hydrophobic and the static contact angles of these modified copolymers were above 80°. XPS analysis revealed that the surface of these modified BBL copolymers were dominated by acrylate monomer moiety. Additionally, the BBL-g-PBA copolymers can be used as dispersion modifiers in PLA-based materials to enhance UV absorption.
    International journal of biological macromolecules 04/2014; · 2.37 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The preparation of silica-containing organic-inorganic hybrid materials composed of kraft lignin, alkoxysilanes, and organic linkers was investigated. 3-Glycidyloxypropyltrimethoxysilane, 3-(triethoxysilyl)propylisocyanate (IPTES), and bis(trimethoxysilyl)hexane were selected as the most promising linkers. The best materials obtained showed improved mechanical and thermal properties compared with lignin itself. The reaction of the hydroxyl groups with IPTES and the sol-gel reaction between the organic linker molecules were studied by attenuated total reflectance FTIR and solid-state (29) Si magic-angle spinning NMR spectroscopy. The homogeneous composition was demonstrated by electron microscopy and energy-dispersive X-ray spectroscopy mapping. The mechanical properties were investigated by microindentation and dynamic mechanical thermal analysis.
    ChemSusChem 07/2012; 5(9):1778-86. · 7.48 Impact Factor


Available from
Jul 23, 2014