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The reaction of 4-(dibromoboryl)styrene with 2-pyridylmagnesium chloride resulted in the formation of 4-styryl-tris(2-pyridyl)borate free acid (StTypb), a new polymerizable nonpyrazolyl “scorpionate” ligand. StTypb did not undergo self-initiated polymerization under ambient conditions and proved to slowly polymerize through standard radical polymerization at 90 °C. Nitroxide-mediated polymerization (NMP) of StTypb at 135 °C proceeded with good control, resulting in a polymer of Mn = 27400 and PDI = 1.21. The TEMPO-terminated homopolymer successfully initiated the polymerization of styrene, generating an amphiphilic block copolymer with DPn of 1200 and 78 for the PS and the StTypb block, respectively. A similar block copolymer with DPn of 29 and 20 for the PS and the StTypb block respectively was obtained in a reverse polymerization procedure from a PS macroinitiator. The self-assembly of these block copolymers was examined in selective solvents and preliminary metal complexation studies were performed.

In a manner similar to crude oil, technical lignins need refining if their potential as reactive polyphenols of well-defined molecular weight polymers and oligomers is to be actualized. In this paper, we demonstrate that a continuum of narrow fractions can be isolated by the incremental addition of a nonpolar solvent (hexanes) in a polar (acetone) solution of softwood wood kraft lignin. Three distinct commercial samples of softwood kraft lignin were used to examine the validity of the developed protocol using detailed chromatographic and quantitative functional group analytical methods. It was shown that all samples contain a common relatively monodisperse fraction of a polyphenolic material that can be isolated from the different lignins in yields ranging between 10 and 20% w/w. The versatility of the developed fractional precipitation protocol was further validated by creating artificial physical mixtures of the examined lignins in different proportions and isolating from them precisely calculated fract...

In this effort we aim at documenting our understanding of using the phenolic hydroxyl groups of technical softwood kraft lignin in replacing the multifunctional phenolic component required for the synthesis of poly(arylene ether) sulfones. To do this we use a two-pronged approach that uses fractionated softwood kraft lignin whose phenolic hydroxyl groups have been systematically protected in order to avoid gelation when copolymerized with 4, 4′-diflourodiphenyl sulfone (DFDPS). This has been done by careful 31P NMR profiling of the various hydroxyl groups present in the lignin as a function of the degree of phenolic hydroxyl group protection. For all copolymers, weight average molecular weights (Mw), polydispersity indices (PDI), glass transition temperatures (Tg), and thermal stability profiles (TGA) were obtained, providing an integrated picture of the scientific and technological ramifications of this work. Overall, this effort provides the foundations for creating lignin copolymers of controlled and m...

Sandwich-like metal complexes (Tpyb)2M (M = Mg, Fe, Mn) that are based on the novel t-butylphenyltris(2-pyridyl)borate ligand were prepared and fully characterized by multinuclear NMR spectroscopy, high-resolution matrix-assisted laser desorption/ionization (MALDI) mass spectrometry, and single crystal X-ray crystallography. The unique steric and electronic nature of the Tpyb ligand led to structural parameters and properties that are quite different to those of previously reported tris(pyrazolyl)borate and tris(2-pyridyl)aluminate complexes. Most importantly, depending on the crystallization procedure, supramolecular structures could be generated with relatively smaller (ca. 4-5 Å) or larger (ca. 8 Å) diameter pores propagating throughout the crystal lattice. Although the supramolecular structures are held together only by weak intermolecular C-H···π interactions, the solvent in the larger channels could be completely removed without any loss of crystallinity or degradation of the framework. Surface area and gas uptake measurements on the Mg complex further confirmed the permanent porosity, while the calculated non-localized density functional theory (NLDFT) pore diameter of 8.6 Å proved to be in excellent agreement with that obtained from single crystal X-ray crystallography. Our new materials are remarkably thermally stable as degradation did not occur up to about 400 °C based on thermogravimetric analysis (TGA), and a sample of the Mg complex showed no loss of crystallinity even after heating to 140 °C under high vacuum for 72 h according to single crystal X-ray diffraction data.

This work offers a comprehensive understanding of the conditions required for the selective masking of the phenolic hydroxyl groups in technical kraft lignins, which is pivotal in determining their subsequent chemical and thermal reactivity. To this effect, we have examined the chemistry and developed the conditions for the facile, mild, and selective masking of the phenolic hydroxyl groups in softwood and hardwood kraft lignins. We have compared two series of methylated softwood kraft lignins synthesized using different methylation chemistries. Our data show that (when used as specified) dimethyl sulfate in aqueous NaOH selectively converts the phenolic hydroxyl groups of kraft lignin to its methylated derivatives without apparent side reactions. In contrast, methyl iodide (in the presence of excess K2CO3 in N,N-dimethylformamide) was found to be rather ineffective and unselective. Various milder methylation conditions were also examined for both softwood and hardwood kraft lignins using dimethyl sulfate, and the details of this work are documented. In addition, a series of oxypropylation reactions were also carried out using propylene oxide in aqueous NaOH. Propylene oxide was shown to selectively add (at room temperature, 0.5 M NaOH, 18 h) less than two units on average per phenolic hydroxyl group without significant additional polymerization or other side reactions.

The amphiphilic organoboron block copolymer poly (styreneboronic acid)-block-polystyrene (PSBA-b-PS )h as been prepared through a postpolymerization modification route from the silicon-functionalized block copolymer poly(4- trimethylsilylstyrene)-block-polystyrene (PSSi-b-PS). PSBA-b- PS is obtained through highly selective reaction of PSSi-b- PS with BBr3 at room temperature and subsequent hydroly- sis of the BBr2-functionalized intermediate. Transmission electron microscopy studies demonstrate that PSBA-b-PS undergoes pH dependent micellization in aqueous solution. Different morphologies could be realized by using different mixtures of water and organic solvents. V C 2010 Wiley Period- icals, Inc. J Polym Sci Part A: Polym Chem 48: 2438-2445, 2010

A cationic poly(ferrocenylboronium) derivative was prepared by postpolymerization modification reaction of poly(ferrocenylbromoborane) (P1) with 4,4′-dinonyl-2,2′-bipyridyl (Rbipy). The polymer was found to show good stability under ambient conditions and was well soluble in polar organic solvents. Dialysis in MeOH allowed for isolation of a high molecular weight fraction that was further examined. The number-average of repeat units was estimated by GPC analysis relative to PS standards to be n =17, and MALDI−TOF analysis confirmed the chemical structure of the polymer repeat units. A characteristic purple color was observed in solution, which is due to charge-transfer from the electron-rich ferrocenyl to the electron-deficient bipyridylboronium moieties along the polymer main chain.

A new class of amphiphilic organometallic block copolymers with cationic organoboron pendant groups was developed. Selective replacement of one of the bromine substitutents on each boryl group of the block copolymer PSBBr2-b-PS with an organometallic reagent ArM (ArM = 2,4,6-trimethylphenyl copper, 4-t-butylphenyltrimethyl tin) followed by treatment with 2,2′-bipyridine gave the novel block copolymers [3Ar](Br)n as light yellow solid materials that show good stability in air and moisture and high solubility in most organic solvents. Their structure and composition were confirmed by multinuclear NMR, GPC, and elemental analysis. Highly regular micellar aggregates form in block-selective solvents (e.g., MeOH, toluene) as demonstrated by 1H NMR, dynamic light scattering, and transmission electron microscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6612–6618, 2009

Borane-end-functionalized polymers have been prepared through (i) atom transfer radical polymerization (ATRP) of styrene using a silylated initiator, 1-bromo-1-(4-trimethylsilylphenyl)ethane (PEB-SiMe3), (ii) exchange of the SiMe3 end groups with BBr3, and (iii) modification of the Lewis acidic boron centers with nucleophiles. Ditelechelic α,ω-borane-functionalized polymers were obtained through atom transfer radical coupling (ATRC) of the silane-end-functionalized polymers followed by exchange with BBr3 and subsequent reaction with nucleophiles. Self-assembly of the borane-functionalized mono- and ditelechelic polymers into supramolecular structures by means of reversible noncovalent and covalent interactions including Lewis acid−base complexation and boroxine formation has been explored.

Their preparation generallyinvolves either direct polymerization of boron-function-alized monomers or functionalization of polymers withboron groups. Polymerization of boron monomers hasoverall received more attention for the placement ofboron substituents in the side chains of non-cross-linkedpolyolefins. The method of choice usually is standardfree radical polymerization due to the reasonably goodcompatibility with boron-carbon bonds and the rela-tively straightforward synthetic procedures involved.Thus, heat-induced or AIBN (2,2′-azobis(2-methylpro-pionitrile)) initiated free radical polymerization has beenapplied to the homo- and copolymerization of olefinscontaining boronic acid and boronic ester

Selective functionalization of polystyrene with weakly coordinating organoborate functionalities BAr(4)(-) (Ar = Ph, C(6)F(5)) has been accomplished by a polymer modification strategy. The first examples of perfluoroarylborate block copolymers have been prepared; light scattering and TEM studies confirm the formation of reverse micelles, in which the weakly coordinating anion sites are covered by a shell of "inert" polystyrene. The core of the micelles was successfully loaded with a cationic rhodium complex.

Block copolymers of poly(ethylene glycol) (PEG) and poly(ε-caprolactone) (PCL) with chemically addressable functional groups were synthesized and characterized. Ring opening polymerization of ε-caprolactone (CL) and 1,4,8-trioxaspiro-[4,6]-9-undecanone (TSU) using α-methoxy, ω-hydroxyl poly(ethylene glycol) (mPEG) as the initiator afforded a copolymer with cyclic ketals being randomly distributed in the hydrophobic PCL block. At an initiator/catalyst molar ratio of 10/1 and a TSU/CL weight ratio of 1/4, a ketal-carrying copolymer (ECT2-CK) with Mn of 52 kDa and a ketal content of 15 mol% was obtained. Quantitative side chain deacetalization revealed the reactive ketones without noticeable polymer degradation. In our study, 10 mol% of cyclic ketals were deprotected and the ketone-containing copolymer was designated as ECT2-CO. Reaction of ECT2-CO with 2-(2-(aminooxy)acetoxy)-ethyl acrylate gave rise to an acrylated product (ECT2-AC) containing an estimated 3–5 acrylate groups per chain. UV-initiated radical polymerization of ECT2-AC in dichloromethane resulted in a crosslinked network (xECT2-AC). Thermal and morphological analyses employing Differential Scanning Calorimetry (DSC) and Atomic Force Microscopy (AFM) operated in PeakForce Tapping mode revealed the semicrystalline nature of the network, containing stiff crystalline lamellae dispersed in a softer amorphous interstitial. Macroscopic and nanoscale mechanical characterizations showed that ECT2-CK exhibited a significantly lower modulus than PCL of a similar molecular weight. While ECT2-CK undergoes a plastic deformation with a distinct yield point and a cold drawing region, xECT2-AC exhibited a compliant, elastomeric deformation with a Young’s modulus of 0.5 ± 0.1 MPa at 37 °C. When properly processed, the crosslinked network exhibited shape memory behaviors, with shape fixity and shape recovery values close to 1 and a shape recovery time of less than 4 s at 37 °C. In vitro studies showed that xECT2-AC films did not induce any cytotoxic effects to the cultured mesenchymal stem cells. The crosslinkable polyester copolymers can be potentially used as tissue engineering scaffolds and minimally invasive medical devices.

This work focused on providing a molecular understanding of the way the polymeric properties of kraft lignin and its derivatives are affected by various thermal treatments. This information was then correlated with the polymeric properties of the materials (glass transition temperature (Tg), molecular weight characteristics, and thermal stability) for a series of selectively and progressively derivatized softwood kraft lignin samples. Softwood kraft lignin was highly susceptible to thermally induced reactions that caused its molecular characteristics to be severely altered with the concomitant formation of irreversible cross-linking. However, by fully methylating the phenolic OH groups from within the structure of softwood kraft lignin, the thermal stability of these materials was dramatically enhanced and their Tg reduced. While optimum thermal stability and melt re-cycling was observed with the fully methylated derivatives, fully oxypropylated phenolic substitution did not offer the same possibilities. The accumulated data is aimed at providing the foundations for a rational design of single component, lignin-based thermoplastic materials with reproducible polymeric properties when thermally processed in a number of manufacturing cycles.

Tris(2-pyridyl)borates are introduced as a new robust and tunable "scorpionate"-type ligand family. A facile synthesis of this hitherto unknown ligand and its complexation to Fe(II) are described; the optical and electrochemical properties of the resulting iron complex are compared to complexes derived from tris(pyrazolyl)borate, tris(2-pyridyl)aluminate, and corresponding charge-neutral ligands.

The facile preparation of organoboronium polymers via spontaneous reaction of bromoborylated polystyrene with 2,2'-bipyridine is reported; these novel polycations represent an interesting alternative to commonly used ammonium-based polycations.