Polymers and plastics dominate our rapidly developing daily needs and show enormous potential for the development of new technologies. The future of polymer chemistry will be influenced by the elaboration of new functional polymers. At the beginning of the application of synthetic materials, naturally occurring polymers as cellulose or polyisoprene were simply modified, for example by esterification or cross-linking to obtain the desired properties. Nowadays, the development of various functional polymers is becoming increasingly important in specific areas of application. In terms of technical applications, functional polymers are important, for example in the fields of optics, electronics or catalysis. They are also widely used for analytical devices, (e.g. columns for chromatography), for membranes and in the solid phase synthesis of peptides and oligonucleotides.
Graphical Abstract
Scheme 1: Bisacylphosphine oxide with improved solubility in polar solvents.
Scheme 2: Etherification of 3-(chloromethyl)-2,4,6-trimethylbenzoic acid and chlorination of 1.
Scheme 3: Rearrangement of 2 under formation of 4.
Scheme 4: Synthesis of WBAPO starting from P,P-dichlorophenylphosphine and 2.
Figure 1: 1H NMR spectra (400 MHz, CDCl3) of BAPO and WBAPO.
Scheme 5: Structure of the main impurity in isolated WBAPO.
Figure 2: UV–vis absorption spectra of WBAPO and CQ dissolved in acetonitrile (10−3 mol/L).
Figure 3: DSC-plot of a mixture of Bis-GMA (42 wt %), UDMA (37 wt %), TEGDMA (21 wt %) and the PI WBAPO or BA...
Graphical Abstract
Scheme 1: Synthesis of M2.
Scheme 2: Synthesis of poly(M1-b-M2) and of the micellar catalyst poly(M1-b-M2)-Rh.
Figure 1: Conversion (%) of 1-octene, product formation, product distribution, as well as time dependant n:iso...
Figure 2: Conversion of 1-octene, product formation and product distribution in the hydroformylation in water...
Graphical Abstract
Scheme 1: Synthesis of polysulfone macromonomers.
Figure 1: FT-IR spectra of PSU-2000, PSU-DA-2000 and PSU-DM-2000.
Figure 2: 1H NMR spectra of PSU-2000 (a), PSU-DA-2000 (b) and PSU-DM-2000 (c) in CDCl3.
Figure 3: Rate (a) and conversion (b) of photo induced polymerization of PSU-DA-2000 and PSU-DM-2000.
Figure 4: Rate (a) and conversion (b) of photo induced polymerization of PSU-DAs with different molecular wei...
Figure 5: TGA thermograms of the precursor oligomers (PSU-2000) (a), and macromonomer, PSU-DA-2000 before (b)...
Figure 6: DSC results of the precursor oligomer (PSU-2000) (a), and macromonomer, PSU-DA-2000 before (b), and...
Graphical Abstract
Scheme 1: Synthesis of oligoPPEs by a unidirectional (a) or bidirectional (b) repeating unit by repeating uni...
Scheme 2: Three divergent-convergent routes to oligoPPEs. R denotes solubilising substituents such as hexyl.
Scheme 3: Synthesis of the building blocks 11, 21, and 31. The depicted alkene configuration of 5 was chosen ...
Scheme 4: Carbometalation, an occasionally detected side reaction. The depicted alkene configuration was chos...
Scheme 5: Iodination of 1,4-dihexylbenzene.
Scheme 6: Different routes to compound 14, a representative of the large group of functionalized oligoPPEs.
Graphical Abstract
Figure 1: Preparation of the 8-azido-3,6-dioxaoctyl α-D-mannopyranoside.
Figure 2: Preparation of poly(propargyl-co-N-vinyl pyrrolidone) and subsequent addition of the mannose deriva...
Figure 3: Size of the nanoparticles stabilized with Pluronic® F-68/NVP-PA-Man (0.8/0.2), after addition of in...
Figure 4: Hydrogen and carbon numbering for NMR assignment.
Graphical Abstract
Scheme 1: Grubbs G1–G3 and Umicore U1–U3 catalyst.
Scheme 2: Synthetic pathway to BCP-AnTm using Grubbs’ (1–3) and Umicore (4–6) type catalysts.
Figure 1: 1H NMR spectrum of the homopolymer A50 synthesized with the catalyst U3.
Figure 2: 13C NMR spectrum of the homopolymer A50 synthesized with catalyst U3.
Figure 3: Kinetic progress monitored via 1H NMR spectroscopy of the polymerization of monomer A 7 with cataly...
Figure 4: Kinetic progress monitored via 1H NMR spectroscopy of the polymerization of 7 with catalyst U3; [7]...
Figure 5: ln([M]0/[M]t) vs. time (t) plot obtained from 1H NMR spectra for homopolymer-A50 using catalyst U3;...
Figure 6: Mn vs. time (t) kinetic plot and Mw/Mn (PDI) of the polymerization of monomer T 9 with catalyst U3;...
Figure 7: GPC trace of the block copolymer A25T25 synthesized with catalyst U3.
Figure 8: MALDI-TOF mass spectra of homopolymer A25 4 synthesized with catalyst U3: (a) full spectrum, (b) ex...
Figure 9: MALDI-TOF mass spectrum of BCP-A25T1 synthesized with catalyst U3.
Figure 10: MALDI-TOF mass spectrum of BCP-A25T2 13 synthesized with catalyst U3.
Figure 11: MALDI-TOF mass spectrum of BCP-A25T25 synthesized with catalyst U3.
Graphical Abstract
Scheme 1: Homopolymerization of vinylferrocene 1.
Figure 1: Dynamic light scattering of methyl-β-CD 2 (solid line), vinylferrocene 1 complexed with methyl-β-CD...
Figure 2: The cyclic voltammetry for the complexed PVFc/PVFc+-system 3/6: 1.0 × 10−3 M substance in Na2SO4 | ...
Figure 3: Redox behaviour of PVFc 3: (a) the complexed PVFc 3 mixed with aqueous hydrogen peroxide solution w...
Scheme 2: Copolymerization of vinylferrocene 1 with NiPAAM 5 (1:20).
Figure 4: Lower critical solution temperature of PVFc-co-P(NiPAAM) 7 (1:20) (solid line): 17 °C and complexed...
Graphical Abstract
Figure 1: Synthetic route to hb-PG-b-(P)GA multi-arm star copolymers in a two-step sequence. The well-establi...
Figure 2: SEC-elugrams of the obtained multi-arm star block copolymers derived from PG38. The grafting of pol...
Figure 3: 1H NMR analysis of the star block copolymers with increasing glycolide to poly(glycerol) ratio, usi...
Figure 4: 1H, 1H-correlation COSY NMR: this experiment visualizes correlations of terminal groups with their ...
Figure 5: Comparison of average number of repeat units vs the theoretical number based on the ratio of PG and...
Figure 6: DSC heating traces (second heating run at 20 °C/min) for hb-PG38-b-GA4 (bottom), hb-PG38-b-GA8 (mid...
Graphical Abstract
Scheme 1: Synthesis of (oligo)phenothiazinyl thioacetates 2 and 4.
Figure 1: Normalized absorption (solid line) and emission (dashed line) spectra of thioacetate 2d (recorded i...
Figure 2: Cyclic voltammogram of thioacetate 2d (recorded in CH2Cl2, T = 293 K; 0.1 M electrolyte [Bu4N][PF6]...
Scheme 2: Preparation of SAMs from (oligo)phenothiazinyl thioacetates 2 or 4 on a Au{111}-coated silicon wafe...
Graphical Abstract
Scheme 1: Synthesis of carbonitrile 1.
Scheme 2: Coupling of the β-DMCD-caged carbonitrile derivative 1-DMCD with PVAm to yield the fluorophore-func...
Figure 1: Solid state 13C-{1H}-CP-MAS NMR spectra of pure PVAm (a), functionalized PVAm 1-P (b) and the model...
Scheme 3: Synthesis of 1-Si by nucleophilic aromatic substitution of 1 adsorbed onto silica particles.
Figure 2: Wide-scan X-ray photoelectron spectra (left), C 1s and N 1s high-resolution spectra (right) of bare...
Figure 3: Pore-size distribution of bare silica, PVAm/silica and 1-Si.
Figure 4: UV–vis absorption and emission diffuse reflectance spectra of sample 1-Si.
Figure 5: Normalized absorption and emission spectra of 1-M (a) and 1-P (b).
Figure 6: Normalized emission spectra of 1-P in water at four different pH values and a sketch of the assumed...
Graphical Abstract
Scheme 1: Synthesis of the nitroxide-terminated P2VP-macroinitiator.
Figure 1: Plots of ln(M0/Mt) and molecular weight distribution vs time of the homopolymerization of 2VP at ■ ...
Figure 2: Plots of number average molecular weight vs conversion for the homopolymerization of 2VP for ■ 90 °...
Figure 3: Plot of number average molecular weight vs conversion for the homopolymerization of 2VP at 110 °C w...
Figure 4: MALDI-TOF MS of P2VP obtained for polymerizations stopped after 2, 4, 6, and 8 h. The samples were ...
Scheme 2: Degradation of nitroxide-terminated P2VP-macroinitiator by laser light irradiation.
Figure 5: MALDI-TOF MS of P2VP obtained for polymerizations stopped after 2 h. The samples were prepared by t...
Scheme 3: Synthesis of the bi-responsive block copolymers.
Figure 6: SEC traces for P2VP-block-PNIPAAm (solid line) and P2VP macroinitiator (dashed line).
Figure 7: Demonstration of the solution behavior. Polymers from left to right: P2VP, PNIPAAm, P(2VP)85-block-...
Figure 8: Titration of P2VP105-block-PNIPAAm332 (1g/L) in 0.02 N HCl with 0.1 N NaOH at room temperature.
Figure 9: Hydrodynamic radius distribution of P(2VP)105-b-P(NIPAAm)332 at ○ pH 7, T = 20 °C and ● pH 2, T= 45...
Graphical Abstract
Figure 1: Schematic representation of the investigated strategy for the synthesis of star-shaped poly(2-ethyl...
Scheme 1: General reaction scheme for the preparation of multi-tosylates from multifunctional alcohols (top) ...
Figure 2: MALDI-TOF MS spectra of TetraTos a) and HexaTos b) Matrix: dithranol.
Figure 3: Molecular structure a) and packing diagram b) of the structure of diethyleneglyclol ditosylate (DiT...
Figure 4: Molecular structure a) and packing diagram b) of the structure of 1,4-butanediol ditosylate (DiTos-...
Figure 5: Molecular structure a) and packing diagram b) of the structure of penthaerythritol tetra-tosylate (...
Figure 6: Molecular structure a) and packing diagram b) of the structure of dipenthaerythritol tetra-tosylate...
Figure 7: SEC traces obtained for the polymerization of 2-ethyl-2-oxazoline initiated with TetraTos a) and He...
Scheme 2: Schematic representation of the synthesis of a porphyrin initiated four-armed star-pEtOx starting f...
Figure 8: MALDI-TOF MS spectrum of the tetra-tosylate-porphyrin (TetraTos-B). Matrix: dithranol.
Figure 9: a) 1H NMR spectra (in CDCl3) of the porphyrin initiator TetraTos-B (bottom) and star-pEtOx (top). b...
Figure 10: SEC spectrum obtained for star-pEtOx utilizing a photodiode-array detector (eluent: DMF containing ...
Graphical Abstract
Figure 1: Membrane based separation process.
Figure 2: Chemical structure of the 6FDA (= 4,4′-hexafluoroisopropylidene diphthalic anhydride).
Figure 3: Plasticization phenomenon and resulting effects on separation characteristics.
Figure 4: Synthesis of cross-linkable copolyimide structures.
Figure 5: Investigated cross-linking variations (non cross-linked, covalently and ionically cross-linked).
Figure 6: Hybrid process for the separation of propylene/propane.
Figure 7: Total permeability (left) and selectivity (right) for the 6FDA-4MPD (●) and the 6FDA-4MPD/6FDA-DABA...
Figure 8: Conventional separation process for reformates containing extraction and stripping unit.
Figure 9: Hybrid process for the separation of aromatics/aliphatics.
Figure 10: Pervaporation results for the 6FDA-6FpDA/6FDA-4MPD/6FDA-DABA 3:1:1 copolyimide cross-linked with et...
Figure 11: Pervaporation results for 6FDA-4MPD/6FDA-DABA 4:1 copolyimide (non cross-linked) conditioned in pur...
Figure 12: Pervaporation results for conditioned 6FDA-4MPD/6FDA-DABA 4:1 copolyimide membranes, 100% cross-lin...
Figure 13: Hybrid process for the removal of CO2 in tertiary oil production processes.
Figure 14: Pure CO2 permeabilities at 35 °C for the 6FDA-4MPD (■), the 6FDA-4MPD/6FDA-DABA 4:1 copolyimide ion...
Figure 15: CO2/CH4 separation characteristics for the 6FDA-4MPD/6FDA-DABA 4:1 copolyimide ionically cross-link...
Graphical Abstract
Figure 1: Structure of 3,6-diphenyl-substituted 2,5-diketopyrrolo[3,4-c]pyrrole (DPP).
Scheme 1: Synthesis of DPP monomers.
Figure 2: Plot of current density and light intensity versus voltage of polymer light-emitting diode containi...
Scheme 2: Pd-catalyzed coupling reactions for preparation of DPP-containing polymers.
Figure 3: Optical properties of some diphenylDPP-based conjugated polymers.
Figure 4: Optical properties of copolymers P-21 and P-22 based on two isomeric diphenylDPP monomer units (fro...
Figure 5: Absorption spectroelectrochemical plots of P-25 and P-26 as thin films on ITO glass. Scan rate: 100...
Scheme 3: Thiophenyl-DPP-based polymers.
Graphical Abstract
Scheme 1: Synthesis of magnetic biocatalyst particles.
Figure 1: Structures of comonomers employed in the synthesis of functional core–shell particles.
Figure 2: TEM images of a) Fe3O4 nanoparticles electrostatically stabilized by citric acid; b) Fe3O4@P(M100) ...
Figure 3: a) Cloud point temperature Tc of Fe3O4@P(OxMy) in water in relation to molar fraction of MEMA χM,ex...
Figure 4: a) Normalized magnetization loops of dispersions based on Fe3O4@CA in water (solid line), Fe3O4@CPS...
Scheme 2:
Reaction scheme of the enzymatic digestion of BAPNA catalyzed by magnetically labeled trypsin ().
Figure 5: a) Cornish-Bowden diagram for the temperature-dependent kinetic data of trypsin activity, and b) Ea...
Scheme 3: Proposed mechanism of catalytic activity after heating magnetic biocatalyst particles above Tc.
Figure 6: a) Turnover number kcat and b) Michaelis constant Km of particle- immobilized trypsin vs free tryps...
Graphical Abstract
Scheme 1: One-pot synthesis of epoxide-amine adducts via MW-assisted transfer hydrogenation.
Figure 1: 13C NMR spectra of 4, measured in CDCl3.
Figure 2: MALDI-TOF MS spectra (linear mode) of epoxide-amine product 4.
Figure 3: GPC curve of epoxide-amine product 4 detected by UV absorption.
Figure 4: Number-average hydrodynamic diameters of compound 4 prepared via the one-pot (continuous line) and ...
Scheme 2: Ring-opening polymerization of ε-CL using alcohol units as initiator.
Figure 5: GPC curves of the new formed graft copolymer 6 detected by UV absorption (continuous line) and RI (...
Figure 6: Number-average hydrodynamic diameters of compounds 4 (left) and 6 (right).
Graphical Abstract
Figure 1: Copolymerization of 2 monomers A and B with different polarities in direct miniemlusions with the d...
Figure 2: Interfacial alternating radical copolymerization between dibutyl maleate and vinyl gluconamide for ...
Figure 3: Chemical structures of the surfmers for radical polymerization in miniemulsions: a: sodium vinylben...
Scheme 1: Synthesis of the macroinitiator for ROMP in direct miniemulsion [71].
Figure 4: Monomers used in ionic miniemulsion polymerization. a: octamethylcyclotetrasiloxane [9,74], b: 1,3,5-tris...
Figure 5: Enzymatic reactions in miniemulsion droplets (reproduced with permission from [91]. Copyright (2003) Wi...
Figure 6: Chemical structure of a: polyaniline (leucoemeraldine), b: polypyrrole, c: poly(ethylene dioxythiop...
Figure 7: Transmission electron micrograph of polyurethane capsules synthesized by interfacial polyaddition i...
Figure 8: Schematics for the polycondensation reaction between hydrophobic alcohols and carboxylic acids surr...
Scheme 2: Polyimide from the reaction performed in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoro...
Figure 9: a: TEM micrograph of the cubic structures, b: proposed mechanism for the production of the nanocube...