Synthesis and physical properties of highly branched perfluorinated polymers from AB and AB2 monomers

Highly branched perfluorinated aromatic polyether copolymers were prepared from the polycondensation of the AB₂ monomer, 3,5‐bis[(pentafluorobenzyl)oxy]benzyl alcohol with a variety of fluoroaryl and alkyl bromide AB comonomers. The structures and comonomer distribution of the resulting polymers were characterized in detail. ¹H NMR data from kinetic trials illustrated that perfluoroaryl AB comonomer distribution correlated to AB comonomer sterics. ¹⁹F NMR data revealed that fluorinated AB monomers and 3‐bromo‐1‐propanol AB monomers were distributed within the AB₂ polymer backbone, while longer alkyl bromide AB monomers, 6‐bromo‐1‐hexanol, were mostly distributed along hyperbranched polymer chain ends. In general, as AB comonomer incorporation increased for nonsterically hindered copolymers, thermal decomposition onset increased and glass transition temperatures decreased. The combined data demonstrated the effect of comonomer distribution and sterics on physical properties of AB₂‐based polymer systems. The resulting materials were used to cast thin polymer films for measurement of contact angle, which were shown to be directly related to comonomer content. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1880–1894     

Novel hyperbranched polymers synthesized via A3 + B(B′) approach by radical addition‐coupling polymerization

In this study, a novel application of radical addition‐coupling polymerization (RACP) for synthesis of hyperbranched polymers is reported. By Cu/PMDETA‐mediated RACP of 2‐methyl‐2‐nitrosopropane with trimethylolpropane tris(2‐bromopropionate) or a bromo‐ended 3‐arm PS macromonomer, two types of hyperbranched polymers with high degree of polymerization are synthesized under mild conditions, respectively. The chemical structures of the hyperbranched polymers are carefully characterized. By selective degradations of the ester groups and weak bonds of NO? C in the polymers, high degree of alternative connection of the two monomers in the synthesized polymers have been identified. Based on the experimental results, mechanism of formation of the hyperbranched polymer is proposed, which includes formation of carbon radicals from the tribromo monomer through single electron transfer, its capture by 2‐methyl‐2‐nitrosopropane that results in nitroxide radical, and cross‐coupling reaction of the nitroxide radical with other carbon radicals. Hyperbranched polymer can be formed in a step‐growth mode after multiple steps of such reactions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 904–913     

Facile synthesis of linear–hyperbranched polyphosphoesters via one‐pot tandem ROMP and ADMET polymerization and their transformation to architecturally defined nanoparticles

A convenient one‐pot synthesis of linear–hyperbranched polyphosphoesters (l–HBPPEs) was accomplished by a tandem ring‐opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) polymerization procedure. A linear monotelechelic poly(norbornene) with a terminal acrylate and many pendent thiol groups is first prepared through adding an internal cis‐olefin terminating agent to the reaction mixture immediately after the completion of the living ROMP, and then utilized as a macromolecular chain stopper in subsequent ADMET polymerization of a phosphoester functional AB₂ monomer, yielding l–HBPPEs as the reaction time prolonged. These l–HBPPEs bearing lots of pendent thiol groups in linear poly(norbornene) and peripheral acrylate groups in HBPPE could be self‐crosslinked in ultradilute solution through thiol‐Michael addition click reaction between acrylate and thiol to give single‐molecule nanoparticles with comparatively uniform size. This facile approach can be extended toward the fabrication of novel nanomaterials with sophisticated structures and tunable multifunctionalities. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 964–972     

Synthesis and characterization of degradable hyperbranched poly(2‐ethyl‐2‐oxazoline)

Hyperbranched poly(2‐ethyl‐2‐oxazoline) was synthesized by a combination of cationic ring‐opening polymerization and the oxidation of thiol to disulfide groups. A three‐arm star poly(2‐ethyl‐2‐oxazoline) (PEtOx) was first synthesized using 1,3,5‐tris(bromomethyl) benzene as an initiator. The star PEtOx was end‐capped with potassium ethyl xanthate. Similarly, a linear PEtOx was synthesized and end‐capped with potassium ethyl xanthate using benzyl bromide as an initiator. Hyperbranched PEtOx was then obtained by in situ cleaving and subsequent oxidation of the star PEtOx and linear PEtOx mixture with n‐butylamine as both a cleaving agent and a base in tetrahydrofuran. The linear PEtOx was used to prevent the formation of gel. The hyperbranched PEtOx can be cleaved with dithiothreitol to trithiol and monothiol polymer. The hyperbranched PEtOx shows no remaining thiols using Ellman's assay. The resulting hyperbranched PEtOx was hydrolyzed to a novel hyperbranched polyethyleneimine with degradable disulfide linkages. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2030–2037     

Direct synthesis of hyperbranched ethene oligomers and ethene-MA co-oligomers using iminopyridyl systems with weak neighboring group interactions

The synthesis of hyper-branched ethene oligomers through catalytic insertion reactions with late transition metal catalysts is unique in its synthetic and practical scope. In this study, a series of iminopyridyl Ni(II) and Pd(II) complexes with electron-rich distal aryl motifs were synthesized and characterized. These complexes were very efficient in ethene oligomerization and co-oligomerization with methyl acrylate (MA). Hyperbranched ethene oligomers with different microstructures were generated using different metal species in ethene oligomerization. More importantly, hyperbranched ethene-MA co-oligomers with varying incorporation ratios were generated via ethene and MA co-oligomerization using the Pd(II) complexes. Most notably, weak neighboring group interactions of distal aryl motifs in the nickel system are more effective in influencing the microstructure of ethene oligomers than the corresponding palladium system.     

Hyperbranched Kaustamin as an antibacterial for surface treatment

Hyperbranched Kaustamin as a commercially available cationic flocculant adsorbs on a glass surface with formation of the polymer film. Kaustamin has antimicrobial effect on Gram-negative and Gram-positive bacteria, its film on glass keeps integrity and shape after absorption of water from air, which make the polymer appropriate as an antibacterial cover.     

Association,emulsifying, and solubilization properties of amphiphilic hyperbranched poly(acrylic acid) with short polystyrene stickers

Amphiphilic hyperbranched copolymer chains made of large hyperbranched poly(acrylic acid) cores grafted with short polystyrene stickers (HB‐PAA_n‐g‐PS_{n + 1}) with different n values (n = 1, 10, 47) were well prepared and confirmed by size exclusion chromatography, Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance. The study on the interchain association behavior of these amphiphilic chains indicates that larger HB‐(PAA)_n‐g‐(PS)_{n + 1} copolymer chains have a less tendency to undergo interchain association. Moreover, the simple vial‐inversion and rheological experiments show that the apparent critical gel concentration (C_g) decreases with n, but no sol–gel transition was observed for triblock PS‐PAA‐PS even when the concentration is up to 200 g L^?1. Further transmission electron microscopy study of the latex particles prepared with HB‐(PAA)_n‐g‐(PS)_{n + 1} as surfactant reveals that the latex particles are spherical and narrowly dispersed; while the measured latex particle number (N_p) indicates the surfactant efficiency of HB‐(PAA)₄₇‐g‐(PS)₄₈ is poorer than that of triblock PS‐PAA‐PS (n = 1). Finally, pyrene solubilization measurement shows the solubilization efficiency of HB‐(PAA)_n‐g‐(PS)_{n + 1} copolymers decreases with n, consistent with the previous observed interchain association result. The present study demonstrates that both the chain topology and the styrene weight fraction dominates the final solution properties of amphiphilic HB‐(PAA)_n‐g‐(PS)_{n + 1} chains in aqueous solution. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 128–138     

High refractive index hyperbranched polyvinylsulfides for planar one‐dimensional all‐polymer photonic crystals

We report on the growth and characterization of one‐dimensional (1D) planar all‐polymer photonic crystals (PhC) with high dielectric contrast (Δn = 0.3) prepared by spin coating using hyperbranched polyvinylsulfide polymers (HB‐PVS) as high refractive index material and cellulose acetate as low refractive index material. Solution processable HB‐PVS show a near ultraviolet absorption inducing an increased refractive index in the visible‐near infrared (n = 1.68, λ = 1000 nm). HBPVS:Cellulose Acetate Distributed Bragg Reflectors show a very clear fingerprint of the photonic band gap possessing the expected polarized dispersion properties as a function of the incidence angle. Moreover, engineered microcavities tuned on the weak fluorescence spectrum of the HB‐PVS show directional fluorescence enhancement effects due to spectral redistribution of the emission oscillator strength. The combination of all these properties testifies the high optical quality of the obtained photonic structures thus indicating HB‐PVS as an interesting material for the preparation of such PhC. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 73–80     

Hyperbranched Polymer-Based Vaccines for Cancer Immunotherapy

Recently, several immunotherapeutic strategies are extensively studied and entered clinical investigation, suggesting their potential to lead a new generation of cancer therapy. Particularly, a cancer vaccine that combines tumor-associated antigens and immune adjuvants with a nanocarrier holds huge promise for inducing specific antitumor immune responses. Hyperbranched polymers, such as dendrimers and branched polyethylenimine (PEI) possessing abundant positively charged amine groups and inherent proton sponge effect are ideal carriers of antigens. Much effort is devoted to design dendrimer/branched PEI-based cancer vaccines. Herein, the recent advances in the design of dendrimer/branched PEI-based cancer vaccines for immunotherapy are reviewed. The future perspectives with regard to the development of dendrimer/branched PEI-based cancer vaccines are also briefly discussed.     

Dendronized Hyperbranched Macromolecules: Soft Matter with a Novel Type of Segmental Distribution

Dendronization of a hyperbranched polyester with different generation dendrons leads to pseudo‐dendritic structures. The hyperbranched core is modified by the divergent coupling of protected monomer units to the functional groups. Compared to dendrimers, the synthetic effort is significantly less, but the properties are very close to those of high‐generation dendrimers. The number of functional groups, molar mass, and rheology behavior even in the early generation (G1–G4) pseudo‐dendrimers strongly resembles the behavior of dendrimers in higher generations (G5–G8). Comparison of the segmental and internal structure with perfect dendrimers is performed using SANS, dynamic light scattering and viscosity analysis, microscopy and molecular dynamics simulation. The interpretation of the results reveals unique structural characteristics arising from lower segmental density of the core, which turns into a soft nano‐sphere with a smooth surface even in the first generation.