Baolong Zhang

Construction and micellization of a noncovalent double hydrophilic block copolymer

The first noncovalent double hydrophilic block copolymer was constructed through inclusion complexation between beta-cyclodextrin and the adamantyl group; it can further self-assemble into two distinctly different micelles in response to pH and temperature in dilute aqueous solution.

A study on the properties of epoxy resin toughened by a liquid crystal‐type oligomer

A series of novel reactive toughening agents (LCEUPPG) containing both a flexible spacer and rigid liquid crystalline unit were synthesized to modify the bisphenol epoxy resin/dicyandiamide curing system. The curing reactivity, apparent activation energy, curing mechanism, dynamic mechanical behavior, and impact strength of the modified system were systematically studied. Compared with the unmodified system, the results indicate that LCEUPPG have greatly accelerated the curing reaction between epoxy resin and dicyandiamide, reduced the apparent activation energy of the curing reaction, enhanced the impact strength 3–7 times, and maintained high dynamic modulus and good thermal properties. In addition, SEM observation of the fracture surfaces showed a two-phase microstructure in the modified systems.

Synthesis of well-defined poly(N-isopropylacrylamide)-b-poly(L-glutamic acid) by a versatile approach and micellization.

A novel Fmoc-protected chain transfer agent (CTA) was synthesized and applied in the reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAAm), resulting in well-defined Fmoc-protected PNIPAAm and the amino-end capped PNIPAAm by the subsequent hydrolysis. Poly(N-isopropylacrylamide)-b-poly(l-glutamic acid) (PNIPAAm-b-PLGA) with controlled molecular weight and narrow molecular weight distribution was synthesized successfully via ring-opening polymerization (ROP) of alpha-amino acid N-carboxyanhydrides (NCAs) by using PNIPAAm-NH2 as the macroinitiator. Both pH- and thermo-responsive micellization behaviors of the block copolymer PNIPAAm55-b-PLGA35 in dilute aqueous solution were investigated by means of the pyrene fluorescence, circular dichroism, 1H NMR, transmission electron microscopy and dynamic and static light scattering. Spherical PLGA-core and rod-like PNIPAAm-core micelles are formed in response to pH and temperature. The reversible transition between the PLGA-core and PNIPAAm-core micelles was observed. This work provides a versatile approach for synthesizing well-defined stimuli-responsive polypeptide-based double hydrophilic diblock copolymers (DHBCs), and is of great potential for generating useful stimuli-responsive materials in biomedical applications.

A study on properties of epoxy resin toughened by functionalized polymer containing rigid, rod-like moiety

Abstract A series of novel reactive toughening agents defined as LCEUPEG containing both flexible chain and rigid, rod-like moiety were synthesized and used to modify the epoxy resin (E-51)/dicyandiamide (dicy) curing system. The curing reactivity, apparent activation energy Ea, curing mechanism, dynamic mechanical behavior, impact strength of E-51/LCEUPEG/dicy systems was studied. The results show that the addition of LCEUPEG to epoxy resin and dicy curing system has apparently accelerated the curing reaction, reduced the apparent activation energy Ea of the curing reaction by about 60 kJ/mol, and decreased the curing temperature by about 50°C. In addition, the high modulus and good thermal properties are maintained, and the impact strength is enhanced by three to seven times compared with that of the unmodified sample.

Photoresponsive side-chain liquid crystalline polymers with amide group-substituted azobenzene mesogens: effects of hydrogen bonding, flexible spacers, and terminal tails

The synthesis of a series of new photoresponsive side-chain liquid crystalline polymethacrylates with amide group-substituted azobenzene (azo) mesogens and different length of flexible spacers and terminal tails via conventional free radical polymerization is described. The resulting azo polymers proved to have high thermal stability and good solubility in common organic solvents (e.g., tetrahydrofuran and chloroform). Differential scanning calorimetry, polarizing optical microscopy, and small angle X-ray scattering studies confirmed the presence of obvious enantiotropic smectic C liquid crystalline phases (with a bilayer lamellar structure) for all these polymers. The introduction of an amide group into the azo mesogen led to the formation of strong hydrogen bonding among the side chains of the polymers (as revealed by variable temperature FT-IR), which played a decisive role in forming and stabilizing the liquid crystalline mesophases of the polymers. In addition, the length of the flexible spacers and terminal tails also significantly influenced their phase transition behaviors. Furthermore, the photoresponsivity of the polymer solutions was verified and the effects of the molecular structures of the polymers on their photoresponsive properties were also studied.

Protein recognition onto silica particles using chitosan as intermedium substrate

A novel molecular imprinting method was used to prepare twice-coated silica particles with specific recognition sites for hemoglobin. Chitosan was used as an intermedium to be coated on silica particles via phase inversion process, and the abundance of exposed amine groups (NH2) were active sites for introducing aldehyde groups. After hemoglobin was covalently immobilized by forming imine bonds with the aldehyde groups, acrylamide was then polymerized onto chitosan-coated silica particles to form the recognition sites. The obtained hemoglobin imprinted [molecularly imprinted polymer (MIP)] beads were characterized by FTIR spectroscopy, thermogravimetric analysis (TG), and scanning electron microscopy (SEM). The MIP particles exhibited selectively adsorption for the imprinted protein compared to the nonselectively adsorption for most of proteins of the nonimprinted (NIP) beads.

Application of a series of novel chain-extended ureas as latent-curing agents and toughening modifiers for epoxy resin

A series of novel chain-extended ureas (Ui) containing poly(ethylene glycol) (PEG) spacers with different molecular weights were synthesized and the reactive mechanism, reactive activity, impact strength, dynamic mechanical behavior, morphology, and storage properties of the epoxy resin/chain-extended urea system were studied. Experimental results revealed that the impact strength of the epoxy resin modified with chain-extended urea containing a PEG flexible spacer with molecular weight of 1000 is 9.5 times higher than that of the epoxy resin/dicyandiamide system. Results also show that the molecular weight of PEG in chain-extended ureas hardly has any influence on the reactive activity of the chain-extended ureas. The storage life of the epoxy resin/Ui system can be delayed to 38 h at 50°C.

Curing behavior and kinetics of epoxy resins cured with liquid crystalline curing agent

This article describes the synthesis of a liquid crystalline curing agent 4,4′-bis-(4-amine-butyloxy)-biphenyl (BABB), and its application as a curing agent for the epoxy resin (DGEBA) in comparison with normal curing agent, 4,4′-diaminobiphenyl (DABP). BABB was investigated with polarized optical microscopy, differential scanning calorimetry, and small-angle X-ray scatting, and the results showed that BABB displayed smectic liquid crystalline phase. The curing behaviors of DGEBA cured with BABB and DABP were studied by using differential scanning calorimetry (DSC), polarized optical microscopy (POM), and dynamic mechanical analysis (DMA). The results indicated that BABB showed a higher chemical reactivity than DABP. The kinetics was studied under isothermal conditions using an isoconversional method, and the isothermal DSC data can be fitted reasonably by an autocatalytic curing model. The nematic droplet texture was observed for the resulting polymer network of DGEBA/BABB system, while the DGEBA/DABP system showed an isotropic state. The storage modulus of DGEBA/BABB system was enhanced in comparison with DGEBA/DABP system because of the formation of LC phase, whereas the glass transition temperatures decreased because of the introduction of flexible spacer group.

Modification of epoxy resins by acrylic copolymers with side-chained mesogenic units

A series of acrylic copolymer modifiers with mesogenic side chain (LCGMB) were synthesized and used to modify E-51/DDM system. The dynamic mechanical behavior and impact strength of the modified systems were investigated. The results showed that the impact strength and modulus were influenced by the composition and the amounts of the modifiers. With addition of 10% (wt %) LCGMB (molar ratio of GMA : HEMA : MMA : BA = 4 : 10 : 26 : 60) based on the amount of the epoxy resin, the modified systems obtained 100% increase in impact strength, 10% increase in modulus, and a little increase in Tg. The toughening mechanism of the modified systems was also discussed.