ABSTRACT
Aromatic macromolecules tend to form a compact conformation after physically adsorbed on graphene and it brings about great entropy loss for physisorption, due to the strong interaction between aromatic macromolecules and graphene. However, previous researches have validated the availability of aromatic macromolecules to stabilize graphene based on physisorption. In order to clarify the underlying mechanism of this physisorption process on graphene, a series of aromatic polyamide copolymers are used as models in this research. Apart from their adsorbed conformations on graphene, the conformations of these copolymers as the free states in diluted solutions are taken into consideration. Although these copolymers present the fully extended conformation on graphene, their conformations in diluted solutions vary largely with the copolymer composition. It is verified that the copolymer with smaller conformational change could have the better stabilization effectiveness for graphene, rather than the one having stronger interaction with graphene. Therefore, the entropy-tailored behavior for the adsorption of aromatic macromolecules on graphene is put forward. Based on this mechanism, the chemical structure of aromatic polyamide is optimized and furthermore it is utilized to directly exfoliate natural graphite flakes. Eventually, high-quality graphene nanosheets with a large dimension and low defects are obtained. Moreover, its exfoliating effectiveness is superior to those of the commonly used exfoliating agents nowadays.
ABSTRACT
The fabrication of advanced graphene-based nanocomposites with high-performance polymers requires covalent modification of graphene with aromatic macromolecules. Herein, C-N coupling reactions between fluorinated graphene (FG) and aromatic polyamides containing the benzimidazole moiety are successfully achieved. The optimized conditions are presented based on the nucleophilic behavior of the C-N coupling reaction on graphene. Different from the C-N coupling reaction between two small aromatic molecules, the conformation of grafted aromatic polyamide after reaction changes from torsional to paralleled alignment on graphene with the molecular length increment. Non-covalent interactions between graphene and aromatic polyamides result in this conformational change owing to the extended π systems of graphene and aromatic polyamides, and the synergistic effect of covalent and non-covalent interactions is put forward. As a consequence, graphene dispersibility is greatly enhanced in the solution of aromatic polyamide.
ABSTRACT
Because of the strong hydrogen-bond interaction among macromolecular chains, the addition of chloride salts is generally needed to offer Cl- ions for the dissolution of aromatic polyamides. In this paper, poly-(benzimidazole-terephthalamide) which complexed with by-product HCl during polymerization (PABI-HCl) was prepared and imidazole compound as cosolvent was added into dimethylacetamide (DMAc) to dissolve PABI-HCl. Due to stronger affinity to protons, imidazole compound could in-situ complex with HCl of PABI-HCl and form imidazolium hydrochloride. Then imidazolium hydrochloride would ionize and produce much free Cl- ions which acted as stronger hydrogen-bond acceptor to disrupt interaction among macromolecular chains. As a result, solubility of PABI-HCl in DMAc was improved significantly in existence of small amount of imidazole compound. Moreover, DMAc-imidazole mixture was utlized for synthesis of different kinds of aramids and no precipitation was observed with progress of the reaction. So the mixture was suitable to be utlized as solvent for polymerization of aramid.
ABSTRACT
Ultrahigh molecular weight polyethylene (UHMWPE) is an excellent material with high performance, but it is very difficult to covalently introduce functional groups on its surface owing to its inherently inert structure, which constrains its further application. In this study, vinyl triethoxysilane (VTEOS) containing hydrolysable alkoxyl groups was in situ grafted on UHMWPE by air plasma treatment. The plasma treatment conditions for VTEOS grafting were optimized. The structure of the modified UHMWPE was characterized with FTIR and XPS. The relatively high VTEOS content was obtained when the treating conditions were about 20 W, 125 Pa for 10 min. And FTIR results showed that the grafted structure on the surface was stable for long time duration in the ambient environment. After the treatment, the roughness of the surface increased and the water contact angle of the modified sample dropped to 47.5° from 92.8° of the unmodified one. TGA and XRD results indicated that plasma treatment would not change the bulk structure of UHMWPE greatly. Cell culture experiments showed that fibroblasts on the modified samples had notably high viability and proliferation rate with good adhesion shape. Hence, it might be an effective method to improve the surface properties of UHMWPE for biomedical applications by plasma-induced in-situ grafting with VTEOS. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 321-332, 2018.
