Chemistry of multifunctional polymers based on bis-MPA and their cutting-edge applications

Polymers play an important role in the advancement of materials for use in cutting-edge applications. A direct consequence of an increased demand for more sophisticated materials has been a drive toward developing polymers that exhibit a higher level of structural control, especially in terms of the number and type of functionalities provided within the polymer framework. A family of polymers that meets such a challenge is based on the readily available AB₂ monomer 2,2-bismethylolpropionic acid (bis-MPA) building block. Due to the ease with which the monomers can be synthesized, an array of multifunctional polymers have been produced including monodisperse dendrimers and dendrons and well-defined linear polymers as well as linear-dendritic hybridizations. This review outlines the evolution of the synthetic strategies for developing novel polymeric architectures based on bis-MPA and their assessment in both solution and substrate-based innovative applications.     

Electrochemical behaviour of phenylethanolamine at gold in aqueous solution

The electrooxidation of phenylethanolamine (2-amino-1-phenylethanol) at a gold electrode in alkaline electrolyte has been studied. Measurement of the differential capacitance of the electric double layer versus the electrode potential has shown that the adsorption of phenylethanolamine at the gold-solution interface plays a significant role in the oxidation mechanism. The effect of amine concentration, electrolyte pH and potential scan rate on the electrooxidation is analysed.     

我国二氧化碳可降解塑料的研究与应用进展

以CO2为原料合成可降解塑料是CO2资源综合利用的一条有效途径。对CO2与环氧化物共聚合成脂肪族聚碳酸酯在我国的研究开发情况进行了综述，并对其在可降解塑料方面的应用前景进行展望。     

Synthesis and properties of polyimides derived from cis- and trans-1,2,3,4-cyclohexanetetracarboxylic dianhydrides

Cis-1,2,3,4-cyclohexanetetracarboxylic dianhydride (cis-1,2,3,4-CHDA) was synthesized. It was found that under such conditions as heating or boiling in acetic anhydride, cis-1,2,3,4-CHDA could be converted to its trans-isomer. The process of thermal isomerization was monitored by ¹H NMR spectra and the mechanism of conversion was proposed. Their absolute structures of cis- and trans-1,2,3,4-CHDAs were elucidated by single crystal X-ray diffraction. The polycondensations of cis- and trans-1,2,3,4-CHDAs with aromatic diamines such as 4,4′-oxydianiline (ODA), 4,4′-methylenedianiline (MDA), 4,4′-diamino-3,3′-dimethyldiphenylmethane (DMMDA), 4,4′-bis(4-aminophenoxy)benzene (TPEQ), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) were studied. It is easy to obtain higher molecular weight polyimides from trans-1,2,3,4-CHDA using conventional one-step or two-step methods. However, higher molecular weight polyimides derived from cis-1,2,3,4-CHDA could not be prepared by the usual methods (solid content ca. 10%) owing to the trend of forming cyclic oligomers. Increasing the concentration of monomers could give higher molecular weight cis-polymers. All of the cis-polyimides were soluble at room temperature in aprotic polar solvents and phenolic solvents and some of them even soluble in chloroform and tetrahydrofuran, while the corresponding trans-polymers showed poor solubility as compared to cis-polymers. All of the polyimides showed good thermal stability with the 5% weight loss temperatures in air over 415 °C. Furthermore, polyimides derived from cis-1,2,3,4-CHDA have higher glass transition temperatures (T_gs) than corresponding trans-polyimides. The flexible polyimide films possessed a tensile modulus range of 2.1-3.6 GPa, a tensile strength range of 42-116 MPa, an elongation at break of 4-18%. These polyimides exhibited cutoffs at wavelengths around 270 nm and were entirely colorless. All the polyimides showed amorphous pattern according to Wide angle X-ray diffraction measurements. The differences of polymerization and properties were explained by the structural changes resulted from isomerism.     

Branched aliphatic polyesters by ring-opening (co)polymerization

The rapid development of biodegradable and biocompatible materials for biomedical applications is reflected in the search for new methods for aliphatic polyester modification applicable in this field. One possible approach is modification by changes to the polymer topology.This review covers the main methods of synthesis of branched aliphatic biodegradable and biocompatible (co)polyesters, where the ring-opening polymerization (ROP) of cyclic esters or cyclic carbonates is the leading process. First, literature examples of ring-opening multibranching polymerization (ROMBP) of AB₂-type hydroxyl-substituted cyclic lactones, lactides and carbonates are cited followed by the presentation of the application of AB-type cyclic esters and additionally AB₂ cyclic ethers or esters as “branching monomers” for the synthesis of branched polyesters based on polycaprolactone (PCL), polylactide (PLA) and polyglycolide (PGA). In the following part, methods involving the combination of the ROP of AB-type cyclic esters and condensation processes leading to branched structures are summarized. Other related strategies leading to “dendri-star” or “core–shell” copolyesters are also discussed. Several examples of approaches to PCL and PLA graft copolymer syntheses are also shown. The advantages and disadvantages of the presented methodologies of branched polyester synthesis are highlighted. Finally, the influence of the branched structure on the properties of the presented class of polyesters, important from the application point of view, is considered.     

Mild oxidative degradation of spent auricularia auricular substrate and molecular composition of carboxylic acids in the resulting soluble portion

Spent auricularia auricular substrate(SAAS) was oxidatively degraded with aqueous hydrogen peroxide(AHPO)/acetic anhydride(AAH) to produce carboxylic acids(CAs) under mild conditions. The results show that up to 53.6% of the organic matter in SAAS was converted to the soluble species(SSs). In total 122 CAs were detected in the SSs by the analysis with a gas chromatograph/mass spectrometer, which can be classified into 29 group components, mainly being aliphatic acids and along with small amount of aromatic acids. Among the aliphatic acids, normal alkanedioic acids are the most abundant. The detected aromatic acids include benzoic acids,phthalic acids, trimellitic acids, pyromellitic acids, and their derivatives. The synergistic oxidation and the released ·OH, CH_3COO·, and HOO· induced by AHPO/AAH play crucial roles in oxidatively degrading SAAS.     

Japan Flavour and Fragrance Materials Association’s (JFFMA) safety assessment of food-flavouring substances uniquely used in Japan that belong to the class of aliphatic primary alcohols,aldehydes, carboxylic acids,acetals and esters containing additional oxygenated functional groups

ABSTRACT

We performed a safety evaluation using the procedure devised by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) of the following four flavouring substances that belong to the class of ‘aliphatic primary alcohols, aldehydes, carboxylic acids, acetals, and esters containing additional oxygenated functional groups’ and are uniquely used in Japan: butyl butyrylacetate, ethyl 2-hydroxy-4-methylpentanoate, 3-hydroxyhexanoic acid and methyl hydroxyacetate. Although no genotoxicity study data were found in the published literature, none of the four substances had chemical structural alerts predicting genotoxicity. All four substances were categorised as class I by using Cramer’s classification. The estimated daily intake of each of the four substances was determined to be 0.007–2.9 μg/person/day by using the maximised survey-derived intake method and based on the annual production data in Japan in 2001, 2005 and 2010, and was determined to be 0.250–600.0 μg/person/day by using the single-portion exposure technique and based on average-use levels in standard portion sizes of flavoured foods. Both of these estimated daily intake ranges were below the threshold of toxicological concern for class I substances, which is 1800 μg/person/day. Although no information from in vitro and in vivo toxicity studies for the four substances was available, these substances were judged to raise no safety concerns at the current levels of intake.     

EIS study on failure process of two polyurethane composite coatings

The performance of acrylic polyurethane composite coating and aliphatic urethane composite coating in 3.5% NaCl solution under ultra-violet radiation was studied with methods of EIS, SEM and FTIR. For aliphatic polyurethane coating, the coating resistance decreased and the coating capacitance and porosity increased more quickly than acrylic polyurethane coating. The acrylic polyurethane composite coatings showed better performance than aliphatic polyurethane composite coatings. IR spectra showed that under UV irradiation conditions, the failure mechanism of the two polyurethane coatings was the transformation of sec-amide to primary amides. The fractured bonds in acrylic polyurethane were mainly C–O bonds, while in aliphatic polyurethane they were mainly C–N bonds. The lower protection property of aliphatic polyurethane coating may be mainly attributed to the C–N bonds which are more liable to be broken.     

Poly(sulphopropylbetaines): 1. Synthesis and characterization

The synthesis of aromatic and aliphatic poly(sulphopropylbetaines) is described within the series of vinylpyridines and tertiary amino-methacrylates. Two complementary strategies were used: (a) preparation and free radical polymerization in aqueous solution (60°C, 4,4'-azobiscyanovaleric acid) of the monomers; (b) heterogeneous quaternization of preformed poly(vinylpyridines) and poly(tertiary amino-methacrylates) by 1,3-propanesultone in propylene carbonate or tetramethylene sulphone solution (120°C). The high molecular weight poly (zwitterions) ($\text{10}{}^5\text{<}\text{M}\text{?}{}_{\mathrm{W}}\text{< 5 × 10}{}^6$) were characterized by ultra-violet and ¹H nuclear magnetic resonance spectroscopy, and their water affinity at 20°C was estimated by water vapour absorption measurements.