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.     

含螺环结构的二胺及其聚酰亚胺的合成与性能

首先,以双酚A和甲磺酸反应合成出3,3,3',3'-四甲基-6,6'-二羟基-1,1'-螺旋双茚满,然后与2-氯-5-硝基三氟甲苯反应得到3,3,3',3'-四甲基-6,6'-双[4-硝基-2-三氟甲基苯氧基]-1,1'-螺旋双茚满,最后在Pd/C-水合肼还原作用下得到3,3,3',3'-四甲基-6,6'-双[4-氨基-2-三氟甲基苯氧基]-1,1'-螺旋双茚满。采用上述二胺单体分别与1,2,3,4-环丁烷四酸二酐、均苯四甲酸二酐、联苯二酐、3,3',4,4'-二苯醚四酸二酐、3,3',4,4'-二苯酮四酸二酐和六氟二酐通过两步法制备出6种含螺环结构的聚酰亚胺(PI)。采用核磁、红外光谱、X射线衍射、紫外-可见光谱、热重分析、差示扫描量热分析和溶解性测试等手段表征了所得化合物和PI的结构与性能。研究结果表明,这些含螺环的PI主要表现为非晶结构和较大的分子链间距离,且具有良好的溶解性、光学性能和热性能。     

Effect of K0.5Na0.5NbO3 filling particles on the charge carrier trap distribution of polyimide films

Polyimide (PI) films filled with K_0.5Na_0.5NbO₃ (KNN50) particles at different weight 0, 5, 10, and 15 wt % had been prepared by in‐situ dispersion polymerization process. The thermally stimulated current (TSDC) method was used to investigate the charge carrier trap levels and their distribution of the composite films. The TSDC spectra show that pure film has ‐peaks and ‐peak, but the composite films only have ‐peaks and an extraordinary peak at high temperature region. The trap parameters were calculated by an approximate model, and the results indicate that charge released of the shallow traps show a nonlinear behavior. The trap energies decrease from 0.879–0.968 eV to 0.549–0.839 eV with the increase of the KNN50 content. The surface and interface between KNN50 and PI matrix was considered to the variation of the trap levels. The extraordinary peak of the composite films was correlated with the phase transition of the KNN50 particles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39828.     

Synthesis and characterization of pyridine‐containing poly(imide‐siloxane)s and their adhesion to copper foil

A series of pyridine‐containing poly(imide‐siloxane) (PIS) copolymers with different amounts of PDMS with various segmental lengths were synthesized from 2,6‐diaminopyridine (DAP), α,ω′‐aminopropylpoly(dimethylsiloxane) (PDMS), 1,3‐bis(4‐aminophenoxy)benzene (APB), and 4,4′‐oxydiphthalic dianhydride (ODPA). A modified synthetic approach was applied instead of approaches commonly reported in the literature, to ensure the incorporation of DAP and PDMS. The effects of the content and the segmental length of PDMS on the thermal glass transition temperature (T_g), dielectric constant, and surface electrical resistivity of the copolymer are investigated. The copolymers were attached to copper foil by hot‐pressing, and changes in wettability caused the peel strength of the laminates to increase with the PDMS content, but to decrease as the DAP content increased. Furthermore, X‐ray photoelectron spectroscopy was employed to determine the loci of failures (LOF) of the laminates and to monitor the movement of LOF, which varies with the PDMS content. For those laminates with good peel strengths, the LOF occur in the interior of PIS layer, indicating that the adhesion is cohesive rather than adhesive. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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.     

Biodegradable and conductive hyperbranched terpolymers based on aliphatic polyester,poly(D,L-lactide), and polyaniline used as scaffold in tissue engineering

Designing the novel conductive and biodegradable scaffolds based on star-like hyperbranched terpolymers of aliphatic polyester–poly(D,L-lactide)–polyaniline (S-HAP–PLA–PANI) was the purpose of this research. The electroactivity of tissue engineering scaffold, which in the current work was for the presence of PANI, is an essential factor in its performance because the electrical signals are the pivotal physiological stimuli that control the adhesion and differentiation of various cell types. Star-shaped polymers have attracted conspicuous attention, thanks to their low-cost, well-defined highly functionalized structures and low crystallinity, and they also could be an interesting alternative to the linear analogs for their interaction with surrounding tissue and faster degradation rate. In the present work, after 12 weeks, the mass loses for S-HAP–PLA–PANI sample were calculated to be 45%. Scaffolds based on S-HAP–PLA–PANI/PLA nanofibers having the average diameter of 70–200?nm and electrical conductivity of 0.05 S cm^?1 imitated the natural microenvironment of extra cellular matrix to regulate the cell attachment, proliferation, and differentiation.     

Powder coatings technology: new developments at the turn of the century

The growth of the powder coating business is affected by the toxicological effects of the raw materials used in the coating formulation and the saturation of the present market for powder coatings, being limited to general metal applications only. This has a strong influence on the long-term research programmes at both raw materials suppliers and powder paint producers. In the last decade of the 20th century, we witness appearance of several new types of toxicologically-safe powder coating systems on the commercial scale. At the same time, there is strong evidence of efforts to penetrate new market fields where powder coatings are not typically used. This includes the markets for automotive clear top coatings, can and coil coatings, coatings for industrial wood, plastics and paper. The new developments in the chemistry of powder coatings are followed by changes and improvements in the production technology for powder coatings as well as developments of new application techniques. This paper summarises the research work on chemistry, production and application technology of powder coatings and tries to extrapolate the tendencies in the years to come in order to predict the achievements and the impacts on the paint industry.     

Enhancing flame retardant and antistatic properties of polyamide 6 by a grafted multiwall carbon nanotubes

In order to improve the flame retardancy and antistatic properties of polyamide 6 (PA6) at as low amount of additives as possible, an integrated-functional additive was synthesized by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and multiwalled carbon nanotubes (MWCNTs). The results showed 2 wt% of DOPO-MWCNTs distributed in PA6 formed an electric network and decreased volume resistivity sharply to 3.1 × 10⁸ Ω cm. In other words, it helped PA6 to get to the percolation threshold of semiconductor. By using of 3 wt% DOPO-MWCNTs, the severe dripping in burning of PA6 was almost controlled. The possible reason was also ascribed to the network formed by evenly dispersed DOPO-MWCNTs, which strengthened the char structure and held severe dripping of PA6. As a result, the heat and smoke release were also suppressed obviously. The most important is that CO release was about half cut in CONE test.     

Graphene oxide-containing isocyanate-based polyimide foams: Enhanced thermal stability and flame retardancy

Isocyanate-based graphene oxide-containing polyimide foams were synthesized by a semi-prepolymer method. In this method, while the first solution containing pre-polymer was derived from pyromellitic dianhydride and excess polymethylene polyphenylene isocyanate (PM200), the second solution contains dianhydride derivatives, water, catalysts, surfactants, and graphene oxide. PIFs were prepared with 0%, 0.25%, 0.50%, 0.75%, and 1% graphene oxide by weight, respectively. PIFs exhibited a minimum side reaction and urea generation was not seen for all PIFs instead of imide bonding. The addition of graphene oxide (GO) leads to a more close-packed structure. Therefore, crosslinking density and thermal stability of graphene oxide-containing polyimide foams increased. Upon the addition of 1% GO, almost seven times higher compression strength was obtained compared to neat PIFs. Also, LOI values supported the theory that thermally stable and flame retardant PIFs can be synthesized via the isocyanate-based process with GO.     

Excellent Polyimide Dielectrics Containing Conjugated ACAT for High-Temperature Polymer Film Capacitor

In order to meet the requirements of polymer dielectric materials for high thermal stability and excellent dielectric properties in the application of high-temperature film capacitors, a series of polyimide (PI) films are fabricated by introducing a self-synthesized aniline trimer (ACAT) with a conjugated structure in this work. Since the conjugated ACAT in the main chains of PI improves the electron polarization and carrier mobility of the PI molecular chains, the dielectric constant of the ACAT-PI films is greatly enhanced (4.4–7.4). Meanwhile, the dissipation factor does not increase apparently (0.002–0.013). The dielectric properties are stable even when the temperature is up to 200 °C, the thermal degradation temperature is as high as 450 °C, and the mechanical properties are also excellent (70–105 MPa). Among all the films, the PI film with 5 mol% ACAT exhibits the maximal energy density of 3.6 J cm⁻³ under the field of 426 kV mm⁻¹, the high tensile strength (90 MPa) and the excellent thermal stability (T_d5 = 515 °C). The work paves the way to prepare high-temperature polymer dielectric film materials with high energy storage density.