环氧树脂类玻璃高分子研究进展

类玻璃高分子(Vitrimer)是一类具有可逆共价交联网络的高分子,其能够在维持交联结构的同时实现交联网络的重构,兼具热固性高分子和热塑性高分子的双重优势。基于通用热固性树脂形成的Vitrimer材料不仅能具有良好的力学性能和耐溶剂性等,还能表现出类似热塑性树脂的流动性和重复加工性能,为从源头上实现交联树脂的回收和再利用提供了有效的途径。近年来,围绕Vitrimer材料的研究已取得了蓬勃的发展,其中数环氧树脂Vitrimer的研究最为广泛,本文将系统介绍环氧树脂Vitrimer的设计理念及其性能特点,梳理该领域的典型研究体系,并指出可能的发展方向,为传统热固性树脂的可再生和高性能化发展提供参考。     

Polymeric materials for water-lubricated plain bearings

Results of tribological studies of modern polymeric materials (thermoplastics, thermosetting materials, composites) used to fabricate water-lubricated bearings are considered. Particular attention is given to carbon-fiber-reinforced plastics modified with powdered metals, fullerene-containing additives, and carbon nanotubes.     

Quality assurance of recycled engineering plastics using blend technology

The automotive, electrical and electronic sectors account for over 12% of all plastics consumed. A large fraction of these polymers are engineering plastics representing a value considerably higher than that of commodity thermoplastics; hence, mechanical recycling including upgrading efforts appears economically attractive. This paper shows some methods of upgrading the property profile of ABS from dismantled automobiles using polymer blend technology. The results for blends of ABS with PC or PA are reported. The aim of blending of the waste materials is twofold: to reduce the number of plastic materials to be recycled in car dismantling plants, and to improve properties of the ABS scrap, which is the main engineering plastic in the waste stream from automobiles.     

Recent development on bio-based thermosetting resins

Due to the rapid depletion of crude oil and serious environmental pollution, the synthesis of polymers from renewable resource is becoming more and more important. Up to now, a great variety of biomass and bio-based platform compounds have been taken to prepare the polymers. However, as two representative thermosetting resins, epoxy and benzoxazine resin derived from renewable feedstocks only obtain limited attention compared with the popular bio-based plastics, including PLA, PBAT and PHBV etc. The reason might be that the properties of previously reported thermosetting resins directly obtained from biomass are usually unsatisfied, and their application fields are limited. In this paper, the latest development on the synthesis of high-performance bio-based epoxy and polybenzoxazine resins are reviewed. In addition, to further broaden their applications, the functionalization strategies are also summarized. The objective of this work is to help us fully aware the present situation of bio-based thermosetting resins and then promote their faster development, especially practical application.     

The Challenge for High Polymers in Medicine,Surgery, and Artificial Internal Organs

High polymers are used in medicine, surgery, or artificial organs in three ways: 1) to construct complete artificial replacements for human organs, 2) to repair, sustain, or augment function of normal organs, and 3) to provide a biochemical function.

Artificial hearts, heart lung machines, and artificial kidneys are examples of artificial organs that man is designing and building to replace natural organs. Plastics are used widely in their construction. Plastics offer a variety of properties needed for these applications, including ease of fabrication, chemical inertness, and nontoxic properties, and a wide range of physical properties in hardness, flexibility, and permeability.

Externally, as adjuncts or assists to natural organs, there are many applications of plastics in present use from clothing to glasses to dentures. Internally, the applications include vascular prostheses, check valve balls for heart valves, encapsulating resins for pacemakers, meshes and foams for reconstructive surgery, drainage tubes, and cannulae for hemodialysis. The plastics most widely used in surgical implants are polytetrafluoroethylene, polypropylene, saturated aromatic polyesters, and polysiloxanes. Growing use is being made of segmented polyurethanes, acrylics, and epoxy resins. Experimental work is under way on polyelectrolytes and various hydrogels based on polyhydroxyl compounds.

The newest class of applications of high polymers is that wherein the polymer has a definite and specific chemical interaction with the biochemistry of the body, i.e., it plays a pharmaceutical role. Examples of this include: 1) synthetic ion exchange resins for absorbing metabolites from the blood; 2) synthetic polyelectrolytes capable of absorbing specific viruses; 3) synthetic polymers such as (a) polyinosinic-polycytidylic acid (a synthetic ribonucleic acid) or (b) a copolymer of vinyl pyran and an undisclosed comonomer which promotes the production of interferon, a chemical substance normally produced by cells as an antiviral agent; and 4) synthetic natural-like polypeptides, enzymes, and chemical modifications of these with enhanced biologic activity.

The future of the use of high polymers in these applications appears to be in the earliest stages. Half a million Americans die each year of heart disease and 60,000 die of kidney disease, hence the potential for artificial versions of these organs is very large. The use of surgical devices is growing steadily. The use of polymers as drugs has not yet been tapped. In 50 years, biochemists will have a battery of synthetic polymer drugs which will cure many diseases, prevent cancer, speed wound healing, and eventually, it is hoped, provide a chemical regime for regeneration of lost limbs and organs.     

Effects of Water and Chemical Solutions Ageing on the Physical,Mechanical, Thermal and Flammability Properties of Natural Fibre-Reinforced Thermoplastic Composites

Biocomposites comprising a combination of natural fibres and bio-based polymers are good alternatives to those produced from synthetic components in terms of sustainability and environmental issues. However, it is well known that water or aqueous chemical solutions affect natural polymers/fibres more than the respective synthetic components. In this study the effects of water, salt water, acidic and alkali solutions ageing on water uptake, mechanical properties and flammability of natural fibre-reinforced polypropylene (PP) and poly(lactic acid) (PLA) composites were compared. Jute, sisal and wool fibre- reinforced PP and PLA composites were prepared using a novel, patented nonwoven technology followed by the hot press method. The prepared composites were aged in water and chemical solutions for up to 3 week periods. Water absorption, flexural properties and the thermal and flammability performances of the composites were investigated before and after ageing each process. The effect of post-ageing drying on the retention of mechanical and flammability properties has also been studied. A linear relationship between irreversible flexural modulus reduction and water adsorption/desorption was observed. The aqueous chemical solutions caused further but minor effects in terms of moisture sorption and flexural modulus changes. PLA composites were affected more than the respective PP composites, because of their hydrolytic sensitivity. From thermal analytical results, these changes in PP composites could be attributed to ageing effects on fibres, whereas in PLA composite changes related to both those of fibres present and of the polymer. Ageing however, had no adverse effect on the flammability of the composites.     

Production of biological polymers from organic wastes

Biologically-produced polymers, from microbial fermentation are naturally biodegradable and are potential environment-friendly substitutes for some synthetic plastics. However, broader applications are restricted by the high production costs and limitations in physical and mechanical properties. In this study, activated sludge bacteria in a conventional wastewater treatment system treating a wastewater that contained organic pollutants, were induced by nitrogen deficiency to accumulate intracellular storage polymers, which can be extracted as a low-cost source of biodegradable plastics. Chromatographic analysis of the extracted polymers revealed a composition of poly-hydroxyalkanoate and a number of related co-polymers. Alcaligene spp. in the activated sludge microbial consortium was identified as the main genus accumulated these polymers. When the C:N ratio was increased from 20 to 140, the specific polymer yield increased to a maximum of 0.39 g polymer/g dry cell while specific growth yield decreased to 0.26 g dry cell/g carbonaceous matter consumed. The highest overall polymer production yield of 0.11 g polymer/g carbonaceous matter consumed was achieved when the C:N ratio was maintained at a nitrogen-deficient level of 100. The specific polymer yield in the isolated Alcaligene spp. cells were as high as 0.7 g polymer/g dry cell mass. The composition of the co-polymers, and hence the physical and mechanical properties, could be controlled by manipulating the influent organic compositions.     

Alkali resistance of cured rolivsans and glass-reinforced plastics based on them

The effect of strongly alkaline media on the strength and heat resistance of thermosetting polymers and plastics prepared by thermal transformations of Rolivsans (cross-linking and cyclizing polyfunctional aromatic ethers with terminal styrene and methacrylate groups) was studied.     

A Cleavable Crosslinking Strategy for Commodity Polymer Functionalization and Generation of Reprocessable Thermosets

Covalently crosslinked polymeric materials, known as thermosets, possess enhanced mechanical strength and thermal stability relative to the corresponding uncrosslinked thermoplastics. However, the presence of covalent inter-chain crosslinks that makes thermosets so attractive is precisely what makes them so difficult to reprocess and recycle. Here, we demonstrate the introduction of chemically cleavable groups into a bis-diazirine crosslinker. Application of this cleavable crosslinker reagent to commercial low-functionality polyolefins (or to a small-molecule model) results in the rapid, efficient introduction of molecular crosslinks that can be uncoupled by specific chemical inputs. These proof-of-concept findings provide one potential strategy for circularization of the thermoplastic/thermoset plastics economy, and may allow crosslinked polyolefins to be manufactured, used, reprocessed, and re-used without losing value. As an added benefit, the method allows the ready introduction of functionality into non-functionalized commodity polymers.     

The Structure and Moisture Stability of the Matrix Phase in Glass-Reinforced Epoxy Composites

The utilization of reinforced plastic composites is generally limited by their sensitivity to long-term environmental exposure. Glass-reinforced thermosetting polymers in particular are detrimentally affected, reversibly and/or irreversibly, by exposure to water vapor or liquid water. A reinforced composite consists of three mutually interacting regions: fiber, matrix, and the fiber/ matrix interface. Each region may, for purposes of convenience, be further subdivided according to its location or properties. Most common is the listing of regions comprising the “interface”: glass/ coupling agent interface, the coupling agent polymer itself, and the coupling agent/matrix interface. Even the amorphous cross-linked matrix nearby the filler is believed to possess properties dissimilar to those of the bulk. Each region and subregion is altered by moisture exposure to some extent; at this time studies on composite stability still focus on determining which regions are most affected by the environment and on the mechanisms of those effects, as well as on devising systems with minimal environmental sensitivity. Moisture effects on glass-reinforced epoxy composites, the most common of the reinforced plastic systems, will be emphasized in this paper. Multifunctional epoxy resins are typically cross-linked by acid anhydrides, forming 3-D polyesters, and by amine functional compounds, yielding 3-D amine-ether polymers. There are many structural varieties; the same hydrothermal degradation mechanisms apply universally, and hereafter the term “epoxy” matrix will be employed. The stability of the glass reinforcement itself and of the interface will first be briefly reviewed as a prelude to a more detailed consideration of the reversible and irreversible moisture effects on the cross-linked epoxy matrix.     

Extraction of nanofibers from polymer blends: A brief review

This review is about the naturally formed and intentionally produced nanofibrils or nanofibers (NFs) that have been extracted and utilized or expected to be used for special applications. The diameter of NFs ranges between a few to a few hundred nanometers. Methods to arrange synthetic NFs assembly in yarns or pads forms have been examined. High throughput productions, versatility of various thermoplastics, and less environmental pollution are the advantages of the methods of extraction, which seems to make it as an economical process. It can also be used for the polymers that are difficult to be converted to NFs by electrospinning. The process is challenging and scientifically fascinating to attract the investigators. There are many more polymers to be considered, and there are many more envisioned applications that have to be practiced in the future. A theoretical base is needed for the evaluation of the effects of polymer flow parameters on the extracted NFs properties.     

Characterization of Engineering Polymers by Dynamic Mechanical Analysis

There is a growing need for the use of polymers in high-strength and engineering applications, and many new materials and composites have been developed to satisfy this need. Traditionally, thermosetting polymers have been employed as high-strength materials, with the incorporation of various fillers or additives to improve shortcomings in strength and temperature performance. Although these materials are largely unrivaled in high-temperature performance, some of the newer engineering thermoplastics, such as poly(ether ether ketone)(PEEK), poly(ether sulfone) (PES), poly(pheny1ene sulfide) (PPS), and the new backbone liquid-crystal polymers are becoming much more widely used. With this widespread use and with the increasing complexity of polymer blends and composites, there is a strong requirement for a universal means of characterizing such materials in terms of mechanical properties and high-temperature performance. A powerful and versatile analytical technique which is capable of application to a very wide range of materials is that of dynamic mechanical spectrometry. This technique can be used to establish basic material relaxation temperatures and frequencies, the modulus and loss behavior, as well as factors such as degree of cure, fder/matrix bonding, and phase separation.     

Design and synthesis of self-healing polymers

Self-healing polymers represent a class of materials with built-in capability of rehabilitating damages. The topic has attracted increasingly more attention in the past few years. The on-going research activities clearly indicate that self-healing polymeric materials turn out to be a typical multi-disciplinary area concerning polymer chemistry, organic synthesis, polymer physics, theoretical and experimental mechanics, processing, composites manufacturing, interfacial engineering, etc. The present article briefly reviews the achievements of the groups worldwide, and particularly the work carried out in our own laboratory towards strength recovery for structural applications. To ensure sufficient coverage, thermoplastics and thermosetting polymers, extrinsic and intrinsic self-healing, autonomic and non-autonomic healing approaches are included. Innovative routes that correlate materials chemistry to full capacity restoration are discussed for further development from bioinspired toward biomimetic repair.     

Coupling of waste water treatment with storage polymer production

Applied Biochemistry and Biotechnology - Storage polymers in bacterial cells can be extracted and used as biodegradable thermoplastics. However, widespread applications have been limited by high...     

Biopolymers for surface engineering of paper-based products

The combination of biopolymer science and technology with surface engineering of paper-based cellulosic materials has a lot of potential in stepping forward to a sustainable future. Various biopolymers such as oxidized starch, carboxymethyl cellulose, and polylatic acid have been commercially used to engineer paper surface. The paper-based cellulosic products are widely used for printing/writing and packaging applications. However, the production of these products are currently dependent mainly upon the use of petroleum-based materials including synthetic pigment coating latexes and barrier coating materials. The major challenges associated with some biopolymers are their relatively high costs and unsatisfactory performances. Continuing efforts are being made to enable the increased and value-added use of various biopolymers in paper surface engineering. These polymers can be based on cellulose, hemicelluloses, chitosan, alginate, protein, polylactic acid, and polyhydroxyalkanoate. The biopolymer-engineered paper products can be tailored for use as substitutes for various non-renewable materials including plastics and metals as well. Future development in the area of biopolymers for paper surface engineering is likely to lead to new possibilities and breakthroughs, paving the way for a substantially sustainable and green future.     

Poly(lactic acid)‐based nanocomposites

Classic plastics accumulate in nature causing environmental pollution, yet as a counterbalance they benefit society in many ways. They are versatile, cost‐effective, and can be tailored to have desired properties. The global environment has led to the fabrication of commodity plastics from environmentally degradable polymers. Poly(lactic acid) (PLA) is the most promising among the environmentally friendly polymers available. PLA‐based plastics have mechanical, thermal, and transparency similar to traditional plastics, and they can be molded and fabricated using the same equipment and procedures. Their material properties are enhanced through nanocomposites, compatibilizers, plasticizers, and other fillers (flame retardant, ultraviolet filter, etc.). This review summarizes mass production techniques and property reinforcements (focusing on nanocomposites and plasticizers) for PLA‐based plastics for commodity use. Copyright © 2016 John Wiley & Sons, Ltd.     

Matrix-assisted laser desorption ionization mass spectrometry with 2-(4-hydroxyphenylazo)benzoic acid matrix

A novel matrix substance, 2-(4-hydroxyphenylazo) benzoic acid, or HABA, has been found to be very advantageous for matrix-assisted ultraviolet laser desorption ionization mass spectrometry. This compound has been successfully used for the desorption of peptides, proteins, and glycoproteins up to approximately 250 kDa. For these materials, the most abundant analyte-related peaks correspond to [M + H]⁺ ions and multiply protonated molecules. Comparisons with sinapic acid, 2,5-dihydroxybenzoic acid, and α-cyano-4-hydroxycinnamic acid indicate that the new matrix provides comparable sensitivity for peptides and smaller proteins but results in better sensitivity for larger proteins and glycoproteins in protein mixtures. Other matrices discriminate against the higher mass components in these cases. Somewhat reduced mass resolution has been found for smaller proteins, but for larger proteins and glycoproteins the best mass resolution can often be obtained with the new matrix. For other classes of compounds that form ions predominantly via cation attachment, at least as good sensitivity and even better resolution have been obtained. Derivatized glycolipids and synthetic polymers have been studied in detail. For the analysis of many synthetic polymers, the best performance in terms of sensitivity and mass resolution has been observed with HABA matrix. Mass resolution was higher for cation adducts than for the protonated peptide molecules in the same mass range. The new matrix exhibits greatly extended (in time) analyte ion production and reproducibility. Owing to the uniform sample surface with this matrix, barely any spatial variation of the ion signal could be observed. In addition, many hundreds of single-shot mass spectra could be accumulated from the same spot, even for larger proteins.     

Polyethylene like polymers. Aliphatic polyesters of dodecanedioic acid: 1. Synthesis and properties

A series of aliphatic polyesters has been synthesized starting from 1,12-dodecanedioic acid and aliphatic diols, bearing from 2 to 12 carbon atoms. These polymers, which were fully characterized in terms of chemical structure, molecular weight and thermal behaviour, were obtained as crystalline materials with melting points ranging from 70 to 90 °C and with a relatively high molecular weight. All the monomers used can be obtained from biomasses, as a consequence these materials can be an interesting alternative to synthetic polymers produced from petrochemical processes based on nonrenewable resources.     

The comparison of physic-chemical properties of chitosan/collagen/hyaluronic acid composites with nano-hydroxyapatite cross-linked by dialdehyde starch and tannic acid

Scaffolds based on chitosan, collagen and hyaluronic acid, cross-linked by dialdehyde starch with hydroxyapatite were obtained with the use of the freeze-drying method. Scaffolds were cross-linked by tannic acid or dialdehyde starch addition. Composites were characterized by different analyses, e.g. SEM images, porosity, density, liquid uptake, and mechanical tests. In addition, the adhesion and proliferation of human osteosarcoma SaOS-2 cells were examined on the obtained scaffolds.The results showed that the properties of the scaffolds based on chitosan, collagen, and hyaluronic acid can be modified by cross-linkers addition. The compressive modulus for the scaffolds cross-linked by dialdehyde starch was higher than for those cross-linked by tannic acid. The porosity of scaffolds cross-linked by starch was higher than those in which tannic acid was applied. However, the former presented lower density. SEM images showed the homogeneous scaffold structure with interconnected pores. Scaffolds cross-linked by tannic acid exhibited higher biocompatibility than those cross-linked by dialdehyde starch. However, the results showed that both scaffolds, cross-linked by dialdehyde starch and by tannic acid can provide the support required in tissue engineering and regenerative medicine. The scaffolds presented here may be easily operated to fit such small bone defects without causing adverse reactions.     

Conformational,optical, electro-optical,and dynamic characteristics of cross-linked poly(N-acryloyl-11-aminoundecanoic acid)

Polymerizable surfactants now attract a great interest due to high potential of their practical application as components of pseudostationary phase in micellar chromatography, drug carriers, and “building blocks” for molecular design of nanoparticles and nanostructured polymer materials, for encapsulation of various biological preparations. In the present work, we have studied poly(N-acryloyl-11-aminoundecanoic acid) (cross-linked comb-like polymer). Cross-linked polymers were obtained via copolymerization of the surfactant bearing double bond in hydrophobic tail with hydrophobic bifunctional cross-linker in micellar solution. Of special interest was the comparison between cross-linked and non-cross-linked polymers and influence of alkaline medium on characteristics of these samples. Non-cross-linked polymers were obtained by hydrolysis of the cross-linked product (treating with NaOH). The mixture of cyclohexanol and dioxane (1:1 volume ratio) was used as a solvent. Detailed studies of the obtained polymers by viscometry, dynamic light scattering, flow birefringence, and equilibrium and non-equilibrium electric birefringence were performed. It was established that during cross-linking process, two types of bonds are formed (the ones inside individual molecules and between several polymer chains). It was shown that cross-linked macromolecular nanoparticles can be transformed into comb-like polymers.