Thermally degradable maleimides for reworkable adhesives

New thermosetting materials were developed for reworkable adhesive applications by introducing acetal ester groups as thermally degradable linkages into maleimide compounds. The synthesis of compounds containing maleimide functionality and acetal ester linkages was conducted by a one‐step neat reaction from commercially available materials. The polymerization process and thermal degradation of the synthesized materials were studied. It was found that the acetal ester linkage degraded rapidly above 225 °C, and introduction of this linkage into the adhesive formulation led to improved reworkability of adhesively bonded substrates. A mechanism for reworkability was proposed based on the insight provided by experimental and modeling work. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1073–1084, 2009     

Neighboring Molecular Engineering in Diels–Alder Chemistry Enabling Easily Recyclable Carbon Fiber Reinforced Composites

Although a variety of dynamic covalent bonds have been successfully used in the development of diverse sustainable thermosetting polymers and their composites, solving the trade-off between recovery efficiency and comprehensive properties is still a major challenge. Herein, a “one-stone-two-birds” strategy of lower rotational energy barrier (E_r) phosphate-derived Diels–Alder (DA) cycloadditions was proposed for easily recyclable carbon fiber (CF)-reinforced epoxy resins (EPs) composites. In such a strategy, the phosphate spacer with lower E_r accelerated the segmental mobility and dynamic DA exchange reaction for network rearrangement to achieve high-efficiency repairing, reprocessing of the EPs matrix and its composites and rapid nondestructive recycling of CF; meanwhile, incorporating phosphorus-based units especially reduced their fire hazards. The resulting materials simultaneously showed excellent thermal/mechanical properties, superb fire safety and facile recyclability, realizing the concept of recycling for high-performance thermosetting polymers and composites. This strategy is of great significance for understanding and enriching the molecular connotation of DA chemistry, making it potentially applicable to the design and development of a wide range of dynamic covalent adaptable materials toward practical cutting-edge-tech applications.     

A Review on the Potential and Limitations of Recyclable Thermosets for Structural Applications

Abstract

The outstanding performance of conventional thermosets arising from their covalently cross-linked networks directly results in a limited recyclability. The available commercial or close-to-commercial techniques facing this challenge can be divided into mechanical, thermal, and chemical processing. However, these methods typically require a high energy input and do not take the recycling of the thermoset matrix itself into account. Rather, they focus on retrieving the more valuable fibers, fillers, or substrates. To increase the circularity of thermoset products, many academic studies report potential solutions which require a reduced energy input by using degradable linkages or dynamic covalent bonds. However, the majority of these studies have limited potential for industrial implementation. This review aims to bridge the gap between the industrial and academic developments by focusing on those which are most relevant from a technological, sustainable and economic point of view. An overview is given of currently used approaches for the recycling of thermoset materials, the development of novel inherently recyclable thermosets and examples of possible applications that could reach the market in the near future.     

Microporous polycyanurate networks

A general means of generating nanofoams from thermosetting materials was investigated. Foams were prepared from a thermosetting monomer copolymerized with a thermally labile material, such that the thermally labile coblock is the dispersed phase. Upon thermal treatment, the thermally unstable block undergoes thermolysis, leaving pores where the size and shape are dictated by the initial morphology. For this investigation the thermosetting resin was prepared from a cyanate monomer (4,4′-(hexafluoroisopropylidene) diphenyl-cyanate), with either poly(propylene oxide) or a propylene oxide–urethane copolymer as the thermally labile block. The propylene oxide-based oligomers were molecularly miscible with the cyanate resin over the entire range of compositions, and molecular weights investigated, but developed a two-phase structure upon reaction to form the polycyanurate thermoset. The molecular weight and composition of propylene oxide chemically incorporated into the polycyanurate was varied along with the curing condition, solvents, and catalyst. Dynamic mechanical and small-angle x-ray scattering measurements demonstrated a two-phase morphology in the cured networks wherein the propylene oxide domains are dispersed in the polycyanurate matrix. Upon decomposition of the propylene oxide component, however, the foam was found to collapse. Samples with the larger void size retained, to a large extent, their void composition upon the thermolysis of the propylene oxide component. © 1996 John Wiley & Sons, Inc.     

Standardization and certification in the area of environmentally degradable plastics

Environmentally degradable polymers and plastics (EDPs) are a group of polymeric materials experiencing a rapid growth in number as well as in their applications and quantities used. The assessment of their key characteristic - degradability, including eventually biodegradability as the ultimate stage, is scientifically and technically a challenging issue and has led to differing interpretations in the past. In order to standardize techniques and criteria a number of standards were established by different standardization bodies which are also used as a basis for certification schemes. An up-to-date inventory of the rapidly growing standardization body is presented with basic interpretation to help guide the non-expert. A basic introduction to EDPs and polymer degradation is added for clarity.     

The degradation of new thermally degradable thermosets obtained by cationic curing of mixtures of DGEBA and 6,6-dimethyl (4,8-dioxaspiro[2.5]octane-5,7-dione)

The thermal degradation of thermosetting materials prepared by cationic copolymerization of mixtures of different proportions of diglycidylether of bisphenol A (DGEBA) with 6,6-dimethyl (4,8-dioxaspiro[2.5]octane-5,7-dione) (MCP) initiated by ytterbium or lanthanum triflate or using a conventional initiator, BF₃·MEA was investigated. To study the thermal degradation, several techniques were used such as thermogravimetry (TGA), infrared spectroscopy (FTIR) and calorimetry (DSC) and the volatiles evolved during degradation were identified by mass spectrometry. The materials prepared possess the characteristics of thermally degradable thermosets, due to the presence of ester groups in the polymer chain, which are broken at the beginning of degradation. The degradability increased when lanthanide triflates were used in the curing, especially the ytterbium salt and when the proportion of MCP in the material increased.     

Recent advances in stimuli-responsive degradable block copolymer micelles: synthesis and controlled drug delivery applications

(Bio)degradation in response to external stimuli (stimuli-responsive degradation, SRD) is a desired property in constructing novel nanostructured materials. For polymer-based multifunctional drug delivery applications, the degradation enables fast and controlled release of encapsulated therapeutic drugs from delivery vehicles in targeted cells. It also ensures the clearance of the empty device after drugs are delivered to the body. This review summarizes recent development of various strategies to the design and synthesis of self-assembled micellar aggregates based on novel amphiphilic block copolymers having different numbers of stimuli-responsive cleavable elements at various locations. These cleavable linkages including disulfide, acid-labile, and photo-cleavable linkages are incorporated into micelles, and then are cleaved in response to cellular triggers such as reductive reaction, light, and low acid. The well-designed SRD micelles have been explored as controlled/enhanced delivery vehicles of drugs and genes. For future design and development of effective stimuli-responsive degradable micelles toward tumor-targeting delivery applications in vivo, a high degree of control over degradation for tunable release of encapsulated anticancer drugs as well as bioconjugation for active tumor-targeting is required.     

An overview on covalent organic frameworks: synthetic reactions and miscellaneous applications

Covalent organic frameworks (COFs) are an emerging class of porous crystalline materials which are completely constructed from organic building blocks through robust covalent bonds. High surface areas, compositional and structural tunability, low density, and superior stability have rendered COF candidates in a variety of applications, such as adsorption and separation, catalysis, electronics, chemical sensing, optics, and so forth. To better understand the structures and properties of COFs as well as the design principles, it is of great significance to learn about the linkages formed during synthetic reactions that contribute to the high crystallinity and stability of COFs. In this review, we will first discuss various linkages that have been utilized for COF construction up to date, followed by an outline of their miscellaneous applications, providing a comprehensive and detailed overview in this file.     

A General Strategy for Site‐Directed Enzyme Immobilization by Using NiO Nanoparticle Decorated Mesoporous Silica

Mesoporous materials have recently gained much attention owing to their large surface area, narrow pore size distribution, and superior pore structure. These materials have been demonstrated as excellent solid supports for immobilization of a variety of proteins and enzymes for their potential applications as biocatalysts in the chemical and pharmaceutical industries. However, the lack of efficient and reproducible methods for immobilization has limited the activity and recyclability of these biocatalysts. Furthermore, the biocatalysts are usually not robust owing to their rapid denaturation in bulk solvents. To solve these problems, we designed a novel hybrid material system, mesoporous silica immobilized with NiO nanoparticles (SBA‐NiO), wherein enzyme immobilization is directed to specific sites on the pore surface of the material. This yielded the biocatalytic species with higher activity than free enzyme in solution. These biocatalytic species are recyclable with minimal loss of activity after several cycles, demonstrating an advantage over free enzymes.     

Non-enzyme entrapping biohydrogels in catalysis

This review provides an overview of the current status and future directions of the use of biohydrogels (i.e., hydrogels obtained from biopolymers) as heterogeneous catalysts and/or supports for catalytic metal nanoparticles. This review collects a wide variety of biohydrogels used in catalytic applications, including gels made of polysaccharides (chitosan, alginate, carrageenan, dextran, agarose), proteins (gelatin, silk fibroin, ferritin) and nucleic acids (DNA). Additionally, the most significant features about the recyclability of these materials, their structural properties and the type of reactions that they catalyze are discussed.     

Design and fabrication of thermally stable nanoparticles for well-defined nanocomposites

The nanocomposites consisted of polymer and nanoparticles (NPs) have been regarded as one of core materials in the nanotechnology. From the practical viewpoint, the heat treatment is often required in many nanocomposite fabrication processes. However, some NPs such as gold NPs exhibit the low thermal stability due to the dissociation of ligands from the nanoparticle surface at elevated temperature, limiting their use in many applications. Herein, we provide an overview of the recent efforts in strategies for the design and fabrication of inorganic NPs which have enhanced thermal stability. The recent investigation on the phase behavior of thermally stable NPs within the polymer matrices (polymer blends and block copolymer), morphologies of nanocomposites induced by NPs, and examples of their applications are also discussed. These approaches may provide useful strategy to employ the NPs for the fabrication of nanocomposites in diverse applications especially where heat treatment are required. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

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.     

Modular design in natural and biomimetic soft materials

Under eons of evolutionary and environmental pressure, biological systems have developed strong and lightweight peptide-based polymeric materials by using the 20 naturally occurring amino acids as principal monomeric units. These materials outperform their man-made counterparts in the following ways: 1) multifunctionality/tunability, 2) adaptability/stimuli-responsiveness, 3) synthesis and processing under ambient and aqueous conditions, and 4) recyclability and biodegradability. The universal design strategy that affords these advanced properties involves "bottom-up" synthesis and modular, hierarchical organization both within and across multiple length-scales. The field of "biomimicry"-elucidating and co-opting nature's basic material design principles and molecular building blocks-is rapidly evolving. This Review describes what has been discovered about the structure and molecular mechanisms of natural polymeric materials, as well as the progress towards synthetic "mimics" of these remarkable systems.     

开环可控聚合制备脂肪族聚酯的最新研究进展

近年来,作为生物降解高分子材料,脂肪族聚酯由于良好的生物降解性及生物相容性受到人们的广泛关注。脂肪族聚酯在环境友好材料和生物医用材料领域都具有极大的应用价值,目前,部分聚酯材料已经商品化。与此同时,脂肪族聚酯的合成方法尤其是活性开环聚合也成为学术界及工业领域的研究热点。采用开环聚合法得到的聚合产物化学组成精确、分子量分...     

Thermally Responsive Materials for Bioimaging

The last decade has witnessed multiple thermally responsive materials emerge as a significant class of stimuli‐responsive materials. These materials are elaborately designed and exert interesting properties. Herein, an overview of thermally responsive materials with respect to design strategies, fabrication procedures, and their applications is presented. Recently reported thermally responsive materials are highlighted. Then, applications of thermally responsive materials in bioimaging are summarized.     

Biomedical applications of biodegradable polymers

Utilization of polymers as biomaterials has greatly impacted the advancement of modern medicine. Specifically, polymeric biomaterials that are biodegradable provide the significant advantage of being able to be broken down and removed after they have served their function. Applications are wide ranging with degradable polymers being used clinically as surgical sutures and implants. To fit functional demand, materials with desired physical, chemical, biological, biomechanical, and degradation properties must be selected. Fortunately, a wide range of natural and synthetic degradable polymers has been investigated for biomedical applications with novel materials constantly being developed to meet new challenges. This review summarizes the most recent advances in the field over the past 4 years, specifically highlighting new and interesting discoveries in tissue engineering and drug delivery applications. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

深共熔溶剂及其生物催化应用

在绿色化学研究领域,溶剂占据着重要的位置。作为一个绿色溶剂必须满足廉价易得、可生物降解、无毒、可循环使用、无挥发性等标准的要求。但是至今能满足这些要求的溶剂仍然非常有限。近年来,深共熔溶剂（Deep Eutectic Solvents,DESs）被认为可以作为绿色溶剂替代传统的有机溶剂而受到广泛关注。DESs是由两个或多个成分在特定比例下形成的凝固点大大降低室温液态混合物。与离子液体相比,DESs具有廉价、低毒、可生物降解等特点,在许多领域成为研究热点。本文综述了DESs的生物降解性、毒性/细胞毒性及其作为生物催化反应介质的研究现状。基于对研究现状的认识,对DESs未来研究、应用需要解决的问题进行了讨论。作者期望对DESs生物催化应用研究现状的综述更进一步促进DESs研究、应用的发展。     

Progress in Synthetic Polymers Based on Natural Amino Acids

α-Amino acids are one type of the main building blocks of living systems, being the primary components of all naturally occurring peptides and proteins. They are the simplest optically active compound in the nature and have multiple functional groups, which enable them to be transformed into a wide variety of optically active substances. The resulting materials show a wide variety of functions such as electron transfer, information transfer, photo reactivity and selective catalytic function, which cannot be imitated by synthetic compounds. Functional macromolecular materials using biological chiral resources such as amino acids have been drawing much interest due to their biocompatibility and biodegradability easing the ecological trouble because amino acid residues can be targeted for cleaving by different enzymes. Also, this type of polymer contains nitrogen, which the organism needs for their growth and shows excellent hydrophilic character, reasonably high melting points and good materials properties even at relatively low molecular weights. However, polymers composed of amino acids alone have limited thermal stability and are insoluble in many common organic solvents, which make these materials difficult to fabricate and utilize. Preparation of hybrid systems between conventional synthetic polymers and linear sequences of amino acids are interesting because amino acid segments possess unique properties, such as directional polarity, chirality and their capability to undergo specific noncovalent interactions. These properties can potentially be used for designing novel hierarchical superstructures with tunable material properties for a wide variety of applications. Herein, the synthesis and properties of synthetic macromolecules having natural amino acids are reviewed in details up to now with excluding polypeptides.     

Artificial cells in medicine and biotechnology

Since the feasibility of artificial cells was first demonstrated in 1957 [Chang (1, 2)], an increasing number of approaches to their preparation and use have become available. Thus artificial cell membranes can now be formed using a variety of synthetic or biological materials to produce desired variations in their permeability, surface properties, and blood compatibility. Almost any material can be included within artificial cells. These include enzyme systems, cell extracts, biological cells, magnetic materials, isotopes, antigens, antibodies, vaccines, hormones, adsorbents, and others. Since cells are the fundamental units of living organisms, it is not surprising that artificial cells can have a number of possible applications. This is especially so since artificial cells can be “tailor-made” to have very specialized functions. A number of potential applications suggested earlier have now reached a developmental stage appropriate for clinical trial or application. These clinical applications include the use of such cells as a red blood cell substitute, in hemoperfusion, in an artifical kidney or artificial liver, as detoxifiers, in an artificial pancreas, and so on. Artificial red blood cells based on lipid-coated fluorocarbon or crosslinked hemoglobin are being investigated in a number of centers. The principle of the artificial cells is also being used in biotechnology to immobilize enzymes and cells. Developments in biotechnology have also resulted in the use of the principle underlying the artificial cell to help produce interferons and monoclonal antibodies; to create immunosorbents; to develop an artificial pancreas; and to bring enzyme technology usefully into biotechnology and biomedical applications. Artificial cells are also being used as drug delivery systems based on slow release, on magnetic target delivery, on biodegradability, on liposomes, or other approaches. The present status and recent advances will be emphasized in this paper.     

Maintaining the structure of templated porous materials for reactive and high-temperature applications

Nanoporous and nanostructured materials are becoming increasingly important for advanced applications involving, for example, bioactive materials, catalytic materials, energy storage and conversion materials, photonic crystals, membranes, and more. As such, they are exposed to a variety of harsh environments and often experience detrimental morphological changes as a result. This article highlights material limitations and recent advances in porous materials--three-dimensionally ordered macroporous (3DOM) materials in particular--under reactive or high-temperature conditions. Examples include systems where morphological changes are desired and systems that require an increased retention of structure, surface area, and overall material integrity during synthesis and processing. Structural modifications, changes in composition, and alternate synthesis routes are explored and discussed. Improvements in thermal or structural stability have been achieved by the isolation of nanoparticles in porous structures through spatial separation, by confinement in a more thermally stable host, by the application of a protective surface or an adhesive interlayer, by alloy or solid solution formation, and by doping to induce solute drag.