生物基环氧树脂及固化剂研究现状

生物基高分子材料以可再生资源为主要原料,它在减少塑料行业对石油资源消耗的同时,也减少了石油化工原料在生产过程中对环境的污染,具有节约石油资源和保护环境的双重功效。桐油和松香是我国两种重要的天然可再生资源,在目前将化工原料逐步转向可再生资源的时代背景下,它们已被广泛应用于高分子材料的合成和改性。生物基热固性树脂是一个意义重大且前景广阔的研究领域,本文就桐油和松香在生物基环氧树脂和固化剂方面的应用进行了系统的综述和展望。     

以油酸为原料的新型生物基支链十七烷基苯磺酸钠的合成及性质

生物基表面活性剂由于其可再生资源和优异的表面/界面性质吸引了越来越多的关注。本文以可再生的油酸为原料,通过四步反应,制备了新型生物基支链表面活性剂,并评价了其表/界面性质、润湿性和生物降解性能。该新型生物基支链表面活性剂为4-（1-十七烷基）苯磺酸钠（9ΦC17S）,依次经过烷基化反应、脱羧反应、磺化反应和中和反应而制得。其化学结构已通过电喷雾质谱、红外光谱和核磁共振波谱得以确认。4-（1-十七烷基）苯磺酸钠展现出良好的表/界面张力,临界胶束浓度（CMC）为317.5 mg·L^-1,CMC处的表面张力为32.54 mN·m^-1,当水溶液中碳酸钠浓度为8.48×10⁴ mg·L^-1、4-（1-十七烷基）苯磺酸钠浓度为8.36×10⁴ mg·L^-1时,油水的界面张力约为10^-2 mN·m^-1。此外,4-（1-十七烷基）苯磺酸钠在生物降解性和润湿性方面也显示出了良好的性能,最终生物降解评分为2.99,0.500 g·L^-1 9ΦC17S溶液的气液固接触角为63.08°。该新型生物基表面活性剂丰富了以可再生资源为原料的生物基表面活性剂的结构多样性。     

液体闪烁计数法测定生物塑料中生物基含量

研究并建立了液体闪烁计数法测量生物塑料中生物基含量。首先将生物塑料样品充分燃烧,通过碳的转移与固定,最终催化合成液态苯。通过液体闪烁计数器对液体苯中的放射性核素14C衰变进行计数,从而计算生物塑料样品中生物基的含量。生物塑料样品加标回收率为98.5%~101%,相对标准偏差为0.2%。方法可用于生物塑料中生物基含量检测。     

热裂解-气相色谱-质谱法鉴别生物可降解塑料

目前生物可降解塑料主要采用堆肥降解测定其生物降解性能的方法进行鉴别,其检测周期长、费用较高。材料的组成基本决定了其生物降解特性,为了快速鉴别生物可降解塑料,采用热裂解-气相色谱-质谱法(PY-GC-MS)对以聚对苯二甲酸-己二酸丁二醇酯(PBAT)与不同质量比的其他成分包括生物可降解聚乳酸(PLA)、难降解材料聚苯乙烯(PS)或聚对苯二甲酸乙二醇酯(PET)混合样的裂解特征进行了研究。结果显示,PBAT的裂解特征峰明显,未受到PLA的影响;若在PBAT中添加质量分数1%的非降解材质PS和PET也可被检出。方法用于市场上收集到的标识为可降解塑料购物袋样品的分析,结果表明,采用PY-GC-MS可以快速对可降解塑料进行初步鉴别。     

生物基UV固化预聚物制备及性能研究

近年来，随着制造业产能的严重过剩，我国政府对于环境保护越来越重视，传统油性涂料体系受到巨大的冲击，而光固化作为三大环保型涂料技术之一得到迅速发展。生物基原料是一种可再生资源，在不可再生资源越来越少的未来，生物基材料的发展和应用也就成为一种必然趋势。本文把生物基原料引入光固化预聚物体系，在类似结构条件下对比了含有和不含有生物基材料预聚物固化膜的基本物化性能，并对实验结果进行了总结。     

聚乳酸共混改性研究新进展

聚乳酸(PLA)基塑料相比于聚羟基脂肪酸酯、聚氨基酸等生物基塑料具有更佳的抗拉强度、延展性、光泽度和透明度^[1],而相比于传统石油基塑料又具有可完全降解且无毒无害的优点。作为传统石油基塑料的首选替代品,纯PLA塑料也面临着玻璃化转变温度较低、断裂伸长率较差等缺陷,难以完全替代传统石油基材料。因此,自诞生以来,PLA基塑料的改性工作一直是国内外学者的研究热点,其方法主要包括共聚、共混和添加改性剂等。本文主要阐述近些年来PLA共混改性方法的进展,着重分析其方法、特点及应用。最后,对PLA基塑料的发展前景进行了展望。     

热塑性淀粉力学性能的提升途径及作用机理

以可再生资源(如淀粉、纤维素和蛋白质等)为基础发展而来的生物可降解塑料受到人们越来越多的关注,是可降解塑料行业发展的重要方向之一。天然淀粉由于来源广、低成本和可生物降解的特点,广泛用于制备淀粉塑料,并用于农业、食品、医药和包装等行业,有望取代石油基衍生聚合物。淀粉大分子具有结晶结构,所含大量羟基可形成较强的分子间和分子内氢键,使其不能热塑加工,而当加入增塑剂后可破坏其结晶结构,从而用于制备热塑性淀粉。目前,热塑性淀粉的力学性能差,是影响其使用性能的首要问题。近年来国内外开展了大量的研究以试图增强其力学性能。本文主要以不同类型的热塑性淀粉为基础,以淀粉自身改性和外加组分改性两种提高其力学性能的途径为主线,以其力学性能的提升方法和作用机理为重点,系统总结了近年来国内外以提高热塑性淀粉材料的力学性能为目的的研究工作,归纳了影响力学性能的相关因素以及提升途径,并对该领域重点研究的内容进行了总结和展望。     

大肠杆菌“造”出最耐热生物塑料

<正>日本研究人员利用大肠杆菌,通过转基因操作和光反应等方法,制作出400℃左右高温下也不会变性的生物塑料,在当前同类塑料中最为耐热。日本科学技术振兴机构等机构联合发表的公报说,这种塑料是透明的,硬度特别高,可用于汽车上代替玻璃,能大幅度减轻汽车重量,从而节约能源、减少二氧化碳排放。生物塑料用来自植物等的生物质为原材料生产,有利于保护环境。但此前的生物塑料硬度和耐热性都较差,所以用途有限,一般都是作为一次性材料使用。     

CO2/生物基环氢化合物共聚制备绿色聚碳酸酯材料

以CO_2为原料合成脂肪族聚碳酸酯材料不仅利用了廉价、可再生的CO_2资源,而且可以实现全生物降解高分子材料的制备,是一条绿色可持续的高分子材料合成路线。但长期以来,该领域研究多集中在利用CO_2与一些石油来源的环氧烷烃(如环氧丙烷、环氧环己烷等)共聚方面,未能完全摆脱对石油资源的依赖。因此,发展基于生物基的环氧单体制备全生物基高分子材料逐渐成为CO_2基高分子材料研究的热点。生物基来源化合物的引入有助于丰富CO_2基高分子材料的结构和性能,拓展其应用领域。本文综述了近年来利用生物基环氧化合物与CO_2共聚合成全生物基高分子材料的研究进展,并对未来该领域发展的趋势进行了展望。     

气相色谱法测定生物柴油中脂肪酸甲酯含量

生物柴油是利用动植物油脂等可再生资源通过酯交换技术制造的可以替代石化柴油的新型清洁安全燃料[1-3]它的主要成分是脂肪酸甲酯。由于不同油脂原料所生产的生物柴油的脂肪酸甲脂组成不同因而测定时所需的气相色谱条件与方法也不尽相同[4-6]。本文采用HP-innowax毛细管色谱柱,     

Biodegradable Polymeric Materials—Not the Origin but the Chemical Structure Determines Biodegradability

It is completely plausible that unmodified materials of natural origin, such as the native macromolecules cellulose or starch, are biodegradable. If these materials are modified then degradation may, depending on the degree of modification, be more difficult or even impossible. In the same manner synthesized macromolecules, whether from renewable or petrochemical sources, could be inert or completey biodegradable, depending on their chemical structure.     

Needle-free electrospinning of nanofibrillated cellulose and graphene nanoplatelets based sustainable poly (butylene succinate) nanofibers

Sustainable materials have slowly overtaken the nanofiber research field while the tailoring of their properties and the upscaling for industrial production are some of the major challenges. We report preparation of nanofibers that are bio-based and biodegradable prepared from poly (butylene succinate) (PBS) with the incorporation of nanofibrillated cellulose (NFC) and graphene nanoplatelets (GN). NFC and GN were combined as hybrid filler, which led to the improved morphological structure for electrospun nanofibers. A needleless approach was used for solution electrospinning fabrication of nanofiber mesh structures to promote application scalability. The polymer crystallization process was examined by differential scanning calorimetry (DSC), the thermal stability was evaluated by thermal gravimetric analysis (TGA), while the extensive investigation of the nanofibers structure was carried out with scanning electron microscopy (SEM) and atomic force microscopy (AFM). NFC and GN loadings were 0.5 and 1.0 wt %; while poly (ethylene glycol) (PEG) was employed as a compatibilizer to enhance fillers’ interaction within the polymer matrix. The interactions in the interface of the fillers and matrix components were studied by FTIR and Raman spectroscopies. The hybrid filler approach proved to be most suitable for consistent and high-quality nanofiber production. The obtained dense mesh-based structures could have foreseeable potential application in biomedical field like scaffolds for the tissue and bone recovery, while other applications could focus on filtration technologies and smart sensors.     

Recent progress in biodegradable polymers and nanocomposite-based packaging materials for sustainable environment

Plastic-based materials are frequently used in packaging and can be seen universally in both the developed and developing societies. At present, most of the currently used food packaging materials are nondegradable and are creating serious environmental problems. New technologies are being explored and developed to study the complex interaction between the food packaging materials and food. For example, nanocomposite of cellulose constitutes environmentally friendly packaging, which is easily recycled by combustion and requires low power consumption in production. There are several such biodegradable materials which are available at a low price, have good mechanical properties and allow disposal in the soil. This is advantageous because biological degradation produces only carbon dioxide, water, and inorganic compounds to name a few. It has also been discovered that biodegradable plastics made of such materials can be disposed of together with organic waste. The widespread use of biopolymers in the place of standard plastics would help to reduce the weight of waste. Therefore, biodegradable materials take part in the natural cycle “from nature to nature” and play an important role for environmental sustainability. So, in this article, we briefly summarize the different characteristic of biodegradable polymers being used in food packaging applications.     

A furan-derived epoxy thermoset with inherent anti-flammability,degradability, and raw material recycling

The production of multifunctional thermosets with flammability, degradability and raw material recycling from epoxy thermosets made from renewable resources is one of the hottest topics in the context of sustainable development. In this work, we fabricated a fully bio-based epoxy thermoset by curing an as-synthesized furan-derived epoxy monomer (HMF-DDDS-EP) with a furan-based hardener (DFA). Owing to its unique structure containing a Schiff base and disulfide bonds, the cured HMF-DDDS-EP/DFA thermoset integrates a high glass transition temperature, high tensile strength, inherent anti-flammability, degradability, and recyclability. Specifically, a glass transition temperature as high as 171 °C, tensile strength of 62.9 MPa, a storage modulus of 2,356 MPa and outstanding anti-flammability (UL-94 V-0 rating and high LOI of 36.0%) were observed for this fully bio-based epoxy thermoset. Additionally, it was capable of degrading under mildly acidic conditions because of the cleavage of the Schiff base into the original aldehyde monomer. This fully bio-based epoxy thermoset can be considered a representative for fostering the synthesis of advanced thermosetting materials derived from renewable resources.     

To compost or not to compost: Carbon and energy footprints of biodegradable materials’ waste treatment

Many life cycle assessments of bio-based and biodegradable materials neglect the post-consumer waste treatment phase because of a lack of consistent data, even though this stage of the life cycle may strongly influence the conclusions. The aim of this paper is to approximate carbon and energy footprints of the waste treatment phase and to find out what the best waste treatment option for biodegradable materials is by modelling home and industrial composting, anaerobic digestion and incineration. We have compiled data-sets for the following biodegradable materials: paper, cellulose, starch, polylactic acid (PLA), starch/polycaprolactone (MaterBi), polybutyrate-adipate-terephthalate (PBAT, Ecoflex) and polyhydroxyalkanoates (PHA) on the basis of an extensive literature search, experiments and analogies with materials for which significant experience has been made. During biological waste treatment, the materials are metabolised so a part of their embodied carbon is emitted into air and the remainder is stored as compost or digestate. The compost or digestate can replace soil conditioners supporting humus formation, which is a benefit that cannot be achieved artificially. Experimental data on biodegradable materials shows a range across the amount of carbon stored of these materials, and more trials will be required in the future to reduce these uncertainties. Experimental data has also shown that home and industrial composting differ in their emissions of nitrous oxide and methane, but it should be noted that data availability on home composting is limited. The results show that anaerobic digestion has the lowest footprint for the current level of technology, but incineration may become better in the future if energy efficiency in waste incineration plants improves significantly. Home composting is roughly equal to incineration with energy recovery in terms of carbon and energy footprint when carbon credits are considered. The same applies to industrial composting if carbon credits are assigned for compost to replace straw. Carbon credits can therefore considerably affect the results, but there are significant uncertainties in how they are calculated. Incineration may become better than home composting in the future if the average energy efficiency in waste incineration plants improves significantly. However, biological waste treatment options should be chosen when soil carbon is a limiting factor.     

Organocatalytic Upgrading of Biomass Derived Building Blocks

The depletion of finite primary fossil fuels we are facing makes necessary a deep metamorphosis in fundamental parts of the chemical industry. A progressive transition from petro-based starting materials toward renewable biomass-derived sources will have to take place in the synthesis of added-value chemicals, important for our everyday life, such as pharmaceuticals, polymers, agrochemicals etc. Moreover, greener processes, carried out under friendlier reaction conditions, must be designed to address current concerns about the climate change and the resulting pressing need to reduce the environmental footprint of chemical processes. To this end, organocatalysis could offer a valuable opportunity for upgrading biomass-derived platform molecules in line with the principles of Green Chemistry. This review presents some of recent and remarkable advancements in this emerging area. Organocatalysis has proven to be an efficient tool to transform low value bio-based renewable platform building blocks into new high value bio-based chemicals, with potential applications as synthetic intermediates, innovative materials and pharmaceutically active compounds.     

Recent advances in epoxy resins and composites derived from lignin and related bio-oils

This short critical review gives an insight on the potential that lignin and its bio-oils present towards the production of thermosetting epoxy polymers and composites. Green and sustainable ways of producing monomers and polymers from renewable sources are critical and lignin, as an underutilized bio-based waste material, presents a high exploitation potential. Due to its versatile and highly functional phenolic structure, the utilization of lignin or its depolymerized fractions (bio-oils) has been investigated in the last years as alternative for fossil-based epoxy resin pre-polymers and crosslinkers. Lignin can in fact be considered as a crosslinker for epoxy resins, especially after appropriate functionalization with amine groups or with additional hydroxyl groups, or it can be modified with epoxide groups towards the replacement of toxic BPA-based epoxy prepolymers. Furthermore, lignin derived pyrolysis or hydrogenolysis bio-oils may offer highly reactive soluble oligomers that after appropriate functionalization could be utilized as bio-based epoxy prepolymers. The lignin-based epoxy resins and composites exhibit similar or even better and novel properties, compared to those of pristine epoxy polymers, thus rendering lignin a highly valuable feedstock for further utilization in the thermoset polymer industry.     

Derivation and synthesis of renewable surfactants

This critical review focuses on the origins and preparation of bio-based surfactants, defined here as non-soap, amphiphilic molecules in which the carbon atoms are derived from annually renewable feedstocks. Environmental concerns and market pressures have led to greater relevance of these chemicals in commercial applications in recent years and extensive research has gone into exploring new classes of surfactants. Highlighted here are examples of bio-based surfactants that are produced on an industrial scale and/or are based on abundant starting materials. The trend of increasing use of renewable resources as starting materials for surfactants is introduced, followed by extensive discussion of the major classes of bio-derived hydrophobes and hydrophiles. Also discussed is the status of research and development with regard to biosynthetically produced surfactants. Finally, concluding remarks address the potential for new surfactant molecular structures as a result of ongoing development in the chemistry of biorefineries, i.e., that the transformation of lignocellulose into fuels is likely to support the manufacturing of new bio-based coproducts (238 references).     

Thermoplastic Starch

The thermoplastics processing of native starch in the presence of water is a recent development with very wide possible applications. Eventually, oil-based polymer materials have to be replaced in many applications by sustainable, inexpensive, natural materials from renewable resources. The present contribution focuses on the injection moulding of starch. The bases of the processing and the thermal and molecular changes occurring are described. In addition, the rheological behaviour of starch-water melts during processing is analysed quantitatively to give apparent melt viscosities. The dimensional, thermal and mechanical properties of moulded thermoplastic starch polymer (TSP) materials and the products presently being produced from them are discussed.