Biodegradation of Thermoplastic Polyurethanes from Vegetable Oils

Thermoplastic urethanes based on polyricinoleic acid soft segments and MDI/BD hard segments with varied soft segment concentration were prepared. Soft segment concentration was varied from, 40 to 70 wt%. Biodegradation was studied by respirometry. Segmented polyurethanes with soft segments based on polyricinoleic acid degrade relatively slow losing about 11% carbon after 30 days, but faster than corresponding petrochemical polyesterurethanes. Since biodegradation proceeds mainly through the soft segments, higher soft segment content polymers displayed slightly higher biodegradation. Polyurethanes with dispersed hard domains in the soft phase displayed slightly faster biodegradation than those with co-continuous morphology. Polyester diol degrades slower than castor oil but significantly faster than the polyurethanes with built in soft segments from the same diol. Castor oil biodegrades slower than soybean oil.     

Polyacetal Polyols for Polyurethanes

The synthesis of telechelic polyacetals with terminal hydroxyl groups (polyacetal polyols), by the reaction of triethylene glycol divinyl ether with dipropylene glycol in the presence of trimethylolpropane or other triols or diols as starters, in acidic catalysis, has been studied. The synthesized liquid polyacetal triols and polyacetal diols were characterized by hydroxyl number, viscosity, acidity, number average molecular weight (M_n), weight average molecular weight (M_w), molecular weight distribution (M_w/M_n), FT-IR spectra. The obtained polyacetals were transformed in cast elastomers by the reaction with the isocyanate Mondur CD (modified diphenyl methane diisocyanate) with properties very close to the elastic polyurethanes obtained by using conventional polyether triols, copolymers propylene oxide–ethylene oxide. The polyacetal polyols are suitable for the synthesis of elastic polyurethanes (polyurethane elastomers, flexible polyurethane foams). Polyacetals are well known biodegradable polymers. Therefore, the polyurethanes based on polyacetal polyols are expected to be biodegradable.     

Ethoxylated Soybean Polyols for Polyurethanes

Soybean polyols prepared by ring opening reactions of epoxidized soybean oil with hydrogen active compounds (water, alcohols, organic or inorganic acids, thiols, hydrogen etc.) have a low reactivity in the reaction with isocyanates because the hydroxyl groups are secondary. This paper presents a simple and convenient method to increase the reactivity of soybean polyols with secondary hydroxyl groups by ethoxylation reactions with the preservation of triglyceride ester bonds. The method uses mild reaction conditions: low alkoxylation temperature of 35–45 °C, low pressure of 0.1–0.2 MPa (15–30 p.s.i.) and a superacid as catalyst (HBF₄). The new soybean polyols have a higher reactivity toward isocyanates in polyurethane formation due to the high percentage of primary hydroxyl groups. The primary hydroxyl content was determined by the second order kinetics of polyol reaction with phenyl isocyanate.     

Ethoxylated Soybean Polyols for Polyurethanes

Soybean polyols prepared by ring opening reactions of epoxidized soybean oil with hydrogen active compounds (water, alcohols, organic or inorganic acids, thiols, hydrogen etc.) have a low reactivity in the reaction with isocyanates because the hydroxyl groups are secondary. This paper presents a simple and convenient method to increase the reactivity of soybean polyols with secondary hydroxyl groups by ethoxylation reactions with the preservation of triglyceride ester bonds. The method uses mild reaction conditions: low alkoxylation temperature of 35–45 °C, low pressure of 0.1–0.2 MPa (15–30 p.s.i.) and a superacid as catalyst (HBF₄). The new soybean polyols have a higher reactivity toward isocyanates in polyurethane formation due to the high percentage of primary hydroxyl groups. The primary hydroxyl content was determined by the second order kinetics of polyol reaction with phenyl isocyanate.     

From Natural Oils to Epoxy Resins: A New Paradigm in Renewable Performance Materials

The direct conversion of natural products to useful engineering materials is desirable from both economic and environmental considerations. We describe the synthesis and properties of 100?% oil-based epoxy resins generated from three epoxidized oils. The catalyst, tris(pentafluorophenyl)borane (B(C₆F₅)₃) in toluene, allowed for controlled cationic polymerization at a very low concentration. Epoxidized oils (derived from triolein, soybean, and linseed oil) had varying epoxy content, rendering resins of different cross-link density. The polymerization was carried out at room temperature followed by post-curing at elevated temperature to speed up conversion. Epoxy resins were amorphous transparent glasses below glass transitions and hard rubbers above. Despite their high cross-link density, these materials show relatively low T_g’s reflecting the aliphatic nature of fatty acids and the presence of plasticizing “dangling” chains. The structure of the triglyceride starting oils influenced the properties of the resulting materials: the more regular structure of triolein compared to the very heterogeneous structures of soybean and linseed oils seemed to have enhanced some properties of the polymer networks. These epoxy polymers are potentially useful as encapsulating and potting compounds for electronic applications.

     

Bacterial Production of Polyesters from Free Fatty Acids Obtained from Natural Oils by Pseudomonas oleovorans

The carboxylic acids derived from olive oil, hazelnut oil, sesame oil and hamci(anchovy) oil were evaluated as substrates for cell growth and the production of reserve polyesters by Pseudomonas oleovorans. Poly-3-hydroxy alkanoates containing both saturated(mainly 3-hydroxy-octanoate and 3-hydroxy-decanoate) and unsaturated repeating units with 8 to 20 carbon atoms, or more, were produced in 26 to 61% yields based on cell dry weights. The number average molecular weights of these polymers varied from 45,000 to 68,000 Daltons.     

Polyols and Polyurethanes from Hydroformylation of Soybean Oil

This paper compares physical and mechanical properties of polyurethanes derived via the hydroformylation approach and is a part of our study on the structure–property relationships in polyurethanes created from vegetable oils. The double bonds of soybean oil are first converted to aldehydes through hydroformylation using either rhodium or cobalt as the catalyst. The aldehydes are hydrogenated by Raney nickel to alcohols, forming a triglyceride polyol. The latter is reacted with polymeric MDI to yield the polyurethane. Depending on the degree of conversion, the materials can behave as hard rubbers or rigid plastics. The rhodium-catalyzed reaction afforded a polyol with a 95% conversion, giving rise to a rigid polyurethane, while the cobalt-catalyzed reaction gives a polyol with a 67% conversion, leading to a hard rubber having lower mechanical strengths. Addition of glycerine as a cross-linker systematically improves the properties of the polyurethanes. The polyols are characterized by DSC. The measured properties of polyurethanes include glass transition temperatures, tensile strengths, flexural moduli, and impact strengths.     

Utilization of Porous Carbons Derived from Coconut Shell and Wood in Natural Rubber

The porous carbons derived from cellulose are renewable and environmentally friendly. Coconut shell and wood derived porous carbons were characterized with elemental analysis, ash content, X-ray diffraction, infrared absorbance, particle size, surface area, and pore volume. The results were compared with carbon black. Uniaxial deformation of natural rubber (NR) composites indicate the composites reinforced with the porous carbon from coconut shell have higher tensile moduli at the same elongation ratio than the composites reinforced with wood carbon. 40 % coconut shell composite showed a fivefold increase in tensile modulus compared to NR. Polymer–filler interactions were studied with frequency dependent shear modulus, swelling experiments and dynamic strain sweep experiments. Both linear and non-linear viscoelastic properties indicate the polymer–filler interactions are similar between coconut shell carbon and wood carbon reinforced composites. The swelling experiments, however, showed that the polymer–filler interaction is greater in the composites reinforced with coconut shell instead of wood carbon.     

From Aminolysis Product of PET Waste to Novel Biodegradable Polyurethanes

Chemical recycling of PET has been developed by various methods. Aminolysis is one of chemical recycling methods of PET has been developed recently. The obtained product using aminolysis, Bis (2-hydroxy ethylene) terephthalamide (BHETA), has the potential for further reactions to obtain useful products. There are few reports on usage of recycled BHETA from PET waste to synthesis of polyurethanes. On the other hand, various biodegradable polyurethanes have been synthesized using polycaprolactone diol. Therefore, caprolactone is a new potential in synthesis of biodegradable polyurethanes from PET waste. In this work, novel biodegradable polyurethanes have been synthesized using BHETA. In this order, at first polyols with different molecular weights have been synthesized through ring opening polymerization of caprolactone by BHETA, then urethane linkages were formed using HDI (Hexamethylene Diisocyanate) without chain extender. Chemical, thermal, mechanical and dynamic mechanical properties, biodegradability, morphology and UV resistance of synthesized polyurethanes have been investigated.     

Preparation and Characterization of Polyurethanes from Spinifex Resin Based Bio-Polymer

In this paper we explore the preparation of polyurethanes from spinifex resin biopolymer. Polyurethanes were prepared by both one-shot and pre-polymer (two step) processes. Attenuated total reflection??Fourier transform infrared analysis revealed urethane bond formation in both processes, and the peak intensity for N?CH stretching was more sharp when the network was prepared by the pre-polymer method. Gel permeation chromatography revealed that the molecular weight of synthesized polyurethane increased with respect to the resin starting material, and the molecular weight was further increased when polyurethane was synthesized by the pre-polymer method. The glass transition temperature was also increased for the polyurethanes as compared with the starting resin. Thermo-gravimetric analysis revealed that the thermal stability of the PU-spinifex resin was reduced at intermediate temperatures due to the urethane bond formation. However, thermal degradation properties were superior at higher temperatures due to the cyclization degradation reaction of spinifex-polyurethane.     

废油脂制备生物柴油的清洁生产工艺

在固定床反应器中，采用自制固体催化剂催化废油脂与甲醇发生酯交换反应制备生物柴油。最佳反应条件为：甲醇与废油脂摩尔比6，液态空速2h，反应温度290℃。废油脂预处理简单，酸值为180mg／g时，生物柴油的产率可达85％。所制备的，仨物柴油各项物性数据均符合我国轻柴油的标准，也完全达到德国和美国生物柴油的指标要求。该生物柴油制备方法属清洁生产工艺，无废水产生。     

Characterization of Active Polybutylene Succinate Films Filled Essential Oils for Food Packaging Application

Journal of Polymers and the Environment - The development of active packaging for food applications have been increasingly favorable in publicity, industry, and research field, by attributing to...     

A New Approach to Chemical Recycling of Polyamide 6.6 and Synthesis of Polyurethanes with Recovered Intermediates

A new efficient method for the chemical decomposition of polyamide 6.6 by the glycolysis and amino-glycolysis processes was proposed. The glycolysis was conducted using the mass excess of ethylene glycol (EG) as a decomposing agent in the presence of a catalyst. Also, a mixture of EG and triethylenetetramine was used as another decomposing agent in the amino-glycolysis process. The described process of decomposition did not require the use of elevated pressure. The hydroxyl and amine numbers, rheology behavior and the presence of characteristic chemical groups in the obtained glycolysates and aminoglycolysates were determined in order to characterize the reaction products. The decomposition products were defined as non-Newtonian fluids that could be described by suitable mathematical models. The conducted studies showed that the properties of the obtained intermediates depend on the mass excess of the decomposing agent used. The resulting semi-products are suitable for reusing in the synthesis of polyurethanes, which has been confirmed by the exemplary synthesis. In the reaction, 10 and 15 wt% of commercial polyol were replaced with the recovered intermediates.     

Chemical Treatments of Natural Fiber for Use in Natural Fiber-Reinforced Composites: A Review

Studies on the use of natural fibers as replacement to man-made fiber in fiber-reinforced composites have increased and opened up further industrial possibilities. Natural fibers have the advantages of low density, low cost, and biodegradability. However, the main disadvantages of natural fibers in composites are the poor compatibility between fiber and matrix and the relative high moisture sorption. Therefore, chemical treatments are considered in modifying the fiber surface properties. In this paper, the different chemical modifications on natural fibers for use in natural fiber-reinforced composites are reviewed. Chemical treatments including alkali, silane, acetylation, benzoylation, acrylation, maleated coupling agents, isocyanates, permanganate and others are discussed. The chemical treatment of fiber aimed at improving the adhesion between the fiber surface and the polymer matrix may not only modify the fiber surface but also increase fiber strength. Water absorption of composites is reduced and their mechanical properties are improved.     

Photo-oxidation and Photo-toxicity of Crude and Refined Oils

The fate and effects of an oil spill are effected by solar radiation through the action of photo-oxidation and photo-toxicity. Photo-oxidation, an important process in the weathering of oil, produces a variety of oxidized compounds, including aliphatic and aromatic ketones, aldehydes, carboxylic acids, fatty acids, esters, epoxides, sulfoxides, sulfones, phenols, anhydrides, quinones and aliphatic and aromatic alcohols. Some of these compounds contribute to the marine biota toxicity observed after an oil spill. Photo-toxicity occurs when uptake of certain petroleum compounds, e.g. certain polycyclic aromatic hydrocarbons and benzothiophenes, is followed by solar exposure which results in much greater toxicity than after dark uptake. The mechanism of PAH photo-toxicity includes absorbance of solar radiation by the PAH which produces a free radical and this free radical in turn reacts with oxygen to produce reactive oxygen species that can damage DNA and other cellular macromolecules. While most studies on photo-toxicity have been carried out in the laboratory, there are studies showing that water from an oil spill is photo-toxic to bivalve embryos for at least a few days after the spill. Other studies have found that oil contaminated sediments are photo-toxic to several marine invertebrates. More studies are required to determine if marine fauna at an oil spill site are effected by the action of photo-toxicity and photo-oxidation.     

Fungal-modification of Natural Fibers: A Novel Method of Treating Natural Fibers for Composite Reinforcement

Growing interest in green products has provided fresh impetus to the research in the field of renewable materials. Plant fibers are not only renewable but also light in weight and low in cost. Polymer composites manufactured using them find applications in diverse fields such as automobiles, housing, and furniture. However, their hydrophilic nature and inadequate adhesion with matrix limits their use in high performance applications. In this study, a novel method for improving adhesion characteristics of natural fibers has been developed. This method is carried out by treating hemp fibers with a fungus: Ophiostoma ulmi, obtained from elm tree infected with Dutch elm disease. Treated fibers showed improved acid–base characteristics and resistance to moisture. Improved acid–base interactions between fiber and resin are expected to improve the interfacial adhesion, whereas improved moisture resistance would benefit the durability of the composites. Finally, composites were prepared using untreated/treated fibers and unsaturated polyester resin. Composites with treated fibers showed slightly better mechanical properties, which is most probably due to improved interfacial adhesion.     

Utilization of coal gangue for the production of brick

Journal of Material Cycles and Waste Management - Coal gangue, an industrial solid waste discarded from coal mining and processing, was used as the sole raw material to prepare brick. The coal...     

铬渣资源化处理的零排放工艺

采用氧化—还原法对某钢厂的粗铬渣进行提纯回收,对各项工艺参数进行了优化,探讨了铬渣零排放处理工艺的可行性。实验结果表明：在氧化温度80 ℃、氧化时间1.5 h、双氧水加入量2.35 mL/g（以铬渣计）,还原时间15 min、还原pH 1.5、NaHSO₃加入量0.445 g/g（以铬渣计）,沉淀pH 8.0,煅烧温度1 050 ℃、煅烧时间1 h的条件下,所得废渣的w（Cr）为1.29%,回收铬绿产品的w（Cr₂O₃）为97.20%,铬回收率为94.40%;处理后废水的ρ（总铬）约为0.06 mg/L,低于GB 13456—2012《钢铁工业水污染物排放标准》中规定的1.50 mg/L,既可作为循环用水,也可排放;处理后废渣中含大量硅元素,可作为生产水泥发泡节能砖或砌块的原料;整个回收过程清洁无污染,零排放,且具备一定的盈利空间。     

超声波诱导降解甲胺磷

报道了用超声波诱导降解模拟水中低浓度甲胺磷农药的可行性试验.试验中探讨了声强、辐射时间、温度、初始pH和外加亚铁盐或H2O2等对降解效果的影响.试验结果表明,在甲胺磷浓度为1.0×10-4mol/L、起始pH2.5、温度30℃、Fe2+＞50mg/L、充O2至饱和的条件下,用低频超声波(80W/cm2)连续辐照120min,甲胺磷去除率达到99.3%.