Synthesis and properties of castor oil-based waterborne polyurethane cloisite 30B nanocomposite coatings

Waterborne polyurethane dispersions (WPUDs) were synthesized successfully from castor oil-based polyol, isophorone diisocyanate and dimethylol propionic acid with NCO/OH ratio of 1.5. Different weight percentages of cloisite 30B (1, 2, and 3 wt%) were loaded with WPUDs to prepare nanocomposite films. Prepared prepolymer and nanocomposite films were characterized using FTIR, XRD, SEM, TEM, DSC, and TGA techniques, and coating properties, such as pencil hardness, abrasion resistance, impact resistance, and contact angle, were evaluated. The results obtained from different amounts of clay loading were compared with the pristine castor oil-based WPUDs. The FTIR spectra deconvolution technique was used to study the hydrogen bonding effect within the polymer with an increase in clay content. TGA analysis showed that the thermal stability of WPUDs increases with cloisite 30B (C30B) content. The surface morphology and hydrophilicity/hydrophobicity nature of the nanocomposite films were characterized using scanning electron microscopy and contact angle measurement. The results obtained from tensile tests indicated that the mechanical property of the dispersion system improved with C30B content. A high-performance castor oil-based nanocomposite coating with low volatile organic component can be targeted as an outcome of this work.     

A fully bio-based waterborne polyurethane dispersion from vegetable oils: From synthesis of precursors by thiol-ene reaction to study of final material

A new linear saturated terminal diisocyanate was synthesized from castor oil-derived undecylenic acid by thiol-ene coupling (TEC) and Curtius rearrangement. The structure of the diisocyanate was carefully examined using Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance (NMR), and ¹³C NMR. This diisocyanate was used as a starting material for the preparation of a fully bio-based waterborne polyurethane dispersion (BPUD) by reacting with castor oil and castor oil-based carboxylic acid-type hydrophilic chain extender, which was prepared from castor oil by using 3-mercaptopropionic acid via TEC. The thermal/mechanical properties of the formed BPUD film were characterized via differential scanning calorimetry, thermogravimetric analysis, tensile test, hardness test, and water resistance test. The fatty acid-derived diisocyanate and the castor oil-based hydrophilic chain extender were used to produce BPUD with favorable properties.     

Waterborne polyurethane-silica nanocomposite adhesives based on castor oil-recycled polyols: Effects of (3-aminopropyl)triethoxysilane (APTES) content on properties

Waterborne castor oil-recycled polyol based polyurethane-silica nanocomposite adhesives (WPU) with polymer matrix and silica nanoparticles chemically bonded have been successfully prepared through a sol-gel process. A series of waterborne polyurethane adhesives with hard segment contents from 71.3 to 74.5 wt%, were synthesized using an isophorone diisocyanate, 2-bis(hydroxymethyl) propionic acid, recycled castor oil-based as soft segments and (3-aminopropyl)triethoxysilane (APTES) as chain extender. The depolymerized oligoester obtained from glycolysis of poly(ethylene terephthalate) (PET) waste using triethylene glycol (TEG), was transesterified with castor oil (CO) which resulted in the formation of hydroxyl-functional polyester polyol, with hydroxyl value of 414 mgKOH g⁻¹. The molecular structures and mass of glycolyzed PET oligoesters, castor oil-based polyol and castor oil-based polyurethane-silica nanocomposite adhesives were estimated by Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The structure and properties of the resulting films were investigated by FTIR, wide angle X-ray diffraction measurement (XRD), thermogravimetry (TG) and differential scanning calorimetry (DSC). TG analysis indicated that APTES can improve the thermal stability of WPU. XRD showed that the crystallinity of WPU decreased with the increase alkoxysilane content. The extent of crosslinking was investigated to show a dependence on silica concentration, which increased the glass transition temperature and particle size of polyurethane nanocomposites with increasing alkoxysilane content due to the condensation of the alkoxysilane groups. The hardness, adhesion and gloss quality of the polyurethane films were also determined considering the effect of APTES content, so this paper confirmed the suitability of using these castor oil-based waterborne polyurethane-silica nanocomposites as new adhesive materials with high performance coatings materials. The experimental results reveal that the APTES and the hard segment content play a key role in controlling the structure and properties of the PU cast films based on castor oil-recycled polyols.     

蓖麻油基下游产物及蓖麻油增塑剂的研究及其应用进展

随着全球化石资源消耗量的不断剧增, 能源危机问题引起了广泛的关注。在植物资源能源化的利用中, 以蓖麻油为原料开发高附加值下游产品已成为研究热点。本文介绍了国内外蓖麻油基下游产品的制备方法、产品性能及应用领域等方面。回顾了脱水蓖麻油、酯交换蓖麻油、环氧化蓖麻油、蓖麻油基聚氨酯等下游产物的制备与应用性能研究。简述了蓖麻油基增塑剂的种类及应用领域, 具体分析了环氧乙酰蓖麻油酸甲酯的制备方法及产品特性。提出了在我国蓖麻油基增塑剂的生产过程中反应温度、催化剂用量等因素影响环氧基团稳定性的问题, 指出目前我国催化合成蓖麻油基增塑剂的趋势和发展方向。     

Properties of alkoxysilane castor oil synthesized via thiol-ene and its polyurethane/siloxane hybrid coating films

We developed a new silanized castor oil (MSCO) composed of castor oil and 3-mercaptopropyl trimethoxy silane via thiol-ene coupling (TEC). This MSCO was used as a functional polyol in the preparation of a series of bio-based polyurethane/siloxane (SiPU) hybrid coatings through reactions with different castor-oil-and-isophorone-diisocyanate (IPDI) ratios. The SiPU films exhibited better mechanical and thermal properties than castor oil-based coatings without MSCO. The cross-linked structure of the obtained hybrid materials was confirmed by Fourier transform infrared (FTIR) spectroscopy, whereas the morphologies and surface roughness of the hybrid-coating films were observed by scanning electron microscopy (SEM). A slight phase separation was observed in the obtained hybrid materials. The introduction of a silica network can reduce the surface energy of the obtained hybrid materials. The thermal stability of the obtained hybrid materials increases with increasing Si content. The obtained hybrid materials can be applied in coatings as a result of these characteristics, and this study provides an alternative method of preparing hybrid materials from renewable sources.     

From Castor Oil-Based Multifunctional Polyols to Waterborne Polyurethanes: Synthesis and Properties

A novel castor oil-based multifunctional polyol (CM) is fabricated through mild thiol-ene photo induced reactions using castor oil (CO) and 1-thioglycerol (MPD) as building blocks. The effect of the reaction time, molar ratio of thiol to carbon–carbon double bond, and the loadings of photo-initiator are optimized. The resulting CM is combined with CO and employed as cross-linkers to prepare castor oil-based water-borne polyurethane emulsion with desirable mechanical properties and water resistance. Owing to the incorporation of CM cross-linker with high hydroxyl value of 371 mg KOH/g (which is 2.27 times higher than that of the CO), the prepared castor oil-based waterborne polyurethane (CMWPU) possesses compacted 3D network structure with high cross-linking degree, leading to improved glass transition temperature (45 °C), tensile strength (10.8 MPa), water contact angle (87.4°), and decreased water absorption rate (16.12%) with 20% CM additions. Overall, this work illustrates the feasibility of introducing bio renewable CM combined with CO to develop castor oil-based WPU employing a sustainable development strategy.     

Synthesis and properties of siloxane-crosslinked polyurethane-urea/silica hybrid films from castor oil

A novel hybrid diol (HD) crosslinker has been synthesized with hydrolyzable –Si–OR groups from 3-amino propyl trimethoxy silane and 3-glycidoxy propyl trimethoxy silane. Its chemical structure was confirmed by Fourier transform infrared spectroscopy, ¹H and ¹³C nuclear magnetic resonance spectroscopy to introduce it as a crosslinker in the castor oil, a renewable resource, to develop functional organic inorganic hybrid coatings. A series of castor oil-based organic–inorganic hybrid materials were prepared from castor oil, isophorone diisocyanate, and the different weight percentages of synthesized HD. Dynamic mechanical thermal analysis, thermogravimetric analysis, differential scanning calorimetry, and the universal testing machine were employed to characterize the hybrid films. The measured properties were found to be strongly influenced by the weight ratio of HD to the castor oil-based polyurethanes. The glass transition temperatures (T _g) for the cured hybrid films were found to be 26–72°C. Antibacterial activity, in vitro hydrolytic degradation, and swelling properties of the hybrid films have been studied. The cured hybrid films exhibited excellent antibacterial activity, which was enhanced with addition of the HD. The alkoxy silane-crosslinked castor oil-based coatings have shown better mechanical and viscoelastic properties in comparison to the control (uncrosslinked castor oil-based polyurethane-urea) coatings. The results showed that the weight percent of the HD is the main factor that controls the thermal, antimicrobial, mechanical, swelling, and degradation properties of these hybrid films.     

硅橡胶/有机改性蒙脱土纳米复合材料的性能研究

用熔体插层法制备甲基乙烯基硅橡胶(MVQ)/有机改性蒙脱土(OMMT)纳米复合材料并研究其微观结构和性能。结果表明:OMMT改性剂疏水性从优到劣的顺序为I.44P,I.30P,Bengel434,I.44P和I.30P在MVQ中的分散性优于Bengel434;MVQ/OMMT纳米复合材料的物理性能和热稳定性从优到劣的顺序为MVQ/I.44P,MVQ/I.30P,MVQ/Bengel434纳米复合材料;添加40份I.44P的MVQ/I.44P纳米复合材料的100%定伸应力、拉伸强度和撕裂强度比纯胶有较大提高。     

Modified cellulose nanocrystals enhancement to mechanical properties and water resistance of vegetable oil-based waterborne polyurethane

Environmentally friendly and lightweight silylated cellulose nanocrystal (SCNCs)/waterborne polyurethane (WPU) composite films that exhibit excellent mechanical properties and water resistance were prepared. The cellulose nanocrystals (CNCs) of the filamentous structure were surface-modified by γ-aminopropyltriethoxysilane (APTES) and then introduced into a castor oil-based aqueous polyurethane (WPU) matrix by in situ polymerization. The morphology and silylation degree of CNCs were characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and Fourier infrared transform spectroscopy at different APTES concentrations. The results showed that the surface of the nanocellulose crystal has the best silylation morphology and thermal stability with incorporation of 6 wt % APTES. The thermal stability, mechanical properties, surface morphology, and water resistance of the nanocomposites were investigated by TGA, tensile test, SEM and optical contact angle, water absorption test, and mechanical property test after immersed in water. It was found that the effective introduction of modified CNCs resulted in a significant increase in tensile strength at high levels, and the thermal stability and hydrophobicity of the material were improved simultaneously, reaching the percolation threshold at a 0.50 wt % SCNCs as determined theoretically. This study provided an approach to the design and development of surface-modified CNCs/vegetable oil-based polymer composites by using an appropriate concentration of silane coupling agent to modify CNCs and improve the compatibility between nanocellulose and vegetable oil-based polymer matrices. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48228.     

Effect of special structure of clam shell powder on structure and properties of castor oil-based composites

Castor oil (CO) is an environmentally friendly renewable green resource and ideal alternative to petroleum resources. The preparation of high strength and high toughness castor oil-based polyurethane prepolymer (COPU) composites has significant applications such as supporting material and engineering plastic sheet. In this study, unmodified clam shell powder (CSP) with a unique CaCO₃-proteoglycan structure was used as a filler to prepare compatible reinforced COPU composite materials. Investigation of the mechanical properties revealed that the elastic modulus of the composite COPU reinforced with 50 wt% of CSP had increased to 5859.0 ± 8.4 MPa representing 187.77% to obtain stiffer and stronger material over pure COPU (2036.6 ± 196.9 MPa). Moreover, the scanning electron microscopy, thermogravimetric analysis and contact angle results demonstrated that the reinforced COPU composites have better compatibility, thermal stability, and water resistance than pure COPU. This work will promote the application prospects of CO-based polyurethane.     

Preparation and properties of copper-oil-based nanofluids

In this study, the lipophilic Cu nanoparticles were synthesized by surface modification method to improve their dispersion stability in hydrophobic organic media. The oil-based nanofluids were prepared with the lipophilic Cu nanoparticles. The transport properties, viscosity, and thermal conductivity of the nanofluids have been measured. The viscosities and thermal conductivities of the nanofluids with the surface-modified nanoparticles have higher values than the base fluids do. The composition has more significant effects on the thermal conductivity than on the viscosity. It is valuable to prepare an appropriate oil-based nanofluid for enhancing the heat-transfer capacity of a hydrophobic system. The effects of adding Cu nanoparticles on the thermal oxidation stability of the fluids were investigated by measuring the hydroperoxide concentration in the Cu/kerosene nanofluids. The hydroperoxide concentrations are observed to be clearly lower in the Cu nanofluids than in their base fluids. Appropriate amounts of metal nanoparticles added in a hydrocarbon fuel can enhance the thermal oxidation stability.     

水性聚氨酯/蒙脱土复合乳液的合成及性能表征

本文通过蒙脱土插层聚合法制备了水性聚氨酯/蒙脱土复合乳液。通过单体插层于蒙脱土中,与聚氨酯聚合反应,均匀分散于水性聚氨酯中。用FTIR和TEM测试表征,观察到蒙脱土均已聚合入聚氨酯包裹。研究结果表明:当蒙脱土含量在5%左右时,该乳液涂膜具有较好的耐热性、10%分解温度比普通聚氨酯提高了大约20℃,拉伸强度和断裂强度达到最高值,分别为2.31Mpa和17.94N/mm。随着蒙脱土含量的增大,乳液粒子粒径增大,耐水性增强。蒙脱土含量达到5%时,乳液粒径为108nm,吸水率降至31.9%。     

Synthesis and Thermal Characterization of Polyurethane/Clay Nanocomposites Based on Palm Oil Polyol

Polyurethanes (PUs) are very versatile polymeric materials with a wide range of physical and chemical properties. PUs also have desirable properties, such as high abrasion resistance, tear strength, shock absorption, flexibility, and elasticity. Although they have poor thermal stability, it can be improved by using treated clay.

The objective of the present work is to study the thermal stability of polyurethane, polyurethane/montmorillonite (PU CTAB-mont 3% wt), and polyurethane/montmorillonite containing moca (PU Moca CTAB-mont 3% wt) nanocomposites based on palm oil polyol.

The interest of investigating the synthesis of polyurethane/clay nanocomposites based on palm oil polyol is to explore the use of palm oil polyol to partially replace petrochemical-based polyol.

Polyurethane/clay nanocomposites were prepared by a pre-polymer method and evaluated by Fourier Transform Infrared Spectra (FTIR) to determine micro-domain structures of segmented PU, PU CTAB-mont 3% wt, and PU Moca CTAB-mont 3% wt. The morphology of the nanocomposites was characterized by X-ray diffraction (X-RD), and flame retardant was investigated with thermogravimetric analysis (TGA). The result showed that in comparison with the virgin polyurethane, adding clay and moca demonstrated better thermal stability.     

负载羧基有机蒙脱土制备环氧树脂纳米复合材料(英文)

用椰油酰胺丙基甜菜碱(CAB)制备了1种负载羧基的有机蒙脱土,并将这种有机蒙脱土加入甲基四氢苯酐固化环氧树脂体系中制得环氧树脂/蒙脱土纳米复合材料。采用XRD衍射和透射电镜TEM研究了蒙脱土有机化前后和在纳米复合材料中的片层结构和形态。用TGA研究了纳米复合材料的热稳定性能。结果表明,制备的负载羧基蒙脱土充分插层且很容易分散在环氧树脂中得到纳米复合材料。其热稳定性和有机蒙脱土在树脂中的分散状态有关。     

Surfactant-free core–shell hybrid latexes from soybean oil-based waterborne polyurethanes and poly(styrene-butyl acrylate)

Novel surfactant-free core–shell hybrid latexes have been successfully synthesized by seeded emulsion polymerization of 10–60 wt% vinyl monomers (styrene and butyl acrylate) in the presence of a soybean oil-based waterborne polyurethane (PU) dispersion as seed particles. The soybean oil-based waterborne polyurethanes, synthesized by reacting isophorone diisocyanate with methoxylated soybean oil polyols and dimethylol propionic acid, form the latex shell, serve as a polymeric high molecular weight emulsifier, while the vinyl polymers form the core. The structures and thermal and mechanical properties of the PU dispersions and the resulting core–shell latexes have been characterized by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and measurement of the mechanical properties. The core–shell hybrid latex films show a significant increase in thermal stability and mechanical properties when compared with the pure polyurethane films, and exhibit a change in mechanical behavior from elastomeric polymers to tough and hard plastics, due to grafting and crosslinking in the hybrid latexes.     

水性环氧树脂包覆有机蒙脱土制备木材胶粘剂

摘要：水性环氧树脂通常含有水溶性分子或分子链，导致在高温和潮湿条件下作为木材胶粘剂时耐水性及力学性能较差。采用有机改性的纳米蒙脱土改性水性环氧树脂增强水性环氧树脂胶粘剂的耐水性及力学性能。并通过乳液包覆蒙脱土的方法与直接共混的方法对比，研究了不同添加量有机蒙脱土（0%，3%，6%，9%）对胶粘剂性能的影响。胶粘剂的耐水性及力学性能通过测量胶粘剂在干燥及潮湿条件下的剪切强度来表示。通过TGA、SEM、TEM、DSC研究了复合胶粘剂的热稳定性和结构。结果表明，在水性环氧树脂中添加有机改性的纳米蒙脱土，可以有效地提高胶粘剂的粘结强度，此外，采用乳液包有机覆蒙脱土的方法比直接共混的方法制备得到胶粘剂，有机蒙脱土在胶粘剂中分布更均匀，具有更优异的力学性能，说明有机蒙脱土在复合材料中的分散质量是影响复合胶粘剂性能的主要原因。     

PDMS改性蓖麻油基水性聚氨酯的制备及防污性能

本研究以低成本的二甲基二甲氧基硅烷为主要原料，通过水解缩合反应制备合成了聚二甲基硅氧烷（PDMS），进而将其引入蓖麻油基水性聚氨酯（CWPU-SOP）中制备了具有防污性能的蓖麻油基水性聚氨酯(PDMS/CWPU-SOP)。结果表明，当PDMS引入量为8%时，与CWPU-SOP薄膜相比，PDMS/CWPU-SOP薄膜接触角提高了25?，达110?，PDMS/CWPU-SOP薄膜的吸水率下降了7%，为15%；PDMS提高了薄膜疏水性和耐水性。PDMS/CWPU-SOP薄膜在不同酸碱性的液滴在其表面可自由滚落且不留痕迹，具有一定的防污性能。     

马来酸酐改性蓖麻油制备交联型水性聚氨酯

以马来酸酐与蓖麻油制备含碳碳双键的三羧基蓖麻油(MACO)作为内交联剂,合成改性蓖麻油水性聚氨酯乳液(MACO-WPU)。采用FT-IR和XRD对改性聚氨酯的结构进行表征,证实MACO被成功引入到聚氨酯大分子链中且分子链呈现无序状态。通过对力学性能、吸水率、粒径、热重分析等研究了MACO用量对聚氨酯乳液及胶膜性能的影响,结果表明:当w(MACO)=3%时,乳液外观和稳定性好,平均粒径为48.45 nm; 胶膜的拉伸强度和断裂伸长率分别为13.15 MPa、195%;与未改性WPU相比热稳定性略有提高。     

Preparation and characterization of waterborne polyurethane/silica hybrid dispersions from castor oil polyols obtained by glycolysis poly(ethylene terephthalate) waste

Castor oil polyols (COLs) have been synthesized from glycolyzed oligoester polyol in order to produce waterborne polyurethane (WPU)/silica hybrid dispersions. Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis with different molar ratio of poly(ethylene glycol) ( PEG 400), in the presence of zinc acetate as catalyst. The obtained glycolyzed products were reacted with castor oil (CO) to attain castor oil polyols by the process of transesterification. Five castor oil polyols were used with hydroxyl values of 255, 275, 326, 366 and 426 mg KOH g⁻¹. Several castor oil-based, polyurethane/silica hybrid dispersions having soft segment content of 39.6% to 28.2% and two concentrations of SiO₂ nanoparticles (0.5 and 1.0) have been prepared.The incorporation effect of SiO₂ nanoparticles into the PU matrix and the hydroxyl functionality of the COLs on the thermal and mechanical properties of resulting polyurethane films has been examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TG) and measurement of the mechanical properties. The degree of phase separation (DPS) between oxide nanoparticles and hard segment, and particle size in the polyurethane, depends to some extent on nanosilica content and the hydroxyl functionality of the polyols employed in the polyurethane preparation process.Thermal stability of obtained hybrid materials depends on the hydroxyl functionality of the COLs and nanosilica content. The T_10% and T_50% (the temperature where 10 and 50% weight loss occurred) of WPU films decreased with the rise of OH functionality of castor oil polyols, caused by the increase of hard segment content. Glass transition temperature increased with increasing OH functionality and SiO₂ content. The hardness, adhesion and gloss quality of the polyurethane films were also determined with a view to assessing the effect of mole ratios of PET to glycol in glycolyzed products, the hydroxyl functionality and the SiO₂ content.     

蓖麻油型聚氨酯密封胶

阐述了蓖麻油型聚氨酯密封胶的性能与发展现状 ,分析了各种组分对密封胶性能的影响 ,并预测了此种密封胶的发展方向