纳米纤维素晶须改性羧酸型水性聚氨酯的合成及性能
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摘要
以蓖麻油(CO)、2-2-双(羟甲基)丙酸(DMPA)、异佛尔酮二异氰酸酯聚氨酯(IPDI)为主要原料合成了植物油基水性聚氨酯(WPU),通过酸解法制得的纳米纤维素晶须(CNC)与WPU超声物理共混,利用纳米纤维素晶须与WPU基体之间强烈的氢键作用制得纳米复合材料(WPU/CNC)涂膜。通过红外光谱、粒径分析、扫描电子显微镜、热失重分析、超热扫描量热分析等方法来测试涂膜的性能。研究表明,在CNC的添加量为0.25%(质量分数,下同)时,可获得分散性良好及性能优异的聚氨酯涂膜,纳米复合材料的拉伸强度从17.56 MPa增强到27.96 MPa;并且涂膜的热稳定性,硬段的分解温度及软段的玻璃化转变温度(T_g)也得到了很好的改善。
The vegetable oil-based waterborne polyurethane(WPU) was synthesized by using castor oil, 2-2-bis(hydroxymethyl)propionic acid and isophorone diisocyanate polyurethane as raw materials(IPDI) and then was mixed with nano-cellulose whiskers(CNC) by acid hydrolysis under ultrasonication. The coating films of WPU/CNC composite were prepared through strong hydrogen bonding between the CNC filler and WPU matrix. The microstructure, morphology and properties of the coating films were investigated by Fourier-transform infrared spectroscopy, scanning electron microscopy, particle-size analysis, thermogravimetric analysis, differential scanning calorimetry and mechanical measurements. The results indicated that the coating films achieved good dispersibility and excellent performance when 0.25 wt% of CNC was added. The tensile strength of the composites was improved from 17.56 MPa to 27.96 MPa. Moreover, the thermal stability of coating films, the decomposition temperature of hard segment and the glass transition temperature of soft segment were also improved.
The vegetable oil-based waterborne polyurethane(WPU) was synthesized by using castor oil, 2-2-bis(hydroxymethyl)propionic acid and isophorone diisocyanate polyurethane as raw materials(IPDI) and then was mixed with nano-cellulose whiskers(CNC) by acid hydrolysis under ultrasonication. The coating films of WPU/CNC composite were prepared through strong hydrogen bonding between the CNC filler and WPU matrix. The microstructure, morphology and properties of the coating films were investigated by Fourier-transform infrared spectroscopy, scanning electron microscopy, particle-size analysis, thermogravimetric analysis, differential scanning calorimetry and mechanical measurements. The results indicated that the coating films achieved good dispersibility and excellent performance when 0.25 wt% of CNC was added. The tensile strength of the composites was improved from 17.56 MPa to 27.96 MPa. Moreover, the thermal stability of coating films, the decomposition temperature of hard segment and the glass transition temperature of soft segment were also improved.
引文
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[2] 王甲福,俞丹,王炜 . 环氧大豆油-乳酸改性水性聚氨酯乳液的制备及性能研究[J]. 涂料工业,2013,43(11):35-40. WANG J F,YU D,WANG W. Preparation and Properties of Epoxy Soybean Oil-Lactic Acid Modified Waterborne Polyurethane Emulsion[J]. Paint & Coatings Industry,2013,43(11):35-40.
[3] JOSé A J,VANESA G P,VICTOR C,et al. Role of the Interactions between Carbonate Groups on the Phase Separation and Properties of Waterborne Polyurethane Dispersions Prepared with Copolymers of Polycarbonate Diol[J]. Progress in Organic Coatings,2015,88:199-211.
[4] SATYABRAT G,MANISHEKHAR K,BIMAN B,et al. High Performance Luminescent Thermosetting Waterborne Hyperbranched Polyurethane/Carbon Quantum Dot Nanocomposite with in Vitro Cytocompatibility[J]. Composites Science and Technology,2015,118:39-46.
[5] PIOTR K,MAREK Z,MAREK Z,et al. Composites Prepared from the Waterborne Polyurethane Cationomers-modified Graphene. Part II. Electrical Properties of the Polyurethane Films[J]. Colloid and Polymer Science,2015,293(10):2 941-2 947.
[6] QUN Z,GANG S,YAN K L,et al. Novel Bio-antifelting Agent Based on Waterborne Polyurethane and Cellulose Nanocrystals[J]. Carbohydrate Polymers,2013,91(1):169-174.
[7] WU H F,WEI N D,LI Z J,et al. Abrasion Resistance of Waterborne Polyurethane Films Incorporated with PU/Silica Hybrids[J]. Progress in Organic Coatings,2015,86:125-133.
[8] FARHAN A, MIKAEL S, LARS B. Nanostructured Biocomposites Based on Unsaturated Polyester Resin and a Cellulose Nanofiber Network[J]. Composites Science and Technology,2015,117: 298-306.
[9] AHMED S A S,FANNIE A,ALAIN D,et al. Review of Recent Research into Cellulosic Whiskers, Their Properties and Their Application in Nanocomposite Field[J]. Biomacromolecules,2005,6(2):612-626.
[10] PAUL P,SEOK-YOUL C,BONGSUP S,et al. Molecularly Engineered Nanocomposites:Layer-by-layer Assembly of Cellulose Nanocrystals[J]. Biomacromolecules,2005,6 (6):2 914-2 918.
[11] LIU H,SONG J,SHANG S B,et al. Cellulose Nanocrystal/Silver Nanoparticle Composites as Bifunctional Nanofillers within Waterborne Polyurethane[J]. ACS Applied Materials & Interfaces,2012,4(5):2 413-2 419.
[12] ARANTZAZU S E,LORENA U,AITOR A,et al. Two Different Incorporation Routes of Cellulose Nanocrystals in Waterborne Polyurethane Nanocomposites[J]. European Polymer Journal,2016, 76:99-109.
[13] 张新昌,梁金梅 . 纳米纤维素增强磺酸/羧酸型水性聚氨酯的研究[J]. 涂料技术与文摘, 2016,37(5):28-33 ZHANG X C,LIANG J M . Study on Nanocellulose Enhanced Sulfonic Acid/Carboxylic Acid Waterborne Polyurethane[J]. Coatings Technology & Abstracts,2016,37(5):28-33.
[14] 胡令,功能化石墨烯改性水性聚氨酯及其性能研究[D]. 无锡:江南大学,2016.
[15] ALEX O S, LUCIANO H S R, LUZI F M, et al . Influence of Cellulose Nanofibrils on Soft and Hard Segments of Polyurethane/Cellulose Nanocomposites and Effect of Humidity on Their Mechanical properties[J]. Polymer Testing,2014,40:99-105.
[16] GAO Z Z,PENG J,ZHONG T H,et al. Biocompatible Elastomer of Waterborne Polyurethane Based on Castor Oil and Polyethylene Glycol with Cellulose Nanocrystals[J]. Carbohydrate Polymers,2012,87:2 068-2 075.
[17] CAO X D,YOUSSEF H,LUCIAN L,et al. One-pot Polymerization, Surface grafting, and Processing of Waterborne Polyurethane-cellulose Nanocrystal Nanocomposites[J]. Journal of Materials Chemistry,2009,19:7 137-7 145.
[18] 王宇奇,葛硕硕,张萍波等 . 大豆油基多元醇改性水性聚氨酯胶黏剂的制备及性能研究[J]. 化工新型材料,2016, 44(10);191-197. WANG Y Q,GE S S,ZHANG P B et al. Preparation and Properties of Soybean Oil-Based Polyol Modified Waterborne Polyurethane Adhesive[J].New Chemical Materials,2016,44(10);191-197.
[19] CHENG D,WEN Y B,AN X Y,et al. TEMPO-oxidized Cellulose Nanofibers (TOCNs) as a Green Reinforcement for Waterborne Polyurethane Coating (WPU) on Wood[J]. Carbohydrate Polymers,2016,115:326-334.
[20] MARíA L A,STEVE N,et al. Characterization of Nanocellulose Reinforced Shape Memory Polyurethanes[J]. Polymer International,2008,57(4):651-659.
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