双重改性水性聚氨酯分散体的合成及应用

以异氰酸酯、聚己内酯二元醇、环氧树脂E-51、二羟甲基丙酸和蓖麻油为主要原料制备了环氧树脂和蓖麻油双重改性的水性聚氨酯分散体。结果表明,当NCO与OH摩尔比为1.3、DMPA添加质量分数为4%~6%、三乙胺中和度为80%时,所得涂膜铅笔硬度H,耐水性72 h无异常,满足了水性木器面漆的性能要求。     

Preparation and characterization of modified castor oil via photo-click chemistry for UV-curable waterborne polyurethane with enhanced water resistance and low conductive percolation threshold

A castor oil (CO) was modified via thiol-ene click chemistry reaction between CO and 3-mercaptopropyl trimethoxysilane, with the conversion of CC bonds of CO over 99% based on ¹HNMR spectra. The obtained modified castor oil (MCO) was used as a biobased polyol to prepare waterborne polyurethane (WPU) dispersions. The modification of CO exhibited a great effect on the properties of WPU dispersions and coatings, and an obvious change is the improvement of the water resistance of WPU coatings. WPU dispersions with MCO had good storage stability. A WPU coating with 7% MCO had high surface hydrophobicity, and its water absorption was as low as 3.2%. Conductive carbon black filled WPU coatings with MCO were cured by efficient UV radiation, and their conductive percolation threshold could decrease to 0.76%, which could be attributed to the well filler dispersion and strong filler-polymer interaction. The WPU dispersions are ecofriendly, and can be used to produce biobased WPU coatings with a great application potential in antistatic coating fields.     

Insight on Castor Oil Based Polyurethane and Nanocomposites: Recent Trends and Development

Castor oil has gained momentous attention as a valuable bio-based monomer and a potential alternative to the current petrobased polyol for synthesizing polyurethane due to the presence of inherent hydroxyl group. In spite of its huge potentiality very little has been reviewed regarding the development of polyurethane from castor oil. This review thus highlights the recent trends and development in the field of polyurethane and its nanocomposite based on castor oil including its biodegradability and weatherability studies. Further, this review also provides an insight regarding the utilization of castor oil based polyurethane and its nanocomposite for coating application.     

Flame Retardant Modified Bio-Based Waterborne Polyurethane Dispersions Derived from Castor Oil and Soy Polyol

Although tremendous efforts have been dedicated to developing environmentally friendly bio-based waterborne polyurethane (WPU) dispersions from vegetable oil, the fabrication of WPU dispersions solely derived from vegetable oil-based polyol with excellent comprehensive properties is still challenging. In the present work, novel bio-based WPU dispersions derived from castor oil and soy polyol is successfully modified by phosphorus-nitrogen chain extender [bis(2-hydroxyethyl)amino]-methyl-phosphonic acid dimethyl ester (BH). The structure and properties of the dispersions and films are characterized systematically by Fourier transform infrared spectroscopy, thermogravimetric analysis , mechanical test, and limiting oxygen index (LOI), etc. The results indicate that bio-based WPU films display moderate mechanical performance by adjusting BH content, and the WPU film containing 100% BH with 47.8% biobased content has a tensile strength of 8 MPa and the highest Young's modulus of 62.3 MPa. The incorporation of BH can increase the production of char residue. The flame retardancy of WPU films increase gradually with the BH molar content, and the LOI value of the WPU100 with 1.53 wt% phosphorus content can reach as high as 28.1%. This work may provide a new approach to develop high biobased content, eco-friendly, flame retardant WPU for application in the surface coating industry.     

蓖麻油改性聚醚型水性聚氨酯乳液的性能

以聚醚、甲苯二异氰酸酯(TDI)、一缩二乙二醇、蓖麻油为主要原料,二羟甲基丙酸(DMPA)为亲水扩链剂,三乙胺为中和剂制备了稳定的阴离子水性聚氨酯乳液(WPU),研究了NCO/OH摩尔比、DMPA及蓖麻油的加入量对WPU的耐水性、稳定性和力学性能的影响,结果表明:改性后的乳液具有较好的稳定性,适量的蓖麻油可提高胶膜的拉伸强度及耐水性。当聚醚与蓖麻油质量比为7︰3、DMPA为5%、NCO与OH摩尔比为1.3时,WPU综合性能最好。     

室温固化水性聚氨酯树脂的耐水性研究

以甲苯二异氰酸酯(TDI)、聚醚多元醇(PTMG)为主要原料,二羟甲基丙酸(DMPA)为亲水单体,采用三羟甲基丙烷脱水蓖麻油酸酯(TMPDCO)进行改性,通过逐步聚合反应制备了一系列室温固化水性聚氨酯树脂。研究了TMPDCO的含量、亲水基团含量、软段多元醇种类与相对分子质量、封端剂以及氮丙啶交联剂等对聚氨酯涂膜耐水性的影响,从而确定了最佳合成配方,获得了优良耐水性能的水性聚氨酯树脂。     

TMPDCO对封端型水性聚氨酯的改性研究

以三羟甲基丙烷和脱水蓖麻油酸为原料合成了三羟甲基丙烷单脱水蓖麻油酸酯(TMPD-CO),研究了TMPDCO用量对甲基丙烯酸羟乙酯封端的阴离子型水性聚氨酯胶膜的耐水、耐醇、耐热性能和力学性能的影响。结果表明,TMPDCO的加入,增加了水性聚氨酯的不饱和度,有利于交联成膜;当TMPDCO用量占预聚体总羟基的摩尔百分比为40%时,水性聚氨酯的耐水、耐热和耐醇性能较好,并且当预聚体R为5时,力学性能最佳。     

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.     

水性聚氨酯的蓖麻油和环氧改性及其富锌涂层耐蚀性能研究

以蓖麻油和环氧树脂为改性剂,对水性聚氨酯进行了改性,乳液红外分析证实了改性剂的有效接枝.改性后的聚氨酯其耐水性得到明显提高,吸水率降至3%以下.通过扫描电镜(SEM)、腐蚀电位和电化学阻抗谱(EIS)等方法对改性聚氨酯的富锌涂层进行了表征.结果表明,改性水性聚氨酯言锌涂料具有良好的耐蚀性;随着锌粉含量的增加,涂层耐蚀性提高.     

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.     

环氧改性蓖麻油基水性聚氨酯树脂的结构与性能

用蓖麻油（CO）、聚四氢呋喃醚二醇（PTHF）、甲苯二异氰酸酯（TDI）、二羟甲基丙酸（DMPA）、环氧树脂（E—12）合成了水基聚氨酯树脂，去离子水乳化得到蓖麻油交联改性和环氧复合改性的水性聚氨酯乳液。通过拉伸、TG等测试手段表征了乳液的机械性能、热性能及耐化学品性能。结果显示：当蓖麻油的添加量为7．1％，环氧树脂含量为13．7％时，材料的机械性能达到最佳，环氧树脂的引入明显改善了材料的耐水性和耐温性，如耐水性达到120h无异常，耐沸水15min无变化。     

蓖麻油硅氧烷双重交联改善水性聚氨酯的耐水性

以苯酐聚酯多元醇、二羟甲基丙酸和甲苯二异氰酸酯为主要原料,选用蓖麻油及3-氨基丙基三乙氧基硅烷(KH-550)为交联剂,通过预聚物的合成和水相扩链两步反应,制备了水性聚氨酯,研究了蓖麻油和KH-550用量对水性聚氨酯力学性能、附着力和吸水率等的影响.结果表明,当蓖麻油质量分数为10%、KH-550质量分数为1%,经过双...     

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。     

蓖麻油改性的水性聚氨酯涂料的制备及其防蚀性能

以可再生的蓖麻油和环氧树脂改性水性聚氨酯,研究了涂膜的耐水性能等,改性后的水性聚氨酯吸水率下降仅为3%,耐水性好。对该树脂所制成的富锌防腐涂料进行了腐蚀电位和电化学阻抗谱(EIS)的测试分析,考察了富锌涂层在3%NaCl溶液中的电化学行为,结果表明耐水性的提高导致蓖麻油改性的水性聚氨酯富锌涂料耐蚀性的改进。     

氨基硅油微乳液改性水性聚氨酯的合成和性能

合成了水性聚氨酯乳液和氨基硅油(AEAPS)微乳液改性水性聚氨酯乳液,研究了两种水性聚氨酯的性能及在织物上的涂层效果。结果表明,当氨基硅油相对于聚丙二醇的质量百分比为8.18%时,有机硅改性水性聚氨酯乳液的离心稳定性好,乳液胶膜表面硅原子的质量分数为0.92%;该有机硅改性水性聚氨酯软段相与硬段相的微观相分离增大,乳液胶膜的耐水性能和热稳定性提高;该有机硅改性水性聚氨酯乳液作为织物涂层剂时,可以赋予织物柔软、滑爽的风格。     

环氧树脂蓖麻油双重改性水性聚氨酯皮革涂饰剂的合成与性能

以聚氧化丙烯二醇(PPG)和异佛尔酮二异氰酸酯(IPDI)为原料,蓖麻油(CO)和环氧树脂(E-44)为交联剂,采用预聚体分散法合成了一系列用于皮革涂饰的环氧树脂蓖麻油双重改性水性聚氨酯(ECOWPU)。采用FTIR、TEM、DSC、TGA对聚合物结构及膜的性能进行了分析。FTIR表明聚合物中引入了蓖麻油和环氧树脂,羟基和环氧基均参与反应。通过TEM可观察乳液颗粒呈球形,粒径较为均匀。DSC表明,改性后胶膜的微相分离程度增大。TGA表明,环氧树脂和蓖麻油的加入提高了聚氨酯的热稳定性。蓖麻油、E-44含量的增加,均使胶膜拉伸强度逐渐增大,断裂伸长率、吸水率降低。当蓖麻油添加量为4.9%,E-44添加量为7%时,胶膜的综合性能最佳。     

Synthesis and Properties of Waterborne Polyurethane Dispersions with Ions in the Soft Segments

A maleic anhydride modified castor oil (MCO) was used to prepare aqueous polyurethane dispersions (MCPUs) with ionic groups in the soft segments according to the prepolymer mixing process. The aliphatic polyether PU prepolymer was prepared with MCO and polyether glycol (Ng210) as polymeric glycol component. The prepolymer was dispersed under vigorous agitation by adding water and by chain extension with ethylene diamine. The effects of r _m (the mass ratio of MCO and Ng210) on the properties of the resultant waterborne polyurethanes (MCPUs) were studied. Structures and properties of the MCPU dispersions and their films were examined by FT-IR, particle size analyzer, DTG, DSC, WAXD, SEM and tensile tester. The MCPUs exhibit higher phase mixing with increasing of r _m.     

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.     

水性聚氨酯涂料催化剂研究进展

随着环保意识的逐渐加强,水性聚氨酯涂料越来越受到重视.催化剂是水性聚氨酯涂料的重要组成部分.本文综述了水性聚氨酯催化剂(包括胺类催化剂、金属有机化合物类催化剂和复合催化剂等)的研究状况.     

羟基硅油共聚改性水性聚氨酯的制备、表征与性能

引言 水性聚氨酯是一类重要的皮革涂饰剂,它耐磨、柔韧性好,可增加皮革的美观和耐用性.水性聚氨酯链上含有亲水基团,因此形成的涂膜耐水性差,常需要改性.