UV固化氨基胍盐改性蓖麻油基水性聚氨酯的制备及抗菌性能

以蓖麻油（CO）、异佛尔酮二异氰酸酯(IPDI)、阳离子扩链剂N-甲基二乙醇胺（MDEA）、封端剂甲基丙烯酸羟乙酯（HEMA）为主要原料制备一系列紫外（UV）固化型蓖麻油基水性聚氨酯（UWPU）。为进一步提升其抗菌性能，通过引入胍基的方法，成功制备出抗菌型UV固化蓖麻油基水性聚氨酯(GWPU)。通过耐水性测试、抑菌圈测试、抗菌性能测试对实验制备胶膜性能进行检测。 结果表明：GWPU胶膜相对UWPU吸水率有所上升，但均保持在10%以下；GWPU胶膜抗菌方式为接触性杀菌同时不具有溢出性；当氨基胍盐（AH）质量分数为预聚物1.2%时GWPU对金黄色葡萄球菌(S.aureus)、大肠杆菌(E.coli)的抗菌率可达99.9%，且经过抗菌持久性测试后仍能保持99.9%的抗菌性。     

蓖麻油基双重交联防腐蚀水性聚氨酯的制备及性能

以异佛尔酮二异氰酸酯（IPDI）、聚碳酸酯二醇-1000(PCDL-1000)、蓖麻油（CO）、季戊四醇三丙烯酸酯（PETA）为主要原料，使用丙酮法制备了一系列双重交联的CO基水性聚氨酯（CWPU）乳液。采用FTIR、紫外-可见分光光度计、铅笔硬度计、电子万能实验机、SEM、电化学工作站对CWPU薄膜进行了表征，测试了CWPU薄膜的拉伸性能、耐水性、耐磨性及耐腐蚀性，探讨了其耐腐蚀机理。结果表明，当CO含量（以乳液溶质总质量计，下同）为4%时，制备的薄膜CWPU的24 h吸水率仅为4.5%，对Q235钢板基底的附着力为0级，对Q235钢板基底的保护效率可达99.05%，表明所制CWPU薄膜具有优异的耐水、防腐蚀性能。     

有机硅改性蓖麻油基水性聚氨酯的制备及性能

端羟丙基聚二甲基硅氧烷（HP-PDMS）取代部分多元醇原料蓖麻油,通过预聚体法制得植物油基水性聚氨酯（WPU）。利用醇羟基和异氰酸酯基之间的反应,引入不同含量的HP-PDMS到WPU链段中,制备出WPU/HP-PDMS复合材料。同时利用全反射傅里叶变换红外光谱测试、透射电子显微镜测试、热稳定性测定、静态接触角测试及拉伸测试探讨复合材料的疏水性、热稳定性和拉伸性能的变化。结果表明, HP-PDMS成功改性蓖麻油基WPU;随着HP-PDMS含量的增加,复合材料的初始热分解温度（T5 %）从225 ℃增加到248.5 ℃,同时,少量HP-PDMS的引入可以一定范围内提高材料的疏水性及拉伸强度。     

蓖麻油衍生物水性聚氨酯树脂的合成及性能表征

用蓖麻油制备了蓖麻油衍生物,将蓖麻油衍生物用于合成改性水性聚氨酯。与标准品对比后的结果表明,蓖麻油衍生物能提高水性聚氨酯涂膜的交联密度、模量和拉伸强度,改善涂膜的耐水性和耐溶剂性能。用合成的改性水性聚氨酯树脂制备的涂膜外观好,具有良好的干燥性,能代替溶剂型单组分水性聚氨酯涂料。     

环氧树脂基双组分水性聚氨酯的制备及其在木器涂料中的应用

为提高双组分水性聚氨酯的室温交联速度，将 N-苄基乙醇胺引入到环氧树脂制备了环氧树脂基水性多元醇，表征了多元醇的化学结构，并测定了其相对分子质量、粒径分布和玻璃化温度等主要技术参数。将环氧树脂基水性多元醇与多异氰酸酯配合制备了双组分水性聚氨酯，采用红外光谱法研究了室温交联反应过程。研究结果表明：多元醇分子结构中引入苄胺基加快了双组分水性聚氨酯的交联反应速度。将双组分水性聚氨酯制备成水性木器涂料，漆膜具有优异的耐冲击性、附着力、柔韧性、光泽、耐液体介质、硬度、丰满度等性能。     

荧光水性聚氨酯纸张表面施胶剂的制备及应用

以自制5,7-二羟基-4-甲基香豆素（DHMC）为水性聚氨酯荧光增白改性剂,制备了一系列荧光水性聚氨酯（FWPU）乳液,采用FTIR、¹H NMR、DLS和荧光光谱等对荧光水性聚氨酯进行了结构表征和性能测试。将制备得到的荧光水性聚氨酯应用于纸张表面施胶,研究探讨了荧光水性聚氨酯乳液对纸张表面施胶性能的影响。FTIR、¹H NMR分析表明,DHMC已被引入到FWPU分子链中;当w（DHMC）=0.6%时,FWPU乳液粒径为86.17 nm,荧光强度最强为40220.44 a.u.（1 a.u.=27.2114 eV）。FWPU乳液具有良好的纸张表面施胶性能,纸张施胶度51.92 s,白度77.93%。     

UV固化改性蓖麻油基水性聚氨酯的制备及抗菌性能

以蓖麻油(CO)、异佛尔酮二异氰酸酯(IPDI)、阳离子扩链剂N-甲基二乙醇胺(MDEA)、封端剂甲基丙烯酸羟乙酯(HEMA)为主要原料,制备一系列紫外(UV)固化型蓖麻油基水性聚氨酯(UWPU)乳液.为进一步提升其抗菌性能,通过引入胍基的方法,制备出抗菌型UV固化蓖麻油基水性聚氨酯(GWPU)乳液.通过耐水性、抑菌圈、抗菌性能测试对制得胶膜性能进行了检测.结果表明,GWPU胶膜相对UWPU吸水率有所上升,但均保持在10％以下;GWPU胶膜抗菌方式为接触性杀菌,同时不具有浸出性;当氨基胍盐含量为UWPU胶膜质量的1.2％时,GWPU对金黄色葡萄球菌(S.aureus)、大肠杆菌(E.coli)的抗菌率均可达99.9％,且经过10 d抗菌测试后仍能保持99.9％的抗菌性.     

UV固化改性蓖麻油基水性聚氨酯的制备及抗菌性能

以蓖麻油(CO)、异佛尔酮二异氰酸酯(IPDI)、阳离子扩链剂N-甲基二乙醇胺(MDEA)、封端剂甲基丙烯酸羟乙酯(HEMA)为主要原料,制备一系列紫外(UV)固化型蓖麻油基水性聚氨酯(UWPU)乳液.为进一步提升其抗菌性能,通过引入胍基的方法,制备出抗菌型UV固化蓖麻油基水性聚氨酯(GWPU)乳液.通过耐水性、抑菌圈、抗菌性能测试对制得胶膜性能进行了检测.结果表明,GWPU胶膜相对UWPU吸水率有所上升,但均保持在10％以下;GWPU胶膜抗菌方式为接触性杀菌,同时不具有浸出性;当氨基胍盐含量为UWPU胶膜质量的1.2％时,GWPU对金黄色葡萄球菌(S.aureus)、大肠杆菌(E.coli)的抗菌率均可达99.9％,且经过10 d抗菌测试后仍能保持99.9％的抗菌性.     

UV固化改性蓖麻油基水性聚氨酯的制备及抗菌性能

以蓖麻油(CO)、异佛尔酮二异氰酸酯(IPDI)、阳离子扩链剂N-甲基二乙醇胺(MDEA)、封端剂甲基丙烯酸羟乙酯(HEMA)为主要原料,制备一系列紫外(UV)固化型蓖麻油基水性聚氨酯(UWPU)乳液.为进一步提升其抗菌性能,通过引入胍基的方法,制备出抗菌型UV固化蓖麻油基水性聚氨酯(GWPU)乳液.通过耐水性、抑菌圈、抗菌性能测试对制得胶膜性能进行了检测.结果表明,GWPU胶膜相对UWPU吸水率有所上升,但均保持在10％以下;GWPU胶膜抗菌方式为接触性杀菌,同时不具有浸出性;当氨基胍盐含量为UWPU胶膜质量的1.2％时,GWPU对金黄色葡萄球菌(S.aureus)、大肠杆菌(E.coli)的抗菌率均可达99.9％,且经过10 d抗菌测试后仍能保持99.9％的抗菌性.     

蓖麻油聚氨酯-丙烯酸酯复合乳液的合成

采用甲基丙烯酸甲酯（MMA）与蓖麻油水性聚氨酯乳液共聚反应制备聚氨酯丙烯酸酯（PUA）复合乳液,研究了蓖麻油水性聚氨酯性能、MMA添加量、引发剂种类和聚合温度对PUA复合乳液及涂膜性能的影响,并应用傅里叶红外光谱（FTIR）测定反应产物的结构.研究发现,用外观半透明或微透明的PU-M分散液制备的PUA乳液及涂膜性能优良.油溶性引发剂（AIBN）比水溶性引发剂（K₂S₂O₈）更适合本体系的乳液聚合.随着MMA含量增大,PUA复合乳液胶粒粒径增大,黏度减小,涂膜光泽度下降,机械性能变好,耐水性增加.合适的MMA含量为体系总固含量的20%～30%.提出了PUA复合乳液胶粒形成及粒径长大机理.     

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.     

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.     

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。     

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。     

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.     

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。     

Morphology and mechanical properties of UV-curable castor oil-based waterborne polyurethane/organic montmorillonite nanocomposites

Water resistance is a unique advantage of castor oil-based polyurethane, permitting the application of coatings in humid environments. However, its low thermal decomposition temperature remains a limitation. Here, to demonstrate a simple method to improve the thermal stability of cured films, we prepared an organic montmorillonite dispersion utilising 3-(methacryloyloxy)propyltrimethoxysilane and protonated 3-aminopropyltriethoxysilane for modifying the clay. The method was put into practice by directly mixing the dispersion with a UV-curable castor oil-based waterborne polyurethane dispersion. The inclusion of organic molecule chains from the silane coupling agents noticeably improves the compatibility of polyurethane with organic montmorillonite, which imparts the composite latex with better thermal stability and mechanical properties when the organic montmorillonite additive is 5.0?wt-%.     

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。     

Preparation and properties of modified graphene oxide incorporated waterborne polyurethane acrylate

In this study, a new modifier (KPG) was prepared by modifying graphene oxide with γ‐glycidoxypropyl trimethoxysilane (KH560) and polydimethylsiloxane (PDMS). KPG was in turn added to aqueous urethane acrylate for the fabrication of waterborne polyurethane polyacrylate emulsion modified with KH560‐PDMS composite (KPG/WPUA). Textural characterizations of the KPG/WPUA coating were achieved via Fourier transform infrared, SEM, TGA and AFM techniques, which revealed that the KPG/WPUA film possessed a smooth surface. The synthesized KPG/WPUA films were tested for mechanical properties, hydrophobicity and acid/water corrosion performance which suggested their highly hydrophobic surface. KPG/WPUA with 0.1% KPG showed a contact angle of 118.35°, 30.35° higher than that of pristine WPUA. The KPG/WPUA film exhibited higher thermal stability, i.e. a 5% weight loss temperature of 305 °C, which was 30 °C higher than that of pristine WPUA film. The Young's modulus and elongation at break of the KPG/WPUA film were 34.1 MPa and 74.88% respectively, which were higher than that of WPUA film. Furthermore, KPG/WPUA films exhibited greater resistance (without obvious blistering and the white spotting phenomenon) to H₂O₂, HCl and water corrosion than pristine WPUA. The superior performance of KPG/WPUA films was attributed to the network chain structure formed upon the introduction of KPG into WPUA. The outstanding performance of KPG/WPUA films in terms of mechanical properties, thermal stability and high resistance to acidic and water corrosion makes them interesting alternative contenders for target applications. © 2019 Society of Chemical Industry     

环氧树脂改性水性聚氨酯的制备与性能研究

以异氟尔酮二异氰酸酯(IPDI)、聚四氢呋喃醚二醇(PTMG)以及二羟基甲基丙酸(DMPA)为主要原料合成水性聚氨酯(WPU)预聚体,在此基础上加入环氧树脂(EP,E-44)制备了环氧树脂改性水性聚氨酯(PUE)复合乳液。探讨了不同环氧树脂含量对复合乳液性能的影响,并对胶膜的力学性能、吸水率、接触角和热性能等进行了表征。结果表明,适量的环氧树脂改性过后的复合乳液比较稳定;随着环氧树脂含量的增加,乳液粒径和黏度增大,同时胶膜的拉伸强度增大,水的接触角增大,胶膜的热稳定性增加。E-44质量分数为7%~9%时,复合乳液及其胶膜的综合性能较好。