功能化石墨烯和有机硅双重改性水性聚氨酯的结构与性能研究

以异佛尔酮二异氰酸酯(IPDI)、功能化石墨烯(IGN)、聚酯二元醇-2000、二羟甲基丙酸(DMPA)、1,4-丁二醇(BDO)为原料,采用石墨烯表面接枝的方法,通过γ-氨丙基三乙氧基硅烷(KH-550)进行封端、三乙胺中和、乳化后得到了IGN和KH-550双重改性的水性聚氨酯乳液(IGN/Si-WPU)。以IGN/Si-WPU为成膜剂,采用平板制膜法制备了IGN/Si-WPU膜,并研究了IGN质量分数和KH-550对水性聚氨酯涂层力学性能的影响。研究结果表明,当w(硅氧烷偶联剂)为3%、w(IGN)为1%时,所制备的双重改性水性聚氨酯比未改性的水性聚氨酯综合性能更加优异。     

高硬度磺酸型水性聚氨酯涂料的合成及性能研究

采用γ-氨丙基三乙氧基硅烷(KH-550)和环氧树脂(E-44)复合改性磺酸型水性聚氨酯,制得硬度高、耐热性和耐化学品性能优异的水性聚氨酯涂料。通过衰减全反射红外分析了聚氨酯的结构,用DSC、TG等对涂膜进行了表征。考察了KH-550及E-44含量对涂膜硬度、耐化学品性及耐热性的影响,结果表明:KH-550和E-44的加入均明显改善了涂膜的硬度和耐化学品性,当KH-550含量为6%~8%,E-44含量8%~10%时,涂膜的综合性能最优。     

蓖麻油/硅烷双重改性水性聚氨酯黏合剂

以聚醚二元醇(N220和N240)和异佛尔酮二异氰酸酯(IPDI)为主要原料,二羟甲基丙酸(DMPA)为亲水扩链剂,三羟甲基丙烷(TMP)、蓖麻油(CO)和有机硅烷(KH-550)为交联剂,合成了CO/KH-550双重改性WPU(水性聚氨酯)黏合剂。探讨了m(N220)∶m(N240)比例、CO和KH-550用量对WPU黏合剂及其涂料印花织物性能的影响。结果表明:当R=n(-NCO)/n(-OH)=1.4、w(CO)=5%、m(N220)∶m(N240)=2∶1和w(KH-550)=4%时,CO/KH-550双重改性WPU黏合剂的耐水性较好,其涂料印花织物的摩擦牢度及皂洗牢度均明显高于未改性WPU,并且织物手感较柔软。     

有机硅/丙烯酸酯改性水性聚氨酯的合成及性能

以异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)、聚酯二元醇(XH-111)、丙烯酸羟乙酯(HEA)和3-氨丙基三乙氧基硅烷(KH-550)等为主要原料,分别制得HEA封端和HEA、KH-550共同封端的水性聚氨酯乳液,再加入丙烯酸酯单体进行自由基引发聚合,分别制备出丙烯酸酯改性和丙烯酸酯、KH-550共同改性的水性聚氨酯复合乳液。通过傅立叶变换红外光谱(FTIR)、热失重分析(TGA)、X射线衍射分析(XRD)和力学性能测试,对改性水性聚氨酯乳液的结构和胶膜的热稳定性、结晶性和力学性能进行了考察。结果表明,改性水性聚氨酯的结晶性降低,热稳定性提高。当w(丙烯酸酯)增大到20%,w(KH-550)增大到15%时,胶膜的拉伸强度由5.6 MPa增加到23.9 MPa,断裂伸长率由491%降到247%。     

湿固化聚氨酯胶黏剂的制备及耐水性研究

为提高湿固化聚氨酯胶黏剂的耐水性,通过蓖麻油和γ-氨丙基三乙氧基硅烷(KH550)双重交联改性,制备了一系列湿固化聚氨酯胶黏剂.研究了蓖麻油及KH550用量对胶黏剂稳定性、耐水性和力学性能的影响.结果表明,当蓖麻油占混合软段的质量分数为30％、添加KH550质量分数为10％时,制备的湿固化聚氨酯胶黏剂可稳定贮存6个月,...     

3-氨丙基三乙氧基硅烷改性水性聚氨酯的制备及性能研究

以聚醚二元醇（N210）、异佛尔酮二异氰酸酯（IPDI）为主要原料,3-氨丙基三乙氧基硅烷（KH-550）为有机硅改性剂,合成了KH-550改性聚氨酯聚合物。考察了KH-550用量对改性聚氨酯弹性体力学性能的影响,并用傅里叶变换红外光谱法对KH-550改性聚氨酯预聚体的结构进行了表征。结果表明改性后的水性聚氨酯分散体稳定性好,膜的手感柔软,吸水性降低,力学性能得到显著改善。     

KH-550改性自消光水性聚氨酯性能及应用

以二羟甲基丙酸(DMPA)与2-[(2-氨乙基)氨基]乙磺酸钠(A95)为亲水扩链剂,聚四亚甲基醚二醇(PTMEG)为软段,异佛尔酮二异氰酸酯(IPDI)为硬段,应用γ-氨丙基三乙氧基硅烷(KH-550)进行封端改性,采用预聚体分散法,制备了水性自消光聚氨酯(WPU)乳液。应用傅里叶变换红外光谱仪、激光粒度仪、接触角测试仪、万能拉力试验机等仪器设备对合成的乳液进行了测试。研究了KH-550改性水性聚氨酯的作用原理;探讨了KH-550对于WPU体系稳定性、耐水性、力学性能的影响。试验发现,KH-550用量为2%时,乳液粒径为3 367 nm,胶膜吸水率约为8.64%,拉伸强度可达32.19 MPa,断裂伸长率可达382%,胶膜的综合力学性能最佳。皮革涂饰是制革的最后一道工序,也是较为关键的工序之一。涂饰质量的好坏直接影响成品革的质量。水性聚氨酯表处剂具有成膜强度高、弹性好、耐候性强、耐磨性好及天然感观优良等特点,近几年成为行业的焦点与热点。将KH-550改性水性聚氨酯乳液应用于PVC人造革表处剂中,可获得不粘着、耐热、耐搓揉、耐干擦、湿擦色牢度优异、触感好、高档的消光效果等综合性能,具有广阔的市场应用前景。     

蓖麻油改性阳离子型水性聚氨酯的合成及性能

采用蓖麻油、异佛尔酮二异氰酸酯、聚己二酸乙二醇酯、聚丙二醇、一缩二乙二醇、N-甲基二乙醇胺、三羟甲基丙烷,合成了一系列蓖麻油改性阳离子型水性聚氨酯分散液.用红外光谱分析、粒径测试、智能电子拉力试验、摆杆硬度测试、热分析等对所合成的聚氨酯的结构、乳液的粒径和膜性能进行测试.结果表明:随着蓖麻油用量的增加,阳离子型水性聚氨酯乳液的粒径逐渐增加,膜的摆杆硬度及耐水性能逐渐增强:蓖麻油在树脂中质量分数达8.4％时,膜的摆杆硬度达到0.86;而蓖麻油在树脂中质量分数达6.4％时,阳离子型水性聚氨酯胶膜浸泡24 h的吸水率几近为零;且蓖麻油的引入,使胶膜的耐热性也有所提高.     

环氧大豆油和硅氧烷改性水性聚氨酯胶黏剂

以环氧大豆油(ESO)与3-氨基丙基三乙氧基硅烷(KH550)双重交联改性水性聚氨酯(WPU).通过FTIR、TG、DSC、DMA、AFM、粒径分析仪、拉力试验机等仪器对改性的水性聚氨酯进行了表征.研究了ESO和KH550的含量对水性聚氨酯乳液、胶膜以及胶黏剂性能的影响.分析了KH550对水性聚氨酯结晶性能和微相分离的影响.研究发现,随着ESO与KH550的加入,水性聚氨酯乳液的性能得到改善,胶膜的吸水率先减小后增大,拉伸强度逐渐增大,断裂伸张率逐渐减小.水性聚氨酯胶黏剂对PVC的T-剥离强度先增大后减小.随着KH550含量的增加,热稳定性逐步改善,结晶性降低,软段与硬段相混合程度提高.当ESO为4%、KH550为2%(均为质量分数)时,水性聚氨酯胶黏剂的综合性能最好.     

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。     

有机硅改性水性聚氨酯乳液的制备及其性能研究

以甲苯二异氰酸酯(TDI)、聚醚二元醇(N-220)、1,4-丁二醇(BDO)、二羟甲基丙酸(DMPA)和硅烷偶联剂(KH-550)等为主要原料,采用丙酮法合成了有机硅改性WPU(水性聚氨酯)乳液。结果表明:KH-550和DMPA的加料方式对WPU乳液稳定性影响较大;当w(DMPA)=3%～5%时,WPU乳液及其胶膜的综合性能较好。     

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。     

无溶剂型双组分有机硅改性PU胶粘剂的制备与性能研究

以聚醚二元醇(DL-1000)、4,4′-二苯基甲烷二异氰酸酯(MDI)为主要原料合成端-NCO基PU(聚氨酯)预聚体;然后以γ-氨丙基三乙氧基硅烷(KH-550)对其进行嵌段共聚改性,并以3,3′-二氯-4,4′-二氨基二苯基甲烷(MOCA)/蓖麻油作为复合固化剂,制备出无溶剂型双组分有机硅改性PU胶粘剂。研究结果表明:硅烷键已引入PU胶粘剂中;随着KH-550含量的不断增加,胶粘剂的黏度增大、固化时间缩短、室温剪切强度下降且耐热性增强;通过调节不同KH-550含量,可制备出不同性能要求的胶粘剂;该胶粘剂的玻璃化转变温度(-45.9℃)相对较低,说明其耐寒性相对较好。     

纳米SiO_2改性水性聚氨酯乳液的制备及性能研究

以硅烷偶联剂(KH-550)作为纳米二氧化硅(nano-SiO2)的表面处理剂,以甲苯二异氰酸酯(TDI)、聚醚二元醇(N-220)、二羟甲基丙酸(DMPA)和nano-SiO2等为主要原料,制备nano-SiO2改性WPU(水性聚氨酯)乳液。着重探讨了DMPA的加料方式、DMPA和nano-SiO2用量等对WPU乳液稳定性、粒径分布、耐水性和力学性能等影响。结果表明:采用先加入DMPA后扩链的加料方式,可制得外观及稳定性均较好的WPU乳液;当w(DMPA)=5%、w(改性nano-SiO2)=2.0%时,WPU乳液及其胶膜的综合性能较好。     

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.     

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。     

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.     

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.