取代基对N—H…O＝C氢键三聚体中氢键强度的影响

使用MP2方法研究了氢键三聚体中N-H…O=C氢键强度,探讨了氢键受体分子中不同取代基对N-H…O=C氢键强度的影响.研究表明,不同取代基对氢键三聚体中N-H…O=C氢键强度的影响是不同的:取代基为供电子基团,氢键键长r(H…O)缩短,氢键强度增强;取代基为吸电子基团,氢键键长r(H…O)伸长,氢键强度减弱.自然键轨道(NBO)分析表明,N-H…O=C氢键强度越强,氢键中氢原子的正电荷越多,氧原子的负电荷越多,质子供体和受体分子间的电荷转移越多.供电子基团使N-H…O=C氢键中氧原子的孤对电子n(O)对N-H的反键轨道σ~*(N-H)的二阶相互作用稳定化能增加,吸电子基团使这种二阶相互作用稳定化能减小.取代基对与其相近的N-H…O=C氢键影响更大.     

大分子不饱和单体法合成具有核壳结构的丙烯酸酯/聚氨酯乳液及表征

采用丙烯酸酯（AC）对水性聚氨酯（WPU）进行改性,合成了接枝型丙烯酸酯/聚氨酯(PUA)复合乳液。 随着共聚物中丙烯酸酯质量分数的增加,乳液外观由透明变为不透明,乳液粒径随之增大、分布变宽。 TEM显示,PUA乳胶粒子呈现清晰的核壳结构,且形态规整,粒径分布在60~120 nm之间。 FTIR测试表明,随着丙烯酸酯质量分数的增加,聚氨酯(PU)硬段氢键化作用先增强后减弱,硬段的有序度逐渐降低。 DSC分析表明,当AC的质量分数低于75%时,PU、聚丙烯酸酯(PA)两组分相容性较好,只出现一个玻璃化转变温度,并且随着PA质量分数的增加逐渐升高。 PA质量分数的增加,使胶膜的最大热失重速率从363 ℃提高至412 ℃,吸水率从11.3%降低至5.7%,弹性模量从16.4 MPa提高至47.6 MPa,拉伸强度从9.0 MPa提高至23.7 MPa,断裂伸长率从365%提高至408%,同时乳液的粘度下降,干燥时间变短,胶膜的附着力变好。     

聚醚氨酯红外N—H伸缩振动谱带分析

通过快速淬火实验,直接观察到聚醚氨酯中由硬段N—H基与软段—O—形成氢键的N—H伸缩振动谱带位于约3295cm~(-1),低于与硬段本身C=O形成氢键的N—H伸缩振动谱带(约3330cm~(-1))。这两种氢键键连的N—H伸缩振动谱带的位置从聚醚氨酯-四氢呋喃溶液的红外光谱得到证实。在此基础上讨论了三种聚醚氨酯试样的红外光谱中N—H伸缩振动谱带的差异。     

生物滤池中生物膜和出水悬浮物的元素分析和红外光谱比较

对生物滤池中不同高度的生物膜和出水悬浮物的碳氢氮三元素和红外光谱进行了分析比较.元素分析结果表明,悬浮物的无机成份比生物膜高.悬浮物和生物膜的红外吸收光谱图主要由蛋白质的吸收带、碳水化合物的吸收带组成.1655 cm-1处的吸收峰为酰胺Ⅰ带,是C=O的伸缩振动,1542 cm-1的吸收峰是酰胺Ⅱ带,是N-H的弯曲振动和C-N的伸缩振动,1240 cm-1是酰胺Ⅲ带,是C-N的伸缩振动和N-H的弯曲振动引起的.1460 cm-1处的吸收峰为CH3和CH2的弯曲振动峰.悬浮物的蛋白质特征峰强度比生物膜低,而1050cm-1处的吸收峰强度比生物膜大.     

环氧改性水性聚氨酯乳液的制备及其膜性能

以聚己内酯二元醇(CAPA)为软段,异佛尔酮二异氰酸酯(IPDI)和六亚甲基二异氰酸酯(HDI)为硬段,环氧树脂E-44为大分子交联剂,经相转化法合成了一系列环氧树脂改性负离子水性聚氨酯(EPPU)自乳化乳液,并制备了改性水性聚氨酯的固化膜.通过FTIR、TGA及接触角、力学性能测试对聚合物结构及其膜性能进行了研究.通过原子力显微镜(AFM)观察膜表面形态和表面粗糙度.乳液粒径及粒径分布通过动态激光光散射法(DLLS)测定.FTIR分析表明环氧树脂的羟基和环氧基都参与了发应.TGA表明,环氧树脂的加入可以提高聚氨酯的热稳定性.随着w(E-44)增大,改性聚氨酯膜的拉伸强度得到改善,断裂伸长率减小.随着w(E-44)增大,乳液粒径增大,薄膜的接触角增大,改性后的PU膜表面光滑度下降,拒水性增强.     

水性聚氨酯结构与胶膜性能的关系

为制备一种性能优异的水性聚氨酯涂层,以聚丙二醇和异佛尔酮二异氰酸酯为主要原料,用本体聚合法制备了水性聚氨酯,考察了结构组元对胶膜性能的影响,并用激光粒度仪、微机控制电子万能试验机和同步热分析仪进行了表征。结果表明:当硬段含量增加时,乳液粒径增大,胶膜拉伸强度增加,吸水率升高;当异氰酸根指数增大时,乳液粒径增大,胶膜拉伸强度增加,吸水率降低;当亲水性扩链剂含量和中和度增大时,乳液粒径减小,胶膜的拉伸强度增加,吸水率升高;在硬段比例为50%、异氰酸酯指数为1.35、亲水性扩链剂含量为5%、中和度为1的条件下,胶膜性能较佳(拉伸强度为16MPa,断裂伸长率为556%,吸水率为6.2%)且在丙酮和甲苯中均表现出溶胀现象。     

高醚化三聚氰胺甲醛树脂交联水性聚氨酯的制备与表征

合成了高醚化三聚氰胺甲醛树脂(HMMM)交联改性含聚乙二醇单甲醚(Ymer N120)亲水基团的阴离子型水性聚氨酯。 通过全反射红外(ATR-FTIR)、差示扫描量热仪(DSC)、电子拉力机等技术手段表征了改性后的水性聚氨酯胶膜结构、热性能和力学性能。 结果表明,随着HMMM质量分数的增加,聚氨酯胶膜中氢键相互作用减弱,胶膜耐热性、耐水性、拉伸强度、粘接性均有所提高;当HMMM为8%时,聚氨酯胶膜的拉伸强度增加了125%,T-型剥离强度增加了7.4 N/cm,硬段最大热分解速率对应温度增加了38 ℃。 此外,交联水性聚氨酯胶膜的耐水性也得到了很大程度的提高。     

盐对甲醇微观结构的影响

利用拉曼光谱研究盐对甲醇微观结构的影响.比较了不同盐/甲醇体系的O—H伸缩谱段和C—O伸缩谱段的超额拉曼光谱,对比给出了阴、阳离子与甲醇的相互作用.O—H伸缩谱段的超额拉曼光谱明显地显示了阴离子与甲醇形成弱氢键,氢键强度排序为CH3OH-CH3OHCl--CH3OHNO3--CH3OHClO4--CH3OH,在这个波段内,基本观察不到阳离子与甲醇的相互作用.在C—O伸缩谱段内,阴阳离子均有显著的体现,且与它们作用的甲醇C—O伸缩振动频率有如下的关系:CH3—OH(阴离子)CH3—OH(体相)CH3—OH(阳离子).根据C—O伸缩谱段的超额拉曼光谱,拟合了该谱段的拉曼光谱,由分解的谱峰强度得到阴、阳离子第一溶剂化层中甲醇分子的数目,结果显示在该浓度(～0.005)下离子对第一溶剂化层以外的甲醇氢键网络结构没有明显影响.     

有机硅蒙脱土复合改性水性聚氨酯的研究

采用插层聚合制备了改性的水性聚氨酯乳液。X射线研究表明,蒙脱土以层间距5．19nm分散在水性聚氨酯基体中。硅烷和蒙脱土改性水性聚氨酯具有性能互补的效果,当有机蒙脱土和有机硅烷的质量分数分别为O．01及O．02时,聚氨酯乳液涂膜的拉伸强度和断裂伸长率比未改性时分别提高了70％、18％,吸水率降低了49％。     

丝素蛋白与聚氨酯共混膜的制备及结构和性能

采用溶液共混法制备了一系列不同组成的聚氨酯/丝素共混膜.利用红外光谱和广角X-射线衍射表征聚氨酯/丝素共混膜的结构;扫描电镜观察共混膜的断面;紫外-可见光谱测定共混膜的透光性;运用拉伸实验研究不同配比聚氨酯/丝素共混膜的力学性能.结果表明聚氨酯和丝素蛋白分子间存在较强的氢键相互作用.当丝素含量低于3 wt%时,试膜的断面较光滑,丝素蛋白分子进入聚氨酯网状结构中,破坏了聚氨酯分子内硬段和软段间的氢键作用.随着丝素含量进一步增大,丝素小颗粒均匀分散在聚氨酯基体中,二者之间具有较好的相容性.本实验所采用的制膜条件有利于促进丝素蛋白大分子的结晶.丝素蛋白对聚氨酯具有良好的增强效果,当丝素含量从0到5.6 wt%变化时,共混试片的断裂强度由0.56 MPa增大到4.60 MPa,杨氏模量由0.14 MPa增大到1.71 MPa,断裂伸长率从1065%下降到988%.丝素蛋白增强聚氨酯共混膜的强度显著增加,但弹性基本保持不变.     

基于CuAAC反应链间自交联有机-无机杂化水性聚氨酯的合成及性能

利用4,4’-二羟甲基-1,4-庚二炔功能单体作为扩链剂合成了一系列炔基接枝量不同的水性聚氨酯（WPU）,然后基于铜催化的叠氮-炔基环加成（CuAAC）反应,采用3-叠氮基丙基三乙氧基硅烷（APTES-N₃）改性炔基功能化WPU,制备了室温链间自交联有机-无机杂化WPU. 采用红外光谱（FTIR）和核磁氢谱（¹H NMR）表征了自交联有机-无机杂化WPU. 探讨了APTES-N₃接枝量对WPU膜性能和WPU乳液形态的影响. 结果表明,随着APTES-N₃含量增加,WPU膜的结晶性逐渐下降;耐水性、耐溶剂性和热稳定性逐渐增强;WPU乳液粒子黏连程度增加. 当APTES-N₃质量分数从0增大到12%时,WPU膜的拉伸强度从14.3 MPa增加到28.6 MPa.     

软段含离子的含氟水性聚氨酯的制备

以单羟基氟碳链一元醇为有机氟改性剂,将含氟基团引入聚氨酯主链中,通过分子设计的方法制备出软段含有离子基团的有机氟阴离子型水性聚氨酯。 比较了传统水性聚氨酯、硬段含氟的水性聚氨酯和软段含氟的水性聚氨酯在合成方法、耐水性、 热稳定性以及结晶性方面的差异;实验证明了软段含氟聚氨酯的水性聚氨酯的性能最为优良。 通过红外光谱的表征确定了氟化聚氨酯的结构,并证明了含氟基团的引入对聚氨酯软硬段间氢键作用的影响;水接触角由73°增加至107°,吸水溶胀率降低了66%,胶膜耐水性提高;热重分析结果表明,含氟聚氨酯的最大热失重温度提高了30 ℃,热稳定性增加;广角X射线衍射结果表明,胶膜的结晶度增加,结晶形式发生了微小程度的转变;扫描电子显微镜结果证明存在不均匀的多相结构。     

Effect of the soft and hard segment composition on the properties of waterborne polyurethane-based solid polymer electrolyte for lithium ion batteries

Journal of Solid State Electrochemistry - A series of waterborne polyurethane (WPU) with various hard segment and soft segment content were synthesized by hexamethylene diisocyanate (HDI),...     

Preparation and characterization of waterborne polyurethane/attapulgite nanocomposites

In this paper, waterbrone polyurethane (WPU)/attapulgite (AT) nanocomposites have been prepared by direct emulsion blending. The WPU was synthesized from poly(tetramethylene glycol), 4,4-diphenylmethane diisocyanate, dimethylol butanic acid, and neutralized by triethylamine. SEM examination of fractured surfaces showed that AT particles were irregularly dispersed in the WPU matrix. FTIR analysis suggested no major chemical structural changed in the presence of a small amount of AT. DMA results showed that the storage modulus of WPU/AT nanocomposites was increased and the glass transition temperatures of both soft and hard segments shifted to higher temperature compared to the pristine WPU. Thermal resistance of the samples measured by TGA was improved with the addition of AT. The mechanical properties of the nanocomposites, examined by tensile tests, showed higher tensile strength and elongation at break than that of the pristine WPU.     

Effect of Molecular Weight of WPU on the Heterogenic PUA Composite Latex Prepared by Soap-Free Emulsion Polymerization

Aqueous acrylic-polyurethane (PUA) composite emulsion was prepared by soap-free seeded emulsion copolymerization. Waterborne polyurethane (WPU) was used as the seeded emulsion and functioned as surfactant. The effect of molecular weight of WPU on the heterogenic was investigated. The molecular weight of WPU was controlled by varying the NCO/OH mole ratio. The GPC results confirmed that the molecular weight of WPU presented double distribution. And the molecular weight of WPU decreased with the increasing NCO/OH mole ratio. Surface tension test indicated that the molecular weight had little influence on the surface activity of WPU. However, after emulsion copolymerization of acrylic monomers, the morphology and properties of the PUA composite were impacted markedly by the molecular weight of WPU. With an increase in the NCO/OH mole ratio, the morphology of PUA composite latex changed from core-shell structures to fish bowl structure, and the mechanical properties of PUA films changed correspondingly.     

Synthesis and thermal properties of antimony doped tin oxide/waterborne polyurethane nanocomposite films as heat insulating materials

The waterborne polyurethane (WPU) was synthesized from the polycondensation between isophorone diisocyanate (IPDI) and polyoxypropylene glycol (N‐210) and then dispersed into water. Subsequently, the WPU emulsion was modified with antimony doped tin oxide (ATO) nanoparticle by ultrasonic dispersion. The ATO/WPU emulsion was cast onto Teflon molds. After being dried, ATO/WPU films were prepared. TEM indicated that the ATO nanoparticles were homogeneously dispersed in the polymer matrix at the nanometer scale. DSC showed that the ATO/WPU nanocomposites displayed increased glass transition temperatures compared to the control WPU. The mechanical properties of the films were characterized by dynamic‐mechanical analysis (DMA). The higher glass transition temperature and storage modulus indicates the superior mechanical properties of WPU modified by ATO nanoparticles over the conventional unmodified WPU. The thermal behaviors of the films were evaluated by thermogravimetric analysis (TGA). It could be found that the incorporation of ATO into WPU can improve the thermal stability dramatically. The results from UV–visible–near infrared spectra indicated that the ATO/WPU films could decrease the infrared transmission effectively. The heat‐insulation measurements showed that glass coated with ATO/WPU films possessed better heat‐insulating effect than empty glass. Copyright © 2010 John Wiley & Sons, Ltd.     

Chemical hybridization of imidized waterborne polyurethane with silica particle

Chemical hybrids of imidized waterborne polyurethane (WPU) with silica nanoparticle were synthesized by UV cure. Imide groups were introduced into the hard segment of UV curable WPU by extending the NCO-terminated prepolymers with pyromellitic dianhydride where chemical hybridization by UV cure was made between the acrylate-terminated polyurethane prepolymer and vinyltrimethoxysilane-silica oligomer. It was found that imidization of WPU and imidized WPU-silica hybrids showed remarkably high mechanical and dynamic mechanical properties at room and elevated temperatures as well as thermal stability.     

纳米氧化锡锑改性水性聚氨酯的制备与表征

以异佛尔酮二异氰酸酯(IPDI)、聚醚二醇（N-210）、二羟甲基丙酸（DMPA）、一缩二乙二醇（DEG）、三羟甲基丙烷（TMP）及纳米氧化锡锑（ATO）浆料为主要原料,制备了稳定的纳米ATO改性水性聚氨酯(APU)乳液。 粒径测试及透射电子显微镜（TEM）观察显示,纳米ATO在水性聚氨酯中分散较好,乳液粒径均小于100 nm; FTIR分析表明,纳米ATO粒子与水性聚氨酯(WPU)间可能存在化学键; 热重分析(TGA)测试显示,随纳米ATO添加量的增加,胶膜最大热分解温度逐渐提高,最大提高了约20 ℃;紫外-可见-近红外吸收及保温性能测试表明,随着纳米ATO添加量的提高,胶膜在800~2500 nm的透过率逐渐降低,但涂层在可见光区透过率均超过70%,热阻率由1.34×10-2 m2·℃/W提高至3.17×10-2 m2·℃/W。     

Self-assembled fabrication and flame-retardant properties of reduced graphene oxide/waterborne polyurethane nanocomposites

The graphite oxide (GO) was prepared from expandable graphite by the pressurized oxidation method, and samples were characterized using XRD, UV–Vis, and TEM. GO is reduced in situ emulsion using hydrazine to achieve reduced graphene oxide/waterborne polyurethane (rGO/WPU) nanocomposites. The effect of rGO content on the stability, fracture morphologies, mechanical performance, thermal degradation, and flame-retardant properties of rGO/WPU composites was investigated by zeta potential analyzer, TEM, SEM, universal testing machine, TG, and Cone Calorimeter. The results of zeta potential, TEM, and SEM analysis indicate that rGO has a good stability and dispersibility in rGO/WPU nanocomposites. The results of mechanical tests showed that the mechanical properties of rGO/WPU nanocomposites increased consistently with increasing rGO content up to 2 mass%, and TG showed that the thermostability of rGO/WPU nanocomposites decreased slightly compared to pure WPU, but carbon residue increased from 0.99 to 1.99 % when the mass fraction of rGO in WPU is 2 %. Cone Calorimeter test indicated that the flame-retardant and smoke suppression properties of rGO/WPU composites showed significant improvement compared to the WPU alone. When the mass fraction of rGO is 1 %, the total smoke release and smoke factor decreased by 25 and 38 %, respectively, compared to those of pure WPU.     

The polyurethane/polyacrylate soap-free emulsion formation: effects of hydrophilic polyurethane

The vinyl group terminated water-borne polyurethanes (WPU) with different DMPA content were prepared. Subsequently the core-shell polyurethane/polyacrylate (PUA) composite emulsions were synthesized by soap-free emulsion copolymerization. The WPU as sole surfactant was used in copolymerization, and the lowest surface tension could be achieved to 38.8?mN m^?1. Furthermore, the final conversion of acrylic monomer was reached to 98% in the case of WPU reactive seed. The FTIR-ATR indirectly confirmed the core-shell structure of PUA, simultaneously combined with DSC results found that the compatibility of WPU and PA was enhanced by growing grafting efficiency. The TEM results further indicated that the amount of DMPA in WPU had a great significant role in polymerization and final morphology structure. The PUA composite particles changed from scattered structure, core-shell structure to multi-core structure with increasing DMPA content. Correspondingly, the reinforcing and toughening effects were also found in PUA films with the increase content of DMPA by tensile testing.