不同硬段含量聚天冬氨酸酯聚脲结构和性能研究

通过聚天冬氨酸酯、端氨基聚醚与脂肪族异氰酸酯六亚甲基二异氰酸酯三聚体/预聚物反应,合成了纯硬段聚脲和不同硬段含量的聚脲,并考察了硬段含量对聚脲的结构形态、动态力学性质和力学性质的影响。硬段含量为73%~50%的聚脲呈现微相分离的形态,随着硬段含量降低,软段和硬段相的混合程度提高,脲羰基的氢键化程度增加,NH基氢键键长增加,硬段玻璃化转变温度Tgh降低,软段玻璃化转变温度Tgs的变化幅度较小,微相分离程度降低。材料的拉伸强度、模量和硬度随着硬段增加而提高,弹性则随之降低。     

乙烯脲改性水性聚氨酯脲的制备与性能

采用一种新型的扩链剂乙烯脲(EU),在聚氨酯硬段引入具有刚性环状二取代脲基团,通过控制脲含量、交联度以及软段相对分子质量来制备一系列的EU改性水性聚氨酯脲(PUU-EU),并利用透射电镜(TEM)、广角X射线衍射(WAXD)、动态力学机械分析(DMA)、热失重分析(TGA)等测试方法,系统地研究PUU-EU微观结构与氢键化程度、微相分离、耐热性、力学强度的关系,并与1,4-丁二醇(BDO)扩链制备的水性聚氨酯(WPU)进行对比。结果表明,在一定范围内,PUU-EU随脲含量增加,其氢键化程度愈发完善,微相分离程度随之增加,力学强度逐步提高。     

聚醚型聚氨酯的氢键、微相分离及性能

用本体一步法合成了5种不同硬段含量(11.0％～46.9％)的二苯甲烷-4,4′-二异氰酸酯/环氧乙烷封端型聚环氧丙烷聚醚/乙二醇的聚醚型聚氨酯,并借助于IR,DSC,DMS和材料试验机等手段对该聚氨酯的氢键、微相分离及力学性能进行了表征。结果表明:随着硬段含量的增加,其>NH与微区中的>C=O的氢键化程度逐渐提高,软段微区中—O—的氢键化程度逐渐降低;微相分离程度逐渐提高;拉伸强度及硬度随之增加,扯断伸长率在硬段含量40％左右出现极大值。     

混合聚醚配比对聚氨酯脲结构和性能的影响研究

以PPG600和PPG2000混合聚醚、异佛尔酮二异氰酸酯（IPDI）和异佛尔酮二胺（IPDA）为原料合成溶剂型聚氨酯脲（Puu）树脂，通过改变PPG600和PPG2000配比调节树脂硬段含量。利用FTIR．DSC．TG等研究PPG600和PPG2000配比对聚氨酯脲微观结构、耐热性及力学性能的影响。结果表明，随着混合聚醚中PPG600含量增加，聚氨酯脲软段的玻璃化转变温度（Tg）升高，软硬段的相容性增强，脲羰基氢键化程度降低，树脂的定伸强度增大。     

硬段含量对脂肪族阴离子水性聚氨酯性能的影响

以异佛尔酮二异氰酸酯和聚酯多元醇为主要原料,用预聚混合法合成了一系列硬段含量不同的脂肪族阴离子水性聚氨酯纳米乳液。通过FTIR、GPC、DSC等,研究了硬段含量对产品结构和性能的影响。结果表明,随着硬段含量增加,乳液平均粒径逐渐增大但仍小于100nm,粒径分布逐渐变宽;分子结构中成氢键的脲键增多;数均相对分子量略有增加;DSC分析表明软段玻璃化温度向低温漂移,而硬段玻璃化温度向高温漂移,说明两相微相分离程度增加。硬段含量为30%时胶膜拉伸强度最高达52MPa,而断裂伸长率随硬段含量增加从2250%急剧减小到863%。耐水性在硬段含量最高时最佳。     

硬段含量对聚氨酯和聚氨酯脲氢键化程度的影响

以PPG600,PPG2000,甲苯二异氰酸酯(TDI)和1,4-丁二醇(1,4-BD)为原料合成了聚氨酯(PU),通过改变PPG600,PPG2000配比调节产品硬段含量;以PPG2000,TDI和异佛尔酮二胺(IPDA)为原料合成了聚氨酯脲(PUU),通过调节TDI与IPDA在体系中的比例调节产品硬段含量。利用FT-IR,DSC,旋转黏度计研究了硬段含量对聚醚型PU和PUU的微观结构及黏度的影响。结果表明,随硬段含量提高,PU和PUU的氢键化程度均提高,PU较多地形成不完善的氢键,而PUU倾向于形成完善有序的氢键结构。此外随硬段含量增大,PU和PUU的黏度增大,PU软段的玻璃化转变温度升高。     

新型聚天门冬氨酸酯聚脲的结构与性能

将聚天门冬氨酸酯(PAE)和端氨基聚醚与脂肪族异氰酸酯4,4′-二环己基甲烷二异氰酸酯预聚物反应,合成了4种新型PAE聚脲。用傅里叶变换红外光谱和差示扫描量热法考察了PAE聚脲的结构形态和热性质。结果表明,PAE聚脲脲羰基的总氢键化程度为69.9%～74.3%,其中较完善氢键化程度占47.8%～63.8%。采用不含侧甲基的PAE、降低软段用量或提高固化温度均可提高氢键化程度。PAE聚脲呈现部分微相分离状态,若采用不含侧甲基的PAE或增加软段含量,则软段和硬段相的混合程度提高。     

MDI异构体对聚氨酯弹性体微观结构和性能的影响

以聚氧化丙烯二醇(DL-2000)为软段,不同2,4′-异构体含量的二苯基甲烷二异氰酸酯(MDI)和1,4-丁二醇(BDO)为硬段,采用预聚法合成了不同异构体含量的MDI型聚氨酯弹性体。采用FT-IR、DSC和DMA等分析手段对其结构和性能进行了表征。结果表明,随着2,4′-MDI异构体含量的增加,硬段间的氢键结合化程度降低,硬段区聚集结晶的能力也不断下降,硬段趋于均匀分散在连续相软段区中,两相相容性增加,聚氨酯弹性体的T和tanδ大幅度提高。     

脂环族阴离子水性聚氨酯分散体的结构及表征

以异佛二酮二异氰酸酯（IPDI）为原料，采用内乳化法合成了不同羧基含量的阴离子水性聚氨酯分散液，利用FT-IR、DSC、TEM、TGA、XRD对其结构进行了表征。结果表明，所合成的水性聚氨酯中氢键主要存在于硬段的亚氨基与硬段的氨酯羰基和脲羰基之间。在-100～220℃的温度范围内出现了2个玻璃化转变，其热分解主要经历了两个阶段。随着羧基质量分数增加，水性聚氨酯硬段与硬段间的氢键增加，软段的玻璃化温度向低温方向移动，硬段的玻璃化温度向高温方向移动，其胶束粒子的平均粒径变小。     

蓖麻油作交联剂的聚氨酯弹性体的合成及性能

以不同摩尔比的四氢呋喃均聚醚（PTMG）和1,6-亚己基二异氰酸酯（HDI）合成聚氨酯（PU）预聚体,再分别用丁二醇（BD）、蓖麻油（CO）以及BD和CO混合物进行扩链交联,合成了一系列不同CO含量的PU.通过FTIR、AFM、拉伸实验和TGA,对不同硬段含量和CO含量PU的氢键化程度、相形态结构、力学性能和热性能进行了比较。结果表明,二异氰酸酯和扩链剂的种类及用量对PU的性能均有很大的影响。随着PU中二异氰酸酯用量的增加,其力学性能和热稳定性能提高。随着扩链剂中CO用量的增加,PU氨酯键的氢键化程度降低,其软、硬段的微相分离程度降低,导致其力学性能降低。但CO用量的增加会提高PU分子链的交联和支化,因而其热稳定性能得到提高。     

Impact of hydrogen bonding on inclusion layer of urea to cellulose: Study of molecular dynamics simulation

Molecular dynamics simulation was applied for investigating the inclusion layer of urea to a single cellulose chain in urea-water solvent mixture. The formation of urea layer surrounding the cellulose chain, which mediated by different patterns of hydrogen bonding, was confirmed by radial distributing function and angular number distribution. Furthermore, the temperature properties of hydrogen bonding revealed that urea molecules are more favorable to interacting with cellulose than water molecules at a certain temperature range. Cellulose-urea interaction energy and hydrogen bond number were also calculated as a function of temperature and the result of calculation further proved the hypothesis that there exists a dominative hydrogen bonding pattern between cellulose and urea, in which oxygen atoms of urea as proton-acceptors and hydroxyl hydrogen atoms of cellulose as proton-donors. The cellulose-urea interaction is dependent of temperature, in which hydrogen bonding between cellulose and urea decreased gradually with temperature increasing at temperature above 265 K and it reached a plateau phase with temperature above 283 K.     

Miscibility and physical properties of conducting poly(urea‐urethane) thermoplastic elastomers

A series of amine‐terminated polyaniline oligomer (OPA)‐based conducting poly(urea‐urethane) thermoplastic elastomers (PUUs) was synthesized by two‐stage solution polymerization and characterized by FTIR. Various percentages of OPA were introduced into PUUs as chain extenders to form hard segments of PUUs with urea‐linkages. Spectroscopic and differential scanning calorimetry, as well as dynamic mechanical analysis, were conducted to elucidate the interaction and degree of miscibility between hard and soft segments, which were related to the stress–strain properties of PUUs. The hydrogen bonding index (HBI) measured by FTIR was employed to show the degree of interchain hydrogen bonding. Copolymer films with higher OPA content exhibit higher HBI and the degree of miscibility is significantly improved. The resultant conducting copolymers have higher tensile strength, higher Young's modulus, and lower elongation at break, because of the long rigid structure of OPA and the increase in the number of hydrogen bonds among the copolymers blocks. Incorporating OPA in PUUs increases the mass of the residue at temperatures over 600°C, according to thermogravimetric analysis. The conductivity of PUUs is found to range from 0.83 S/cm for neat OPA to 6.11 × 10^?5 S/cm for PUUs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3803–3810, 2007     

尿素/甲酰胺增塑PVA的性能研究

采用流延成膜法制备了以尿素/甲酰胺为复配增塑剂改性的聚乙烯醇(PVA)改性薄膜。采用FTIR研究了复配增塑剂尿素/甲酰胺和PVA之间的相互作用,采用XRD、DSC、TGA和拉伸性能测定对改性后的PVA膜性能进行了测试表征。结果表明,尿素/甲酰胺能与PVA形成氢键作用,破坏PVA的结晶结构,降低PVA膜的结晶度。尿素/甲酰胺的加入降低了PVA的熔点,提高了PVA的热分解温度。改性后的PVA膜的拉伸强度降低,断裂伸长率提高。     

NaOH/尿素冷冻活化木材纤维的工艺研究

利用NaOH/尿素混合水溶液在冷冻条件下对木材纤维进行活化处理,通过无胶胶合压制纤维板的力学性能测试、傅里叶变换红外光谱以及X射线衍射分析表征了木材纤维的冷冻活化效果。结果表明：冷冻条件下NaOH/尿素的混合水溶液对木材纤维具有一定的活化效果,优选的活化工艺为NaOH和尿素的总质量（NaOH与尿素质量比为7：12）与木材纤维质量比为1：12,冷冻温度-15℃,冷冻时间1.0 h,木材纤维含水率20%。木材纤维经NaOH/尿素混合水溶液冷冻活化后,所得无胶胶合板材的静曲强度和内结合强度分别由未处理的32.16和0.29 MPa提高至45.53和1.21 MPa,吸水率和厚度膨胀率由未处理的53.95%和22.57%降低至43.62%和10.34%。傅里叶变换红外光谱和X射线衍射表征发现,NaOH/尿素混合水溶液的冷冻活化破坏了木材纤维中纤维素的氢键结构,促使了纤维素I型晶格扩张,产生了新的结晶变体,使分子缔合程度变小,木材纤维表面的羟基活性增强。     

Understanding the influence of hydrogen bonding and diisocyanate symmetry on the morphology and properties of segmented polyurethanes and polyureas: Computational and experimental study

Quantum mechanical calculations (QMC) and dissipative particle dynamics (DPD) simulations were utilized to understand the nature of the short and long-range hydrogen bonding and its influence on the microphase morphology in segmented polyurethanes and segmented polyureas prepared without chain extenders through the stoichiometric reactions of hydroxy or amine terminated poly(tetramethylene oxide) (PTMO-1000) with 1,4-phenylene diisocyanate (PPDI) and 1,3-phenylene diisocyanate (MPDI). The possibility of long-range connectivity due to a network of well-ordered hydrogen bonds between symmetrical PPDI and kinked MPDI based model urethane and urea compounds were also investigated. Special emphasis was given on the understanding of the influence of diisocyanate symmetry and nature of the hydrogen bonding between hard segments on the morphology development. QMC results obtained clearly indicated the possibility of long-range ordering of hydrogen bonds between PPDI based urethane and urea groups, while MPDI based systems did not display such a behavior. DPD results strongly supported the QMC studies and clearly demonstrated the possibility of long-range connectivity of hydrogen bonds between urethane and urea groups in PPDI based segmented copolymers, leading to the formation of microphase separated morphologies in these systems, which was not observed in the kinked MPDI based segmented urethane and urea copolymers. Computational results obtained strongly supported the experimental observations reported on the morphology and thermal and mechanical properties of these segmented polyurethanes and polyureas based on PPDI and MPDI.     

软段分子量对氨纶的微相分离程度与拉伸性能的影响

分别采用分子量为1 400,1 800,2 200,2 600,3 000的不同聚四亚甲基醚二醇和4,4'–二苯基甲烷–二异氰酸酯反应,得到预聚体,用N,N–二甲基乙酰胺作为溶剂配制34.5%的预聚体溶液,后用乙二胺/丙二胺混合物扩链,制成纺丝原液。然后采用溶液干法纺丝得到5种氨纶样品,利用傅立叶变换红外光谱分析仪测试分析了上述样品的氢键化程度,再采用小角X射线系统和动态力学分析仪研究了软段分子量对氨纶的微相分离程度的影响,最后选择万能材料试验机测试其拉伸性能。结果表明:随着软段分子量增加,硬段含量减少,氨纶的氢键化程度、微相分离程度和断裂强力均为先增大后减小,在分子量为2 200时达到最大值;同时,断裂伸长率先减小后增大,在分子量为2 200时为最小值。     

Adsorption of Urea and Thiourea by Wool

The adsorption of urea and thiourea by wool has been measured. Although both compounds rapidly penetrated wool fabric, there was only a small degree of apparent binding by urea. This contrasts with a much higher degree of apparent binding by thiourea, perhaps because of its greater potential for bonding of the van der Waals' type. There is an indication that the concentration of urea in the fibre phase is less than in the bulk solution at urea concentrations greater than 5 M.     

木质素磺酸钠在活性炭/水界面的吸附机理

为了探究木质素磺酸钠在活性炭/水界面的吸附机理,研究了温度、pH 值、无机盐、脲以及直链醇对其吸附动力学及吸附等温线的影响.吸附动力学结果表明,木质素磺酸钠在活性炭/水界面的吸附约在10 min 内快速达到平衡;随着离子强度的增加及脲的加入吸附速率常数增大,pH值增加,吸附速率常数先增大后减小.不同pH值条件下的木质素磺酸钠在活性炭/水界面的吸附等温线符合 Langmuir 方程;随着离子强度增大、脲或直链醇的加入,吸附过程更符合 Freundlich 模型.增加离子强度、降低 pH 值及加入直链醇都可显著提高木质素磺酸钠的平衡吸附量,而脲的加入降低平衡吸附量.在中性条件下木质素磺酸钠主要通过疏水作用和氢键作用吸附在活性炭/水界面,疏水作用有利于加快吸附速率及增加吸附量,该吸附过程不受温度的影响.