固化剂用量对苯甲基化木材制得的聚氨酯树脂微相分离的影响

以二价酸酯与乙酸丁酯混合溶剂为液化试剂,将苯甲基化木材溶液化,得到的木材溶液与三羟甲基丙烷与甲苯二异氰酸酯的预聚物反应制备聚氨酯树脂。利用FTIR、SEM、DTA、TG及DSC等测试手段,研究了固化剂用量对聚氨酯树脂的微观结构和热性能的影响。结果表明,由于木材结构的特殊性和复杂性,使木材溶液得到的聚氨酯树脂较传统的聚氨酯热稳定性提高,表现在其软段、硬段的初始分解温度比传统的聚氨酯分别提高了 4℃和 99℃;随着w(固化剂)由 23. 8%增大到 69 .9%,树脂的玻璃化转变温度提高,微相分离程度增大,并出现相转变;且相转变完成后,即w(固化剂) =69. 9%时,涂膜各项性能指标发生明显的改善,其铅笔硬度可达 4H,附着力≥1级。     

PEA/PCL型聚氨酯弹性体的性能研究

采用预聚法制备混合软段聚氨酯弹性体,考察了以聚己二酸乙二醇酯二醇(PEA)、聚己内酯二醇(PCL)及不同比例的PEA/PCL混合物为软段得到的聚氨酯材料的力学性能及微相分离。结果表明,与以纯PEA为软段的聚氨酯弹性体相比,以混合软段制备的聚氨酯在保持PEA型聚氨酯力学性能的基础上,其微相分离好于PEA型聚氨酯,同时常温至80℃的储能模量提高。     

UV固化含氟聚氨酯丙烯酸酯的合成及其热稳定性研究

氟碳树脂具有优异的热稳定性,可以改善聚氨酯的耐热性,文章以异佛尔酮二异氰酸酯(IPDI)、聚丙二醇1000(PPG1000)、1,4-丁二醇、含氟丙烯酸酯共聚物二醇和甲基丙烯酸羟乙酯(HEMA)为主要原料合成可UV固化含氟聚氨酯丙烯酸酯预聚体。研究了含氟丙烯酸酯共聚物以及双键单体种类对聚氨酯涂膜热稳定性的影响。结果表明,将含氟丙烯酸酯共聚物引入聚氨酯中,可以显著的提高其热稳定性,同时,降低了聚氨酯硬段与软段的微相分离程度。     

H_(12)MDI聚氨酯弹性体微相分离研究

以4,4′-二环己基甲烷二异氰酸酯(H12MDI)/1,4-丁二醇(BDO)为聚氨酯硬段,分别以聚四氢呋喃醚二醇(PTMEG)、聚己二酸丁二醇酯(PBA)为软段合成了硬段含量(质量分数,下同)为23%～50%的聚氨酯弹性体。借助IR、DSC等分析手段研究了其微相分离结构,并针对所制备弹性体进行力学性能表征。结果表明,硬段含量对H12MDI基弹性体的软段玻璃化温度影响很小;硬段含量的增加,PTMEG型PU的微相分离程度随之先降低后增加,而PBA型PU的微相分离程度则随之降低;以PBA为软段的H12MDI基弹性体在硬段含量为40%时力学性能达到最优。     

PTMG/TDI聚氨酯梯度固化的红外光谱分析

采用梯度温度场固化的方法,制备得到了PTMG/TDI(聚四亚甲基醚二醇/甲苯二异氰酸酯)聚氨酯弹性体,并使用红外光谱对所制备的试样进行了研究分析。研究结果表明:从高温一侧到低温一侧,聚氨酯弹性体的微相分离程度呈现梯度渐变的特点;固化剂的用量、温度梯度、预固化时间以及物料的温度都会直接影响聚氨酯弹性体微相分离程度的梯度。     

微相分离对聚氨酯弹性体耐热性能的影响研究

在聚氨酯弹性体固化过程中添加微相分离促进荆,对不同温度下的热失重分析（TGA）和力学性能高温保持率进行了对比分析,分析表明,添加了微相分离促进剂的聚氨酯弹性体耐热性能得到了提高。     

硬段对聚酯型聚氨酯弹性体微相分离的影响

以聚己二酸-1,4-丁二醇酯二醇(PBA)、4,4′-二苯基甲烷二异氰酸酯(MDI)、乙二醇(EG)、1,4-丁二醇(BDO)和1,6-己二醇(HD)等为主要原料,采用预聚体法制备了一系列热塑性聚氨酯弹性体(TPU)。通过对TPU流变性能、结晶性能、硬度与力学性能的研究,考察了不同扩链剂及不同硬段含量对TPU体系内部微相分离的影响。结果表明,HD-TPU与BDO-TPU微相分离情况相当,均大于EGTPU,且HD-TPU具有较好的结晶性能、拉伸强度及断裂伸长率;随TPU体系硬段含量增加,硬度和拉伸强度增加,断裂伸长率减小,相分离发生越早越快,结晶熔融温度越高,但相分离程度并不高。     

软段对IPDI基透明聚氨酯弹性体微相结构与性能的影响

采用不同结构的软段、扩链剂l,4-丁二醇和异佛尔酮二异氰酸酯(IPDI)为主要原料合成了透明聚氨酯弹性体。研究了软段结构变化对聚氨酯弹性体的微相结构、力学性能、热稳定性及光学透明性的影响。结果表明,相对分子质量高的软段比相对分子质量低的软段更易结晶,耐低温性能更好;与聚氧四亚甲基二醇(PTMG)相比,聚酯型聚己二酸丁二醇酯二醇(PBAG)更易结晶。结晶尺寸在纳米级,材料的透明性可达85％以上。软段含量增加对软段区的结晶影响较小,但力学性能下降明显。混合多元醇的加入进一步提高了聚氨酯弹性体的微相分离程度,有利于软段结晶,在宏观上表现为拉伸强度和弹性模量明显增加。     

一种可用于复合材料电缆支架的新型SMC树脂的制备和研究

以分子量为2 000的聚己二酸丁二醇酯二元醇(PBA)、甲苯二异氰酸酯(TDI)、1,4-丁二醇(BDO)、马来酸酐(MA)和苯乙烯为主要原料,制备了3种可用市售活性氧化镁(Mg O)进行增稠、并制备SMC(Sheet Molding Compound)片材的聚氨酯树脂。通过FT-IR、GPC、DSC、TGA、AFM及万能测试仪对树脂的结构、片材及固化后的制品进行了表征。测试结果表明,合成路线完全可行。随硬段含量和交联密度的增加,片材熔点升高,固化后制品的耐热性能提高,微观上硬段微区由分散相转变为连续相;2~#样品由于硬段含量和交联密度较为适宜,综合力学性能最好。     

热处理对聚氨酯微相分离行为的影响

聚氨酯弹性体是由软段和硬段构成的多嵌段共聚物,区内部通常存在一定程度微相分离。热处理可以对微相分离程度产生明显的影响。选择适当的热处理温度和时间可以改善材料的性能。本文综述了不同的热处理方式、时间对聚氨酯微相分离行为以及氢键的影响。     

微相分离促进剂对MDI型聚氨酯弹性体的耐热性能影响研究

在聚氨酯弹性体固化过程中添加微相分离促进剂,通过差示扫描量热分析（DSC）和动态力学性能测试（DMA）表明,微相分离促进剂的加入提高了4,4′-二苯基甲烷二异氰酸酯（MDI）弹性体的微相分离程度;通过不同温度下的热失重分析（TGA）和力学性能高温保持率对比分析表明,添加了微相分离促进剂的聚氨酯弹性体耐热性能得到了提高。     

Study on microstructure of UV-curable polyurethane acrylate films

UV-curable polyurethane acrylates (UVPUA) were prepared, and Fourier transform infrared (FTIR) was used to monitor the synthesis process and cured films. Effects of soft segment length, isocyanate type, reactive diluent type and level, quenching, annealing and different UV-cured degree on the microstructure of UVPUA films have also been studied. With soft segment length increasing, the degree of hydrogen bonding between soft segment and hard segments decreases, and microphase separation of UVPUA becomes better. Soft segment crystallization appears with its molecular weight exceeding 2000, when its value reaches 4000, an even more obvious melting peak in differential scanning calorimetry (DSC) curve was observed. Congregation of hard segment domains and the improvement of phase separation were due to symmetry and regularity of isocyanate, while rigid benzene ring was beneficial to crystallize and increase the glass transition temperature (T_g). The increased crosslink density with increasing the function degree of diluent resulted in better phase separation, on the contrary, increasing the reactive diluent content led to the opposite because of a phase reversion. Microphase separation lower during quenching and annealing due to post-curing of 1,6-hexa-nediol diacrylate (HDDA) at high temperature, and with the UV-cured degree increasing, the phase separation got better first and then became worse.     

软段结构对聚氨酯弹性体性能的影响

分别以聚四氢呋喃二醇(PTMG)、聚己内酯二醇(PCL)、高顺式端羟基聚丁二烯(HTPB)和自由基聚合制得的端羟基聚丁二烯(FHTPB)为软段,采用溶液聚合两步法制得了四种聚氨酯弹性体(PUE)。通过拉伸试验、动态力学性能分析(DMA)、差示扫描量热(DSC)和热重分析等手段,考察了软段结构对它们室温及低温下力学性能、热性能等的影响。结果表明,四种PUE低温(-30℃)下的拉伸强度和断裂伸长率均大于室温下的对应值。这不仅与低温下软段诱导结晶所产生的自增强效应有关,也与软、硬两段的微相分离程度增大有关。相较于其他三种PUE,HTPB-PUE软段不仅玻璃化温度(T _g)最低,而且极性也最弱,因而微相分离程度高,具有优异的柔性,-30℃下其断裂伸长率仍达660%以上。PCL-PUE和PTMG-PUE因软段易结晶,且软段与硬段的微相分离程度低,则刚性强。低温循环拉伸试验表明,-30℃下HTPB-PUE和FHTPB-PUE有较强的弹性恢复能力,而PCL-PUE和PTMG-PUE则相对较差。DSC和DMA结果显示HTPB-PUE的T _g远低于其他三种PUE,其T _g(DSC)低至-103℃。此外,四种PUE的初始分解温度十分相近,均在270℃左右。     

环氧树脂改性MDI型聚氨酯弹性体的性能研究

采用聚己二酸乙二醇丙二醇酯（PEPA）和4,4’-二苯基甲烷二异氰酸酯（MDI）为原料合成了聚氨酯预聚体,在预聚体固化剂中掺入环氧树脂,制备了环氧树脂改性MDI型聚氨酯弹性体,并对弹性体的结构和性能进行表征。结果表明,环氧树脂改性MDI型聚氨酯弹性体中存在嗯唑烷酮结构,提高了弹性体的热分解温度和耐热性能,但弹性体的动态性能变差,微相分离程度变弱。     

相变材料步冷过程模拟分析

大部分的相变材料都具有一定的过冷度,这限制了相变材料的广泛应用。充分了解相变材料在凝固过程中的温度变化情况对于相变材料性能分析具有重要意义。基于集中参数法和等效比热容法建立了相变材料步冷过程温度变化模型,并通过实验验证了该模型。同时运用模型研究了相变材料过冷度与有效潜热值对其凝固过程中温度变化的影响并得出结论：相变材料开始凝固的时间与相变持续时间均与其过冷度呈指数关系;相变材料开始凝固的时间随着过冷度的增大而增长,相变持续时间随着过冷度的增大而缩短;相变材料开始凝固的时间与其有效潜热大小没有关系,而相变持续时间与其有效潜热值呈明显的线性正比关系。     

Adhesion properties and phase separation behavior of glycidyl-terminated polyurethanes

2,3-Epoxy-1-propanol has been introduced into isocyanate-terminated polyurethane to form glycidyl-terminated polyurethane resins. A series of glycidyl-terminated polyurethanes based on hydroxyterminated poly(oxypropylene) (poly(oxypropylene) glycol, PPG), toluene diisocyanate (TDI), and 1,4-butanediol (BD) was synthesized with various PPG soft segment lengths (MW 700, 1000 and 2000) and soft segment concentrations (30, 50 and 70 wt.-%). The effects of glycidyl-terminated polyurethane on the adhesion properties and the phase separation were investigated. The adhision properties at liquid nitrogen temperature coincide with the phenomenon observed in the phase separation behavior of polyurethane. Differential scanning calorimetry (DSC) and infrared technique (IR) were used to assess the phase separation content. The enthalpy jump at the glass transition temperature (ΔC_p) and the unique spectroscopic features in the N? H and C?O stretching regions were applied to characterized the phase separation behavior. It was found that the modified resins do not only show superior adhesion at liquid nitrogen temperature but also exhibit some unique properties, e.g., room temperature curing and good storage stability.     

Relationship between structure and dynamic mechanical properties of thermoplastic polyurethane elastomer containing bi-soft segment

In this work, we investigated the microphase separation, mechanical, and dynamic mechanical properties of thermoplastic polyurethane elastomers (TPUs) with one-soft segment (polypropylene glycol, PPG, or hydroxyl-terminated polybutadiene, HTPB) or bi-soft segment (PPG and HTPB) using FTIR, XRD, SAXS and amplitude modulated-frequency modulated viscoelastic mode of AFM (AM-FM mode AFM) methods. The results showed that the microphase separation process of hard and soft segments (HS and SS) in TPU containing PPG and HTPB soft segments (PPG-HTPB-PU) was restricted by randomly alternated bi-soft segments, which results in formation of a low content of irregular-shaped hard domain (HD). In addition, the microphase separation of PPG-HTPB-PU induced a triple-phased structure of HD, HTPB rich phase and mesophase. The mesophase of PPG-HTPB-PU was formed of HS, PPG and HTPB segments which were excluded out of HD and HPTB rich domains during microphase separation process. The damping temperature range (at tan δ greater than 0.3) of PPG-HTPB-PU was from −14.6 to 32.1°C (46.5°C) which was more broad than that of TPU containing HTPB soft segment (HTPB-PU). The broad damping temperature range of PPG-HTPB-PU is mainly attributed to the enhanced energy consumption caused by the frictional motions of mixed segments of mesophase.     

Dynamic fluorescence quenching precedent to thermally-induced phase separation of poly(ethoxyethyl vinyl ether) aqueous solution

We focused on the stage preceding the thermally-induced phase separation of aqueous solution of poly(ethoxyethyl vinyl ether) (PEVE). Previously, we observed an interesting dynamic quenching just below the phase separation temperature. The dynamic fluorescence quenching disappeared by addition of a surfactant. In systems without the phase separation of both the hexane solution of PEVE and the PEVE bulk, the fluorescence lifetime decreased monotonically with the increase of temperature. These results indicated that the marked decrease is due to the dynamic quenching by the collision between the fluorescent probe and the PEVE segment induced by the thermal fluctuation precedent to the phase separation.     

粒料法合成聚氨酯分散体及性能的研究

以聚四氢呋喃二醇(PTMG)为软段,异氟尔酮二异氰酸酯(IPDI)和1,4-丁二醇(BDO)为硬段,二羟甲基丙酸(DMPA)为亲水单体,采用粒料法合成了聚氨酯离子聚合物粒料,制备了固含量为40%的聚氨酯分散体(PUD),研究了亲水含量和硬段含量对分散体性能及其胶膜性能的影响。PUD的ζ电位处于30~60 mV,黏度小于1100 mPa s。随着亲水含量增加,平均粒径减小,粒径分布变窄,黏度升高;硬段含量增加,平均粒径增大,粒径分布变宽,黏度降低。透射电镜显示,溶胶粒子呈大小不一的球形结构。PUD胶膜吸水率在3.15%~6.67%。力学性能测试表明硬段含量增加,断裂伸长率降低,拉伸强度增强。DMA测试显示胶膜出现相分离,有硬段和软段两个玻璃化转变温度。随着硬段含量增加,相分离程度提高,软段玻璃化温度降低,硬段玻璃化温度升高。     

Morphology control of segmented polyurethanes by crystallization of hard and soft segments

Segmented polyurethanes (SPUs) have been designed with controlled hard to soft segment ratios. The confinement effect of the SPU blocks is induced by phase separation of the SPU segments and has been harnessed to selectively control crystallization. Hard segment (HS) concentrations greater than 50 wt.% allowed for the study of morphological changes and mechanical properties associated with confinement of the soft segment (SS). It was observed that crystallization temperature and normalized percent crystallinity were reduced with increasing HS content, creating a largely amorphous PEG SS at ambient temperature. High temperature annealing further confined the SS because the HS had more time to crystallize, which increased confinement. Considerable insight has been gained through the manipulation and characterization of the SS and HS, in an SPU, towards the design of impact absorbing and structural materials.