阴离子型水性聚氨酯分散液胶束粒径及形态的研究

用甲苯二异氰酸酯(TDI)、二元醇、扩链剂(extender)通过“二步法”合成了阴离子型水性聚氨酯分散体。动态激光光散射对其胶束直径的测试结果表明,胶束的直径与聚氨酯结构中的二元醇/扩链剂摩尔比有密切的关系,同时也依赖于所用二元醇结构的亲水性。当聚氨酯结构中亲水单元与疏水单元的含量比处于某一数值时,胶束直径最小;亲水单元含量太多时,胶束因为水性介质的溶剂化作用而膨胀,直至成为溶液状态;当疏水性单元含量太多时,胶束因为水性介质的排斥而聚集沉淀。     

含氟两亲接枝共聚物的制备及其与牛血清蛋白作用的研究

用端基反应法合成了对乙烯基苄基的聚乙二醇大分子单体,将该大分子单体与甲基丙烯酸六氟丁酯共聚,合成了一种含氟两亲接枝共聚物.利用1H-NMR1、9F-NMR、GPC对大分子单体和两亲接枝共聚物进行了表征.表面张力法测定了两亲接枝共聚物的临界胶束浓度,发现随着共聚物中含氟链段含量的增加,其临界胶束浓度降低.采用荧光光谱研究了含氟两亲接枝共聚物与牛血清蛋白(BSA)的相互作用,结果表明由于含氟链段疏水力的作用,含氟两亲接枝共聚物能与牛血清蛋白发生相互作用使其荧光增强,随着含氟两亲接枝共聚物浓度和共聚物中含氟链段含量的增加,荧光增强幅度加大.通过透射电子显微镜(TEM)和激光光散射粒度仪(PCS)测试发现,当BSA加入到含氟两亲接枝共聚物的胶束溶液后,所得胶束的粒径和粒径分布变大,共聚物胶束由规整的实心核壳结构变为囊泡状核壳结构.     

聚丙烯酰胺/聚L-谷氨酸苄酯接枝共聚物的合成及其胶束制备

以聚丙烯酰胺(PAM)为大分子引发剂, 采用开环聚合方法, 在N,N-二甲基甲酰胺(DMF)中引发L-谷氨酸苄酯环内酸酐(BLG-NCA)聚合合成了两亲性聚丙烯酰胺/聚L-谷氨酸苄酯接枝共聚物(PAM-g-BLG), 采用IR, 1H NMR和GPC方法对共聚物结构进行了表征; 用芘作荧光探针, 研究了共聚物胶束的形成及其临界胶束浓度(cmc), 利用动态光散射(DLS)和透射电镜(TEM)研究了胶束的粒径分布和形态. 结果表明, PAM能够引发BLG-NCA开环聚合得到接枝共聚物, 在一定条件下接枝共聚物能够形成球形的稳定胶束, cmc值和胶束粒径随着共聚物中疏水性聚L-谷氨酸苄酯(PBLG)链段含量的增加而减小.     

单油酸三羟甲基丙烷酯改性水性聚氨酯

利用单油酸三羟甲基丙烷酯(TMPM)、异佛尔酮二异氰酸酯(IPDI)和聚氧化丙烯(PPG)等制备水性聚氨酯。采用透射电镜(TEM)、动态激光光散射(DLLS)、红外光谱(FT-IR)、热重分析(TGA)和表面张力仪表征了乳液胶束形态、产物结构及性能。结果表明:水性聚氨酯(PU)分子上引入脂肪侧链容易在水中形成规整的胶束,但TMPM改性的水性聚氨酯胶束粒径随TMPM含量的增加不断增大,当w(TMPM)=0.07时,乳液不稳定;脂肪侧链的引入降低了水性聚氨酯乳液的表面张力,表面张力随着反应体系中—NCO和—OH摩尔比的增大而降低,随交联度的增大先增加后减小;TMPM的引入可以提高胶膜的热稳定性。     

星形PLA-PEG嵌段共聚物胶束的制备与表征

以胆酸为引发剂,用辛酸亚锡催化丙交酯开环聚合合成星型CA-PLA。利用DCC为脱水剂,将不同分子量的端羧基化PEG与星型CA-PLA偶联,合成一系列以胆酸为核的星形两亲性嵌段共聚物,用透析法制备共聚物胶束,并用TEM和DLS研究胶束的性质。合成了分子量为6000和12000的两种CA-PLA,其分子量可以通过胆酸羟基与丙交酯的比例进行控制。将分子量2000和5000的PEG分别与两种CA-PLA偶联,合成了四种星型CA-PLA-PEG嵌段共聚物。共聚物胶束形貌为均匀的球形,粒径为20-40nm,且随共聚物中PLA链段分子量的增加而增大,随PEG链段分子量的增加而减小。临界胶束浓度(CMC)低于同等链段长度的线型PLA-PEG嵌段共聚物胶束。     

两亲性树状接枝己内酯共聚物的合成与表征

通过树状接枝聚己内酯的侧羟基及端羟基与氯甲酰化的聚乙二醇进行接枝反应,得到带有亲水性聚乙二醇链段的新型两亲性树状接枝共聚物.1H-NMR分析显示,接枝率为50%左右.GPC分析结果表明,共聚物分子量呈较窄的单峰分布,分子量与接枝前相比明显增高.两亲性共聚物能直接分散在水中形成胶束溶液.以芘为荧光探针的测试结果表明其临界胶束浓度有降低.动态光散射测得胶束平均粒径在16至31 nm之间,粒径分散指数适中,PDI在0.25至0.39之间.TEM显示胶束粒子为不规整球形,由更小的粒径为几个纳米的微粒聚集而成,这些微粒的大小刚好与单个大分子的尺寸相匹配.因此,两亲性树状接枝聚己内酯在水相中存在单分子胶束与多分子组装胶束的平衡.得益于支化聚合物结构中的纳米空腔,两亲性树状接枝聚合物胶束对紫杉醇具有优良的包载能力.     

具有还原刺激响应的聚氨酯胶束的制备和表征

以聚ε-己内酯二元醇(PCL)为软段,赖氨酸二异氰酸酯(LDI)和胱胺(cystamine)为硬段,合成了以胱胺封端的线性聚氨酯预聚体,然后利用α-甲氧基-ω-环氧丙基聚乙二醇(EO-MPEG)的环氧基与胱胺的胺基反应,制备了含有二硫键的双亲性聚氨酯.利用GPC测试了聚氨酯的分子量,1H-NMR及FTIR表征了聚氨酯的结构.利用透析法制备了聚氨酯胶束,荧光探针技术测得其临界胶束浓度为5.6×10-3g/L,TEM分析表明胶束形貌为球形,DLS分析表明胶束的平均粒径为82 nm.还原响应实验表明胶束在10 mmol/L的谷胱甘肽的作用下粒径明显增大,表明胶束具有还原刺激响应特性.最后,以抗肿瘤疏水药物氨甲喋呤(MTX)为模型药物,研究了载药胶束在谷胱甘肽作用下的药物释放,结果表明谷胱甘肽的存在可刺激药物的释放,该材料可作为细胞内还原响应的载体材料使用.     

通过正离子聚合原位制备聚谷氨酸苄酯-g-(聚四氢呋喃-b- 聚异丁烯)/银纳米复合材料及其性能研究

采用烯丙基溴官能化聚异丁烯/高氯酸银体系引发四氢呋喃活性正离子聚合制备聚谷氨酸苄酯-g-(聚四氢呋喃-b-聚异丁烯)/银纳米复合材料(PBLG-g-(PTHF-b-PIB)/Ag).研究接枝密度对该纳米复合材料表面组成、形貌及自组装行为的影响,进一步探究纳米复合材料中银的含量、分布、晶型及存在形态,以布洛芬(IBU)作为模拟药物,研究接枝共聚物中接枝密度和平均支链长度对纳米复合材料载药释药行为的影响,通过抑菌圈法和MTT法研究纳米复合材料的抗菌性和细胞毒性.结果表明:通过烯丙基溴官能化聚异丁烯大分子引发四氢呋喃活性正离子开环聚合,可以原位制备不同接枝密度和不同平均支链长度的PBLG-g-(PTHF-b-PIB)/Ag纳米复合材料,其中银的质量含量在0.25%~3.9%之间,与其理论含量基本相吻合,银颗粒以聚集体形态存在,尺寸为5~10 nm,晶型为面心立方结构;该纳米复合材料在四氢呋喃/正己烷(4/1,V/V)混合介质中自组装形成胶束,胶束数目随接枝密度增加而减少,但尺寸增大;随接枝共聚物中接枝密度和纳米银含量增加,纳米复合材料的疏水性增加;随接枝共聚物中接枝密度增加,纳米复合材料表面形貌可由球形结构逐渐转化为双连续相结构;纳米复合材料的载药微球可以通过接枝共聚物中主链PBLG的空心螺旋结构、酰胺键及PTHF支链的醚键结构显示三重载药特性,载药量和累积释药量均随着接枝共聚物中接枝密度或PTHF链段长度增加而增加,且在37oC下的释药率是25oC下释药率的3倍左右.该纳米复合材料的抗菌性能随纳米银含量增加而增加,当纳米银含量为1.48%时,该纳米复合材料1周后细胞存活率为97.7%,即无细胞毒性.     

含UPy侧链聚氨酯的合成与性能

以二苯基甲烷二异氰酸酯（MDI）和聚四氢呋喃醚二醇（PTMG）合成预聚体,用2-甲基-2-UPy（2-脲-4[H]-嘧啶酮）基-1,3-丙二醇为扩链剂制备了一系列侧链含UPy的聚氨酯。利用FT-IR、1 H-NMR、DMA和力学性能测试等手段对该聚氨酯的结构和性能进行了表征。结果表明：该聚氨酯的力学性能与不含UPy基团的聚氨酯相比有较大的提升;UPy的四重氢键效应形成的物理交联网络结构,使该聚氨酯的玻璃化转变温度随UPy含量的增加向高温方向移动,损耗角正切（tanδ）峰减弱;在宽频的频率场中,随着UPy含量增加,tanδ峰向低频移动,峰强减弱,储能模量增大。     

侧链为光敏感基团的可生物降解聚氨酯的合成及表征

设计合成2-甲基-2-肉桂酰氧甲基-1,3-丙二醇(MCO)作为扩链剂,并以聚乳酸二醇(PLA diol)为软段,异佛尔酮二异氰酸酯(IPDI)和MCO为硬段制备了一系列侧链含有肉桂基团的可生物降解聚氨酯.结果表明MCO具有较高的反应活性,可满足制备高分子量聚氨酯的要求.聚氨酯结构中的肉桂双键可在紫外光和光引发剂的共同作用下,发生快速的交联反应,短时间内形成交联结构.软段结构相同时,凝胶含量随MCO含量的增加而增加.硬段结构相同时,凝胶含量随软段分子量的增加而减少.适度的交联可提高拉伸强度和形变回复率.     

Recent Progress in the Synthesis and Property Enhancement of Waterborne Polyurethane Nanocomposites: Promising and Versatile Macromolecules for Advanced Applications

Abstract

Waterborne polyurethanes (WPUs), owing to their environmental friendliness and non-flammability, are considered as a green class of materials for a wide spectrum of applications, like adhesives, coatings, drug delivery, and tissue engineering. However, to strengthen their thermal stability, water resistance, mechanical properties, and introduce new peculiarities to these polymers, the incorporation of different types of (nano) fillers within their molecular state, emerged novel opportunities and challenges in material sciences. This approach provides new vitality to these materials since the strong interactions between WPU matrices and fillers facilitate the formation of desired WPU composites (WPUCs). Therefore, WPUCs have greatly promoted the construction and designing of novel materials, like hyperbranched WPUs and their nanocomposites. Thus, the aim of the present article is to deeply overview the properties and application of WPUCs in the various realm. The review also provides a brief discussion on the design and synthesis of WPUs, WPUCs, hyperbranched WPUs, and their nanocomposites along with the implementation of naturally derived materials for the development of sustainable WPUCs.     

四甲基苯二甲基二异氰酸酯基水性聚氨酯的合成和性能

采用四甲基苯二甲基二异氰酸酯、聚酯二元醇和二羟甲基丙酸为原料,合成了一系列具有不同异氰酸根与羟基摩尔比（n(-NCO)/n(-OH)）的聚氨酯乳液。 研究了n(-NCO)/n(-OH)对水性聚氨酯性能的影响。 结果表明,当该比值增加时,乳液的粒径增大,分布变宽,结晶性降低,耐热性下降,耐水性能呈现降低的趋势。 当异氰酸根与羟基摩尔比为3时,四甲基苯二甲基二异氰酸酯基水性聚氨酯的乳液粒径为10～30 nm,膜的分解温度达到275 ℃,24 h吸水率低于10%。     

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。     

Synthesis and adhesion property of waterborne polyurethanes with different ionic group contents

In this study, a series of waterborne polyurethanes (WPUs) with different ionic group contents were synthesized by varying the amount of the internal emulsifier 2,2-dimethylolpropionic acid (DMPA). The effects of the ionic group content on the stability and adhesion behavior of WPUs were investigated in terms of particle size, viscosity, surface tension, interfacial tension, contact angle, and adhesion performance. It was found that stable WPUs could be obtained when the DMPA content was larger than 3.5 wt% (with respect to the total solid content). Adhesion performance of WPUs to substrates was mainly affected by the wetting of WPUs on the substrates and the molecular interactions between them. With the increase of DMPA content, the surface tension of WPUs as well as the interfacial tension and contact angle between WPUs and polyethylene terephthalate (PET) films increased. Moreover, the adhesion strength of the WPUs firstly increased and then gradually decreased. The type of debonding failure of all the synthesized WPUs on PET films was cohesion failure due to their lower cohesion strength, which was theoretically testified by the comparison between the adhesion energy and cohesion energy.     

固体变温核磁共振碳谱研究主链型热致液晶聚醚聚氨酯弹性体

固体变温核磁共振碳谱研究主链型热致液晶聚醚聚氨酯弹性体陈群，杨光，王源身（华东师范大学分析测试中心上海２０００６２）余学海（南京大学高分子系南京２１０００８）黑子弘道，安藤勋（日本东京工业大学高分子工学科）关键词主链型热致液晶聚氨酯弹性体，固体变温高...     

Synthesis and properties of silanized waterborne polyurethane/graphene nanocomposites

A series of silanized waterborne polyurethane (WPU)/graphene oxide (GO) chemical hybrids were synthesized from polycaprolactone diol, isophorone diisocyanate, dimethylol butanoic acid, and (3-aminopropyl) triethoxysilane with GO as multifunctional crosslink as well as reinforcing filler. With the addition of GO, dispersion size greatly decreased due to the increased water phase viscosity, while it increased after chain extension reaction due to the migration of GO into the PU particles. The GO covalently bonded to WPU via the sol–gel type reaction augmented contact angle, glass transition temperature (Tg), hardness, and Young’s modulus of the cast film up to 1 %. However, the effects were less pronounced at high content (1.5 %) due to the agglomeration of GO particles.     

WPU预聚体中羧基含量及其位置对树脂的粒径及其耐水性之影响的研究

本文先将马来酸酐与多元醇作用，然后再与其它单体反应，合成了含有羧基的聚氨酯预聚体，并用丁酮稀释后，在普通搅拌条件下使预聚体分散于三乙醇胺的水溶液中，合成出以水为分散介质的聚氨酯分散体系（WPU）。并通过改变羧基在预聚体中的含量和位置，发现随着羧基含量的增加，WPU的粒径减小，而耐水性下降。同时发现，在一定的羧基含量下，同侧羧基相比，端羧基更有利于预聚体的乳化，制得的WPU不仅颗粒较小，而且树脂耐水性明显优于侧基羧预聚体制备的WPU，从而提出羧基的运动自由度是影响羧基乳化活性和树脂耐水性的重要因素。     

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.     

Effect of phase separation on the crystallization of soft segments of green waterborne polyurethanes

Effect of phase separation on the crystallization of soft segments of green waterborne polyurethanes (WPUs) was discussed in this paper. Phase separation was studied through dynamic mechanical analysis and energy dispersive spectrometer. Energy dispersive spectrometer was employed originally for the study of phase separation of polyurethanes in our study. Crystallization of soft segments of green WPUs was characterized by differential scanning calorimetry, X-ray diffraction and polarizing optical microscope. Characterization results indicated that phase separation hindered the crystallization of soft segments of green WPUs; higher phase separation degree gave rise to lower crystallization capacity, lower crystallinity and smaller crystals of soft segments.     

Optical and mechanical properties of polyurethane/surface-modified nanocrystalline cellulose composites

in order to improve the optical and mechanical performances of waterborne polyurethane （WPU）, nanocrystalline cellulose （NCC）/WPU composites were synthesized in this study. NCC （prepared by acid hydrolysis of cotton fiber） was modified by （3-aminopropyl）triethoxysilane （APTES） to enhance its compatibility with WPU, and the surface-modified NCC was characterized by grafting ratio, crystallinity and contact angle （CA）. NCC/WPU composites were examined by scanning electron microscopy （SEM）, X-ray powder diffraction （XRD） and thermogravimetric analysis （TG）. The anti-yellowing property, specular gloss, pencil hardness, and abrasion resistance of NCC/WPU composites were investigated by the methods of Chinese National Standards GB/T 23999-2009, GB/T 9754-2007, GB/T 6739-2006 and GB/T 1768-2006, respectively. The results showed that the grafting ratio of NCC modified by 6% APTES was 36.01% and the crystallinity of modified NCC was decreased with the enhancement of APTES. CA of the modified NCC was decreased by 28.8% and the nanoparticles were homogeneously dispersed in the WPU matrix. The XRD patterns of the NCC/WPU composites were relatively steady, while the thermal stability of the composites was enhanced by 6.7% with 1.0 wt% modified NCC. Modified NCC affected the specular gloss of NCC/WPU composites more obviously than the anti-yellowing property. The pencil hardness of NCC/WPU composites was increased from 2H to 4H by addition of NCC and the abrasion resistance of the composites was enhanced significantly. In general, NCC/WPU composites showed significant improvements in the optical and mechanical performances.