室温固化蓖麻油聚氨酯/乙烯基聚合物互穿网络材料的一些规律及其性能

研究了蓖麻油与甲苯二异氰酸酯及丙烯酸酯或苯乙烯等乙烯基单体在室温下生成的互穿网络聚合物(IPN)的一些规律及其性能.用红外光谱追踪表明,聚氨酯的生成快于甲基丙烯酸甲酯的聚合.研究IPN凝胶点指出.凝胶点时间随聚氨酯含量增加及聚苯乙烯含量减少而缩短.丙烯酸甲酯在生成IPN过程中凝胶的生成速度要比苯乙烯的场合快.丙烯酸丁酯、丙烯腈或丙烯酸甲酯与蓖麻油聚氨酯生成的IPN的抗张强度在聚氨酯占一半时呈现最大值.透射电镜观察表明,生成速率较快的聚氨酯的微区存在于聚丙烯酸甲酯中.聚丙烯酸甲酯与蓖麻油聚氨酯形成的IPN在tanδ-T,曲线上呈现一个宽的玻璃化转变温度.     

蓖麻油聚氨酯和乙烯类聚合物互穿网络材料的生成特点及其动态力学性能

研究蓖麻油聚氨酯/取代乙烯共聚物的互穿网络物(IPN)的生成特点指出,其中取代乙烯游离基共聚的氧化还原引发剂组份-过氧化苯甲酰或二甲基苯胺都能加速聚氨酯网络(Pu)的生成。反应温度在 30℃以上蓖麻油也能参与游离基共聚。蓖麻油不仅与TDI反应生成Pu网络,而且也有小部分参与取代乙烯共聚物长枝链的形成。Pu网络的形成较长枝链的生成为快。生成Pu网络时所放出的热促进取代乙烯与少量蓖麻油的双键共聚,最后生成的IPN不溶于甲苯。这表明生成的是接技的半IPN,而不是单纯的半IPN。动态力学研究指出,包含聚苯乙烯或聚甲基丙烯酸甲酯的这种IPN呈现二个T_g,而只包含聚丙烯腈的仅一个T_g,说明后一IPN中相容性较好,有较多的分子混合。随着聚氨酯与聚取代乙烯的比例减少,二个T_g间的差距减少,而较高温度的T_g随取代乙烯共聚物中丙烯腈含量增加而变小。     

锂/钠离子电池材料的固体核磁共振研究进展

固体核磁共振技术是一种定量分析固体材料结构与组成的强有力手段,结合固体核磁共振和常规x-射线衍射(XRD)、 x-射线吸收谱(XAS)等表征方法可对锂/钠离子电池材料在电化学反应中的结构演化过程进行全面的分析. 例如通过固体核磁共振研究, 可获得不同合成与修饰条件下, 锂/钠离子电池电极和电解质材料体相以及电极/电解质界面层的化学组成、局域结构和离子扩散动力学等信息,为高性能电池材料的设计和研发提供重要的基础数据. 本文结合本课题组的研究工作,综述了近三年来国内外固体核磁共振技术在锂/钠离子电池电极、电解质材料以及固体电解质界面膜（SEI）研究中的应用和进展.     

网间交联型增韧环氧树脂/蓖麻油聚氨酯互穿网络聚合物的动态力学性能和形态结构

以增韧环氧树脂(TEP)和蓖麻油聚氨酯[PU(CO)]形成的互穿网络聚合物(IPN),两网络间具有一定数量的交联点,在一定组成下,该IPN的tanδ-T曲线半峰宽达100℃,tanδ最大值接近1,阻尼性能良好。形态研究表明,该IPN既有增韧环氧树脂本身的两相结构,又有IPN的两相结构。     

网间交联型增韧环氧树脂/蓖麻油聚氨酯互穿网络聚合物的动态力学性能和形态结构

 以增韧环氧树脂(TEP)和蓖麻油聚氨酯[PU(CO)]形成的互穿网络聚合物(IPN),两网络间具有一定数量的交联点,在一定组成下,该IPN的tanδ-T曲线半峰宽达100℃,tanδ最大值接近1,阻尼性能良好。形态研究表明,该IPN既有增韧环氧树脂本身的两相结构,又有IPN的两相结构。     

离子-电子导电中呈现协同效应的互穿网络聚合物

用2,4-甲苯二异氰酸酯将蓖麻油及聚乙二醇(PEG)偶联成聚氨酯,同时通过自由基聚合使2-乙烯基吡啶(VP)与蓖麻油的双键共聚,生成互穿网络聚合物(IPN),其产率及凝胶含量大多超过93%,力学性能很好.当IPN与LiClO₄络合后呈现离子导电现象;与TCNE或TCNQ络合后产生电子导电,与LiClO₄及TCNE(TCNQ)络合后,呈现比上述两种导电率更大且具有协同效应的混合导电率,在25℃混合电导率可达到10^-3～10^-2S/cm.     

蓖麻油聚氨酯／乙烯类聚合物交联共聚物的动态力学性能

本文研究了蓖麻油聚氨酯(COPU)/聚甲基丙烯酸丁酯(PBMA)交联共聚物(简称ABCP)的动态力学性能,并将其与COPU/PBMA,IPN的动态力学性能作了比较。发现在ABCP中两组份的阻尼峰互相叠加,形成半相容体系,而在IPN中阻尼峰有个宽的平台。透射电镜照片表明,IPN具有更大的相区结构。这些结果证明,化学交联比物理缠结具有更大的强迫互容性。通过对COPU/乙烯类聚合物(VP)交联共聚物相容性的研究,可知COPU/PBMA,COPU/PST和COPU/PMMA交联共聚物,在动态力学性能上是半相容体系,而COPU/PMA和COPU/PBA交联共聚物是互容体系。     

纤维素/明胶复合膜的超分子结构与性能

通过一种绿色的方法在NaOH/尿素水体系中制备出纤维素和明胶组成的复合膜(C/G),并且证明这两种大分子间存在强的氢键作用,导致明胶耐水性明显改善.同时,用戊二醛作为交联剂对复合膜化学交联,进一步提高其抗水性.通过红外光谱(FTIR)、紫外光谱(UV-Vis)、13C固体核磁共振谱、扫描电镜(SEM),力学和溶胀测试对...     

聚[丙烯酸甲酯-甲基丙烯酸2-(二甲氨基)乙酯]/环氧树脂IPN力学性能的研究

用同步法合成聚[丙烯酸甲酯-甲基丙烯酸2-(二甲氨基)乙酯]/环氧树脂(P(MA-DMA)/EP)互穿聚合物网络(IPN),对其力学性能进行了研究,结果表明,该体系IPN由于两网络间接枝导致相客性比较好,动态力学谱仅出现一个转变温度,当P(MA-DMA)/EP=20/80时,力学性能显示正协同效应,对环氧树脂的增韧效果最佳,不同组成比的IPNT_g实-T_g计与(d_实-d_计)差值成正比。     

聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物的研究 Ⅴ.互穿缠结对相区结构的稳定作用

用定量的甲苯溶胀聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物(PVAc/PMA IPN),使体系处于分相的热力学条件;或醇解其中的PVAc 网络,即增加两组份的化学不相容性.动态力学谱和透射电镜等结果表明,IPN 和网络Ⅰ的交联密度较高的半 IPN 试样,没有发生进一步的相分离,证明网络互穿缠结是永久性的物理缠结,并且有强迫互容作用的存在.     

紫外光同步固化合成互穿聚合物网络研究

互穿聚合物网络是研制高阻尼材料的理想结构,但从目前国内外文献报道的同步法互穿网络体系来看,由于在制备中采用了两种不同的聚合方法,实际上在形成网络结构的过程中都不是十分理想的同步反应,其反应速度均存在着一定程度的差别。     

Synthesis and characterization of novel environmentally friendly shape memory polyurethanes based on poly(epsilon-caprolactone) diol/castor oil mixtures

A new category of polyurethane plastics (PUs) was obtained from poly (ε-caprolactone) diol/castor oil mixture as a dual-component of their soft segment and hexamethylene diisocyanate (HDI) as the hard segment. The main aim of this study was to explore the effect of castor oil on content chemical structure, dynamic and mechanical properties and low temperature heat induced shape memory of the obtained polyurethane system. The chemical structure of samples was confirmed by Fourier transforms infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. Differential scanning calorimetry (DSC) was carried out to study thermal transitions of synthesized polyurethanes. At 50 mol % of oil, the polyurethane showed the highest enhancement in tensile strength (54%) and Young’s modulus (23%) compared to PU-0. The PU containing 50 mol % of oil was nearly recovered by 99%.     

蓖麻油—甲基丙烯酸甲酯AB交联聚合物的研究

将蓖麻油与顺丁烯二酸酐反应,合成端乙烯基蓖麻油,再与甲基丙烯酸甲酯共聚,制得了组成不同的一系列AB交联聚合物,研究了它们的动态性能、力学性能和形态结构与组成的关系.     

Development of completely bio‐based epoxy networks derived from epoxidized linseed and castor oil cured with citric acid

Bio‐based epoxy resins were synthesized from nonedible resources like linseed oil and castor oil. Both the oils were epoxidized through in situ method and characterized via Fourier transform infrared and ¹H‐NMR. These epoxidized oils were crosslinked with citric acid without using any catalyst and their properties compared with diglycidyl ether of bisphenol A‐epoxy. The tensile strength and modulus of epoxidized linseed oil (ELO) were found to be more than those of epoxidized castor oil (ECO)‐based network. However, elongation at break of ECO was significantly higher than that of both ELO and epoxy, which reveals its improved flexibility and toughened nature. Thermogravimetric analysis revealed that the thermal degradation of ELO‐based network is similar to that of petro‐based epoxy. Dynamic mechanical analysis revealed moderate storage modulus and broader loss tangent curve of bio‐based epoxies confirming superior damping properties. Bioepoxies exhibit nearly similar contact angle as epoxy and display good chemical resistant. The preparation method does not involve the use of any toxic catalyst and more hazardous solvents, thus being eco‐friendly.     

酚氧树脂／蓖麻油交联聚氨酯

使2.2-(4’-羟基苯基)丙烷(双酚A)与环氧氯丙烷反应制得了带端羟基的酚氧树脂(HBA),将其与蓖麻油共混,用2.4-甲苯二异氰酸酯(TDI)作固化剂,制得了一系列交联聚氨酯。DSC和DMA测试结果表明,这种聚氨酯只有一个T_g。改变NCO/OH摩尔比及HBA/(HBA 蓖麻油)比可制得具有较好阻尼性能的聚氨酯材料。     

Room temperature synthesis and mechanical properties of two kinds of elastomeric interpenetrating polymer networks based on castor oil

Two kinds of interpenetrating polymer networks (IPNs) composed of two-component polyurethane (PU) and vinyl or methacrylic polymer (PV), namely, (polyether-castor oil)PU/PV IPN(I) and (polybutadiene-castor oil)PU/PV IPN(II), were synthesized at room temperature using benzoyl peroxide and N,N-dimethylaniline as redox initiator and dibutyltin dilaurate as catalyst. The former IPN was prepared by polymerization of castor oil, NCO-terminated polyether and vinyl or methacrylic monomer together and the latter IPN was obtained by polymerization of castor oil, NCO-terminated polybutadiene, NCO-terminated castor oil and vinyl or methacrylic monomer together. Various synthesis conditions affecting mechanical properties of the two kinds of IPNs were studied. Acrylonitrile (AN) is a good monomer for synthesizing IPN(I), but is a poor monomer for preparing IPN(II). At optimum conditions for the synthesis, both the (polyether-castor oil)PU/PAN IPNs and the (polybutadiene-castor oil)PU/polystyrene (PSt) IPNs possess permanent set about 10%, tensile strength over 13 and 11 MPa and ultimate elongation over 240% and 270%, respectively, thus behaving as elastomers. TEM micrograph of a (polybutadiene-castor oil)PU/PSt IPN showed a microphase separation in the IPN.     

INTERPENETRATING POLYMER NETWORKS BASED ON OIL MODIFIED CASTOR OIL URETHANE AND POLY(METHYL METHACRYLATE)

Castor oil was initially subjected to an interesterification reaction with linseed and tung oils and the resulting intermediate was used for the preparation of polyurethanes and their IPNs with poly(methyl methacrylate). They were characterized for their physico-mechanical, swelling, and thermal properties. The morphologies of IPNs were studied with the aid of scanning electron microscopy and differential scanning calorimetry. On comparing the mechanical properties of castor oil polyurethane (CU) and their IPNs (C-IPNs) with those of the castor oil modified with linseed and tung oil (L-IPN and T-IPN, respectively) it was found that L-IPNs showed higher tensile strength, hardness, and better compatibility than C-IPNs. All IPNs showed synergistic effect in elongation and exhibited similar thermal behavior with no significant change with respect to their composition. However, the castor oil polyurethane and their IPNs showed relatively higher elongation and better resistance to solvents.     

STUDY ON CASTOR OIL POLYURETHANE/POLY (METHYL METHACRYLATE) AB CROSSLINKED POLYMERS

Castor oil polyurethane/poly(methyl methacrylate) AB crosslinked polymers (ABCP) were synthesized by free radical copolymerization of MMA and vinyl-terminated castor oil polyurethane which was obtained from isocyanate-terminated castor oil polyurethane and hydroxyethyl methacrylate The mechanical properties, transition and relaxation, as well as compatibility and morphology of the ABCP were investigated by changing the component. The results show that the ABCP is a semicompatible system and the compatibility of the two components decreases with increasing content of the hard segment. The mechanical and damping properties of the ABCP are obviously superior to that of their homopolymers. The damping value is mainly controlled by cross[ink density of the ABCP but the T-g value by component.     

聚丙烯酸丁酯/蓖麻油聚氨酯半互穿弹性体网络研究

用同步预聚合法合成了聚丙烯酸丁酯/蓖麻油聚氨酯半(SEN),通过拉伸试验、TBA和SEM等手段对其性能和形态进行了表征.结果表明,在一定组分比下半SEN的力学性能协同增加.该半SEN为部份相容体系,具有两相结构,相区尺寸约8000um左右.讨论了形态对性能的影响.     

Synthesis,Characterization and Physicomechanical Properties of Novel Water-based Biodegradable Polyurethane Dispersion

Novel water-based biodegradable polyurethane dispersions with an aim to develop environmentally friendly materials, including medicine, various industries, have been prepared in this study. Biodegradable ionic polyurethanes (IPU) were synthesized based on polyols from renewable resources, such as castor oil (CO), in the presence of a polyester polyol and polyethylene glycol (PEG) with hydrophilic property and 1,6-hexamethylene diisocyanate. 1,4-Butanediol and dibutyltin dilaurate, were used as a chain extender and catalyst, respectively. The comprehensive investigations of the structure and properties of five types of synthesized polyurethanes demonstrated biodegradability relationship of these polyurethanes with their structure and composition. In this research effects of different types and content of polyols on biodegradability and physico mechanical properties of prepared PUDs were investigated. The structure, properties and physico mechanical and application behavior of mentioned materials were characterized by ¹H NMR, FTIR spectroscopy, thermogravimetric analysis (TG/DTG) and dynamic mechanical thermal analysis (DMTA). The adhesion properties were measured by pull off test as well. Particle size was measured by dynamic light scattering (DLS) methods. The biodegradability of prepared polyurethane dispersions was confirmed by water uptake, hydrolytic and enzymatic degradation in phosphate buffer saline (PBS) with lipase enzyme in PBS. Results showed that by the incorporation of natural components into the polymer chain, adjusting of hydrophilic and hydrolytic liability properties of soft segments and especial relevant designs, useful polyurethane can be synthesized with desirable property of biodegradability and dispersion stability. Except for one sample, other samples were decomposed totally in enzymatic media.