蓖麻油TDI聚氨酯互穿网络的热降解

互穿网络聚合物;蓖麻油;聚氨酯;甲苯二异氰酸酯;热降解     

聚氨酯／聚（苯乙烯—甲基丙烯酸甲酯—甲基丙烯酸互穿聚合物网络的研究

研究了聚氨酯／聚互穿合笺网络，动态力学性能及透射电镜结果均表明该体系相分离较严重。ＩＮＰ具有两个玻璃化转变温度，它们有不同程度的内移，形成一定程度分子水平的混合。而ＩＰＮ（５０／５０）其分子混合水平较大，互穿缠结程度较高。     

聚氨酯／聚（苯乙烯－甲基丙烯酸甲酯－甲基丙烯酸）互穿聚合物网络的研究

研究了（蓖麻油－聚乙二醇）聚氨酯／聚（苯乙烯－甲基丙烯酸甲酯－甲基丙烯酸）（ＰＵ／Ｐ（Ｓｔ－ＭＭＡ－ＭＡＡ））互穿聚合物网络（ＩＰＮ）．动态力学性能及透射电镜结果均表明该体系相分离较严重；ＩＰＮ具有两个玻璃化转变温度，它们有不同程度的内移，形成一定程度分子水平的混合，而ＩＰＮ（５０／５０）其分子混合水平较大，互穿缠结程度较高。形成ＩＰＮ后，其力学性能得以改善。透射电镜结果表明，聚氨酯网的交联密度直接影响ＩＰＮ的相区尺寸。形成ＩＰＮ后热稳定性提高，易于降解断链的Ｓｔ－ＭＭＡ－ＭＡＡ单体起到了自由基消除剂的作用。     

不饱和聚酯／聚氨酯互穿网络聚合物的合成

以醋酸酐封端的不饱和聚酯（ＦＵＰＲ）与交联聚氨酯预聚物制备了具有互穿聚合物网络（ＩＰＮ）的不饱和聚酯／聚氨酯，通过红外，ＤＳＣ和扫描电镜等分析了ＦＵＰＲ／ＰＵＩＰＮ网络形成的动力学，微相分离行为及力学性能，结果表明，当ＦＵＰＲ／ＰＵ达到某一比值时，产生网络互穿效应，可改善聚氨酯的刚性，提高不饱和聚酯的抗冲性。     

聚氨酯/乙烯基酯树脂互穿聚合物网络阻尼性能的研究

采用二步法制备了聚氨酯／乙烯基酯树脂互穿聚合物网络,动态力学分析法研究了ＩＰＮ的阻尼性能。结果表明,聚氨酯／乙烯基酯树脂互穿聚合物网络出现宽温度阻尼范围。当聚氨酯／乙烯基酯树脂＝４０／６０时,材料的宽温度范围的阻尼性能最好。在体系中引入柔性链可改善低温阻尼性能,而引入刚性链则降低阻尼值、提高阻尼温度、阻尼温度范围变窄。在体系中引入大侧基能显著提高聚氨酯／乙烯基酯树脂互穿聚合物网络的阻尼性能,提高交     

聚氨酯/环氧树脂互穿网络硬质泡沫塑料反应过程和微观结构

聚氨酯／环氧树脂互穿网络(PU／EPIPN)硬泡中异氰酸根的消耗速度较纯PU硬泡高，是由于环氧树脂的固化荆同时也是异氰酸根反应的催化荆。而PU／EP IPN硬泡中环氧基的反应速度和反应程度均较纯EP网络低，归因于互穿网络对基团扩散的阻碍。在互穿网络硬泡形成过程中，存在环氧开环中所新产生的羟基与异氰酸根的反应、大分子多元醇中羟基与环氧基的反应以及异氰酸根与环氧基形成嗯唑烷酮的反应三种形成网络间的化学键的途径。同时由于PU／EPIPN硬泡高度的交联，使得IPN硬泡中两个网络具有良好的相容性。动态力学性能表明所有IPN样品都只有一个玻璃化温度。透射电镜表明IPN样品无明显的相界面。     

Synthesis and characterization of novel h‐HTBN/PEG PU copolymers for tissue engineering: degradation,phase behavior,and mechanical properties

The phase behavior of the as‐prepared polyether polyurethane (PU) elastomers was investigated by dynamic mechanical analysis (DMA), polarized optical microscope (POM), and atomic force microscopy (AFM). This PU copolymers were composed of different compositions of two soft segments, poly(ethylene glycol) (PEG) and hydrolytically modified hydroxyl‐terminated poly(butadiene‐co‐acrylonitrile) (h‐HTBN) oligomers. The microphase separation behavior is confirmed to occur between soft and hard segments as well as soft and soft segments as the h‐HTBN is incorporated into the PU system, depending on soft‐soft and/or soft‐hard microdomain composition, molecular weight (MW) of PEG, and hydrolysis time of HTBN. The driving force for this phase separation is mainly due to the formation of inter‐ and intramolecular hydrogen bonding interaction. The PU‐70, PU‐50 samples with non‐reciprocal composition seem to exhibit larger microphase separation than any other PU ones. The hydrolysis degradation, thermal stability, and mechanical properties of the copolymers were assessed by gravimetry, scanning electron microscope (SEM), thermal gravity analysis (TGA), and tensile test, respectively. The experimental results indicated that the incorporation of h‐HTBN soft segment into PEG as well as low MW of PEG leads to increased thermal and degradable stability based on the intermolecular hydrogen bond interaction. The PU‐70 and PU‐50 copolymers exhibit better mechanical properties such as high flexibility and high ductility because of their larger microphase separation architecture with the hard domains acting as reinforcing fillers and/or physical crosslinking agents dispersed in the soft segment matrix. Copyright © 2009 John Wiley & Sons, Ltd.     

Interpenetrating Polymer Networks of Uralkyd Resin Based on Hydrogenated Castor Oil and Poly(Butyl Acrylate)

Abstract

Semi‐ and full‐interpenetrating polymer networks (IPNs) of uralkyd (UA) resin based on hydrogenated castor oil and poly(butyl acrylate) (PBA) were prepared by the sequential mode of synthesis. These IPNs were characterized for their resistance to thermal behavior, swelling (%), and mechanical properties. The morphology of the IPNs was studied by scanning electron microscopy (SEM). The effect of the variations of the blend ratios on the above‐mentioned properties was examined. The mechanical properties significantly enhanced by increasing UA component in the blend. Full‐IPNs exhibited higher apparent densities, mechanical properties, and thermal stability than the corresponding semi‐IPNs.     

Mechanical and Morphological Properties of Bio-Phenolic/Epoxy Polymer Blends

Polymer blends is a well-established and suitable method to produced new polymeric materials as compared to synthesis of a new polymer. The combination of two different types of polymers will produce a new and unique material, which has the attribute of both polymers. The aim of this work is to analyze mechanical and morphological properties of bio-phenolic/epoxy polymer blends to find the best formulation for future study. Bio-phenolic/epoxy polymer blends were fabricated using the hand lay-up method at different loading of bio-phenolic (5 wt%, 10 wt%, 15 wt%, 20 wt%, and 25 wt%) in the epoxy matrix whereas neat bio-phenolic and epoxy samples were also fabricated for comparison. Results indicated that mechanical properties were improved for bio-phenolic/epoxy polymer blends compared to neat epoxy and phenolic. In addition, there is no sign of phase separation in polymer blends. The highest tensile, flexural, and impact strength was shown by P-20(biophenolic-20 wt% and Epoxy-80 wt%) whereas P-25 (biophenolic-25 wt% and Epoxy-75 wt%) has the highest tensile and flexural modulus. Based on the finding, it is concluded that P-20 shows better overall mechanical properties among the polymer blends. Based on this finding, the bio-phenolic/epoxy blend with 20 wt% will be used for further study on flax-reinforced bio-phenolic/epoxy polymer blends.     

不同异氰酸酯固化的蓖麻油／酚氧树脂聚氨酯的力学性能

以ＢＦ３·ＯＥｔ２为催化剂，４，４－二羟基二苯基丙烷与环氧氯丙烷反应，生成端羟基的酚氧树脂（Ａ），Ａ与蓖麻油（Ｂ）混合，用３种异氰酸酯（ＴＤＩ、ＩＰＤＩ和ＨＤＩ）作为固化剂，制得交联聚氨酯。研究了这３种聚氨酯的力学性能及形态与组成和二异氰酸酯结构的关系；改变ＮＣＯ／ＯＨ摩尔比及Ｂ与Ａ的质量比，可以制得具有较好力学性能的聚氨酯材料。蓖麻油，酚氧树脂，聚氨酯，力学性能     

The Thermal Degradation Mechanism and Thermal Mechanical Properties of Two High Performance Heterocyclic Polymer Fibers

The thermal mechanical properties and degradation behaviors were studied on fibers prepared from two high-performance, heterocyclic polymers, poly(p-phenylenebenzobisthiazole) (PBZT) and poly(p-phenylenebenzobisoxazole) (PBZO). Our research demonstrated that these two fibers exhibited excellent mechanical properties and outstanding thermal and thermo-oxidative stability. Their long-term mechanical tensile performance at high temperatures was found to be critically associated with the stability of the C—O or C—S linkage at the heterocyclic rings on these polymers' backbones. PBZO fibers with the C—O linkages displayed substantially higher thermal stability compared to PBZT containing C—S linkages. High resolution pyrolysis-gas chromatography/mass spectrometry provided the information of the pyrolyzates' compositions and distributions as well as their relationships with the structures of PBZT and PBZO. Based on the analysis of the compositions and distributions of all pyrolyzates at different temperatures, it was found that the thermal degradation mechanisms for both of these heterocyclic polymers were identical. Kevlar®-49 fibers were also studied under the same experimental conditions in order to make a comparison of thermo-oxidative stability and long-term mechanical performance at high temperatures with PBZO and PBZT fibers. The data of two high-performance aromatic polyimide fibers were also included as references.This revised version was published online in November 2005 with corrections to the Cover Date.     

BaTiO3 / (PU/UP-IPNS)复合材料的相容性、力学性能和阻尼性能研究(英)

以水热法合成的BaTiO3纤维和同步法制备的互穿聚合物网络为原料，采用原位分散聚合法获得了一系列BaTiO3/(PU／UP-IPNs)复合材料。采用傅立叶交换红外分光光度计跟踪考察了IPNs的聚合过程，用透射电镜观测了IPNs及其复合物的形貌。结果表明，IPNs中两相相畴尺寸在纳米级范围内，在此基础上，实现了BaTiO3纤维状的复合。动态力学性能的检测结果表明，相较纯IPNs，复合材料的阻尼损耗模量和阻尼损耗因子值均有所提高，且在低温区均出现了肩峰。复合物的最大损耗因子值均大于0．4，在约50℃范围内，E’值提高100MPa。力学性能检测结果表明，IPNs中的连续相是决定材料力学性能的主要因素；有机／无机组分间混溶性的降低，使BaTiO3/IPNs复合材料的抗张强度和断裂伸长率均下降。     

P(VA-co-DBM)/PVA乳胶IPN阻尼材料的合成及动态力学性能

用种子乳液聚合法合成了聚（醋酸乙烯酯－co-马来酸二丁酯）／聚醋酸乙烯酯乳胶互穿聚合物网络阻尼材料,动态力学谱结果表明,该阻尼材料在较宽的温域具有很高的阻尼因子。     

新型聚合物互穿网络PP／PnBA的合成与表征

采用原位聚合法在聚丙烯微孔膜基材内复合聚丙酸丁酯制备了一种新型聚合物互穿网络ＰＰ／ＰｎＢＡ。用傅立叶扫描红外光谱，偏光显微镜，扫描电镜，Ｘ射线光电子能谱，广角Ｘ射线衍射及力学拉伸等手段进行了表征。发现复合膜表面ＰｎＢＡ的多少依赖于聚丙烯微孔膜基材表面微孔的量及分情况，复合膜基本上保持了聚丙烯微孔膜基材的骨架结构，交联聚丙烯酸了脂填入了几乎全部微孔，成为一个与聚丙烯相互穿的连续相，形成了真正互穿网络     

Simulation of Electrical and Thermal Behavior of Poly(propylene) / Carbon Filler Conductive Polymer Composites

PP-carbon CPC show interesting thermo-electrical properties, smooth resistivity increase with temperature up to 150°C and consequently high power dissipation on a wide temperature range. The addition of short carbon fibers to PP already formulated with carbon black increases sharply the electrical conductivity of the CPC but does not have much influence on thermal conductivity as it could have been expected from the favorable aspect ratio of the fibers. The simulations of the thermo-electrical behavior of the CPC under tension put into evidence a temperature gradient at high heat flux due to the low thermal conductivity, which may damage the material itself.     

交联密度对聚氨酯／聚苯乙烯互穿聚合物网络动态力学性能的影响

采用同步法合成了聚氨酯／聚苯乙烯（ＰＵ／ＰＳ）互穿聚合物网络（ＩＰＮ）．通过改变ＮＣＯ／ＯＨ比、三元醇／二元醇（３ＯＨ／２ＯＨ）比、异氰酸酯类型、多元醇分子量、二乙烯基苯含量及丙烯酸β－羟乙酯的含量，研究了单网及网间交联密度对ＰＵ／ＰＳＩＰＮ动态力学性能影响的规律．结果表明：对相容性差的ＰＵ／ＰＳＩＰＮ体系，采用增加交联密度、加快网络固化速度导致“强迫互容”，能提高两网的互穿与缠结，增进组份的互容．但单网固化速度过快相容性反而下降．     

瓜胶/聚丙烯酸互穿聚合物网络水凝胶对模型药物的负载与控制释放

考察了以牛乳清蛋白(BSA)为模型药物,通过相平衡分配法制备载药瓜胶(GG)/聚丙烯酸(PAA)互穿聚合物网络(IPN)水凝胶的工艺条件.借助紫外可见光谱仪研究了载药水凝胶在结肠酶存在下的控制释放行为.结果表明:载药容量(CM)随瓜胶、丙烯酸用量的增加而下降,半IPN水凝胶的Cm较全IPN的略大;结肠酶能明显提高半IPN与全IPN中的BSA释放速率,且提高幅度随GG含量的增加而加快,GG/PAA IPN水凝胶具有结肠定位降解的特性,有望成为靶向结肠给药的理想载体材料.     

An Investigation into PEO/Crosslinked‐Silicone Semi‐Interpenetrating Polymer Network Using 1H Solid‐State NMR Spectroscopy under Fast MAS

Microstructure and phase behavior of a semi‐interpenetrating polymer network consisting of 10% poly(ethylene oxide) and 90% crosslinked‐silicone have been studied using various ¹H solid‐state NMR methods under fast magic angle spinning in combination with well‐known polymer characterization techniques. Both, ¹H double‐quantum MAS NMR spectroscopy as well as NOESY MAS measurements indicate a mixing of the two components on a molecular level.