蓖麻油聚氨酯／聚取代乙烯互穿网络聚合物作为带锈涂料及粘合剂的可能性

在室温用氧化还原引发剂将蓖麻油、甲苯二异氰酸酯及取代乙烯合成了蓖麻油聚氨酯／聚取代乙烯互穿网络聚合物（ＩＰＮ），研究了不同组成对带锈铁板搭接剪切强度的影响。指出搭接剪切强度随取代乙烯均聚物的玻璃化温度增加而增。ＮＣＯ／ＯＨ之比愈大，搭接剪切强度也愈大。以蓖麻油聚氨酯／（丙烯腈－苯乙烯）共聚物的反应液作为带锈铁板的涂料，其涂膜性能良好。用扫描电镜观察了此种涂料与带锈铁板的结合状态，并讨论其成因。     

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。     

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.     

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。     

蓖麻油型聚氨酯IPN的结构与性能研究

本文用蓖麻油,甲苯二异氰酸酯和甲基丙烯酸β-羟乙酯组成的加聚型网络(Ⅰ)和蓖麻油,甲苯二异氰酸酯和聚丙二醇组成的缩聚型聚氨酯(Ⅱ),以同步法形成了一组新型的IPN。用动态力学法和固体核磁共振法研究了它们的结构和性能,形成IPN后,力学数据显示出机械强度的提高,动态力学损耗谱上表现出,tanδ的增宽,固体核磁共振谱计算的结果是界面层的比例增高,但界面层比例并不随配比的改变而变化,它揭示出此IPN可能具有壳核结构。     

两组份互穿网络聚合物的合成研究

以蓖麻油聚氨酯和聚醚聚氨酯的不同重量比与光敏剂、催化剂、稀释剂、促进剂所组成的多相体系为反应物,分别在紫外光照射和加热的条件下合成网络Ⅰ和网络Ⅱ的互穿网络聚合物(IPN)。改变网络Ⅱ聚醚聚氨酯中各组份的摩尔比制得系列样品。红外光谱,应力-应变曲线和动态力学性能测定发现,样品的力学性能与两组份重量比和网络Ⅱ中不同组成都存在着一定关系。这些结果,为该体系IPN的合成和应用提供了一定依据。     

聚氨酯/聚甲基丙烯酸甲酯离子聚合体型互穿聚合物网络生成动力学研究

本文采用在聚氨酯中引入丁基二乙醇胺,形成带有叔氮原子的聚氨酯(NPU)和聚甲基丙烯酸甲酯中引入甲基丙烯酸的方法,合成了带有离子键的离子聚合体型互穿聚合物网络(IPN),动力学研究表明,离子聚合体型IPN形成速率明显低于非离子聚合体型IPN,两网络的聚合速率相互抑制,并随离子键浓度增加而显著,两网络的聚合机理互不干扰。     

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。     

聚二甲基硅氧烷与聚甲基(苯基)硅氧烷嵌段共聚物的分子运动

用振簧法在-150℃至100℃温度范围内测定了聚二甲基硅氧烷和聚甲基(苯基)硅氧烷嵌段共聚物及与其组份相同的共混物的动态力学温度谱。在研究的温度范围内嵌段共聚和共混试样都有两个内耗峰、分别为橡胶相和树脂相的玻璃化转变T_g1和T_g2。嵌段共聚或共混对T_g1和T_g2峰位置的影响较小。用归一化作图法比较了T_g1和T_g2内耗峰的形状,发现嵌段共聚的T_g1峰较共混者宽,而T_g2峰较共混者为窄,并从第二组份对分子运动影响的观点对此现象作了解释。研究了橡胶链段长度对嵌段共聚物T_g1位置和峰形影响的规律。估算出聚二甲基硅氧烷玻璃化转变运动单元的链段长度(Si—O)_n,n大约是80。     

磁性半互穿网络智能水凝胶的合成及性质评价

以甲基丙烯酸(MAA)、N-异丙基丙烯酰胺(NIPAAm)、丙烯酰胺(AM)为原料,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,利用IPN技术并结合磁性的γ-Fe2O3增强剂,在水溶液中制备了半互穿网络水凝胶(PMAA/PAM-NIPAAm/γ-Fe2O3),研究了水凝胶的溶胀性﹑热稳定性和电磁性。实验表明,水凝胶形成稳定的IPN互穿网络结构且该水凝胶具温度、pH双重敏感性和顺电磁性。所合成的水凝胶在低临界溶解温度31℃以下,具有明显正向温敏性,高于此温度,水凝胶的温度敏感性会逐渐减弱。产品成功克服了NIPAAm类水凝胶的温缩性。     

海藻酸钠和聚N-异丙基丙烯酰胺半互穿网络水凝胶的溶胀动力学研究

以海藻酸钠 (SA)和N 异丙基丙烯酰胺 (NIPAM)为原料 ,制备出具有温度敏感性的半互穿网络水凝胶 (SA PNIPAMsemi IPN) .主要研究了海藻酸钠用量、水介质温度及pH值对该凝胶溶胀速率的影响 .结果表明 ,在PNIPAM最低临界溶解温度 (LCST)以下 ,该凝胶的溶胀速率随着凝胶网络中SA组分的增加而增大 ,且溶胀速率取决于高分子链的松弛速率 ;pH对凝胶溶胀速率的影响与温度有关 ,温度对溶胀速率的影响与pH有关 .     

Interpenetrating polymer network (IPN) nanogels based on gelatin and poly(acrylic acid) by inverse miniemulsion technique: synthesis and characterization

Novel interpenetrating polymer network (IPN) nanogels composed of poly(acrylic acid) and gelatin were synthesised by one pot inverse miniemulsion (IME) technique. This is based on the concept of nanoreactor and cross-checked from template polymerization technique. Acrylic acid (AA) monomer stabilized around the gelatin macromolecules in each droplet was polymerized using ammonium persulfate (APS) and tetramethyl ethylene diamine (TEMED) in 1:5 molar ratio and cross-linked with N,N-methylene bisacrylamide (BIS) to form semi-IPN (sIPN) nanogels, which were sequentially cross-linked using glutaraldehyde (Glu) to form IPNs. Span 20, an FDA approved surfactant was employed for the formation of homopolymer, sIPN and IPN nanogels. Formation of stable gelatin-AA droplets were observed at 2% surfactant concentration. Dynamic light scattering (DLS) and scanning electron microscopy (SEM) studies of purified nanogels showed small, spherical IPN nanogels with an average diameter of 255 nm. In contrast, sIPN prepared using the same method gave nanogels of larger size. Fourier-transform infrared (FT-IR) spectroscopy, SEM, DLS, X-ray photoelectron spectroscopy (XPS) and zeta potential studies confirm the interpenetration of the two networks. Leaching of free PAA chains in sIPN upon dialysis against distilled water leads to porous nanogels. The non-uniform surface of IPN nanogels seen in transmission electron microscopy (TEM) images suggests the phase separation of two polymer networks. An increase of N/C ratio from 0.07 to 0.17 (from PAA gel to IPN) and O/C ratio from 0.22 to 0.37 (from gelatin gel to IPN) of the nanogels by XPS measurements showed that both polymer components at the nanogel surface are interpenetrated. These nanogels have tailoring properties in order to use them as high potential drug delivery vehicles for cancer targeting.     

Compatibility and crystallization in poly(ethylene oxide)-poly(methyl methacrylate) semi-interpenetrating polymer network

Differential scanning calorimetry together with dynamic mechanical analysis were employed to investigate the crystallinity and the miscibility in poly(ethylene oxide)/crosslinked poly(methyl methacrylate) semi-IPN (interpenetrating polymer networks). The crystallinity of poly(ethylene oxide) in the semi-IPN is found to depend on the crosslink density of PMMA as well as the overall content of PEO. Of special interest is that an increase in the crosslink density tends to increase the crystallinity contrary to our expectation, indicating crystallization and phase separation may proceed simultaneously during IPN formation. The investigation of glass transition behaviors with dynamic mechanical analysis suggests phase separation (i.e., there exist two amorphous phases: one PEO-rich phase, the other a PMMA-rich phase). © 1993 John Wiley & Sons, Inc.     

P and n dopable semi-interpenetrating polymer networks

Electrochemical oxidation of thin films of 9-(2,3-epoxypropyl)carbazole (OEPC) oligomer deposited on an electrode leads to the formation of an in-situ cross-linked structure with biscarbazyl redox sites due to the anodic coupling of pendant carbazole units. Electrochemical, optical, and thermal characterizations confirm the formation of a conducting network containing electroactive biscarbazolyl units. When the electrochemical cross-linking takes place in a starting thin film containing a mixture of OEPC and a perylene bisimide polymer [poly(Pery-EO₃)], a semi-interpenetrating polymer network is formed which possesses both electron donor and electron acceptor properties. Indeed, the electrochemical behavior of the semi-interpenetrating polymers network (IPN) is characterized by two reversible oxidations and two reversible reduction waves corresponding to the biscarbazolyl and perylene redox moities, respectively. The energy levels of the highest occupied molecular orbital E _HOMO and lowest unoccupied molecular orbital E _LUMO of each donor and acceptor in the semi-IPN have been evaluated and indicate a possible electron transfer from biscarbazole to perylene, which could be taken advantage of in the field of solar cells application.     

PROPERTIES AND MORPHOLOGY OF LIQUID CHLOROPRENE-METHACRYLIC ACID COPOLYMER MODIFIED EPOXY RESIN/POLY (BUTYL METHACRYLATE) SEMI-IPN

A series of liquid chloroprene-methacrylic acid copolymcr (CP--co-MAA) modified epoxy resin (ER)/poly (butyl methacrylate) (PBMA). semi-IPN were synthesized. Some physical properties were investigated. DSC diagrams showed two indistinct and inward endothermal transitions corresponding to the transitions of two networks in the semi-IPN system. By observing morphology with SEM technique it shows that there is a multiphase structure, in which CP-co-MAA's. domain sizes arc about 0.10--0.80μ. With increasing C/E ratio, the domain eizes are getting smaller, which is due to effect of mixing network of CP-co-MAA promoting entanglement and interpenetrating of PBMA and CP-co-MAA-ER network. In most of the semi-IPN's compositions, ER phase readily maintains its phase continuity while PBMA phase presents a band shape structure. Consequently, crosslinking network keeps in its continuous phase more readily than uncrosslinking one, thus it influences dominantly on the physical properties.     

聚(N-异丙基丙烯酰胺)/聚丙烯酰胺无机/有机互穿网络水凝胶的制备及表征

通过紫外引发聚合方法制备了无机交联的聚(N-异丙基丙烯酰胺)(PNIPAAm)/有机交联的聚丙烯酰胺(PAAm)互穿网络(IPN)水凝胶.利用FTIR和SEM分别表征了凝胶的化学结构和内部形态;测定了凝胶在高温(50℃)时的退溶胀性能;利用DMA和DSC分别研究了凝胶的储能模量随温度的变化及热相转变行为.研究表明,该IPN凝胶具有温度敏感性;与未互穿的无机交联PNIPAAm凝胶相比,IPN凝胶具有多孔的网络结构和超快的响应速率,如10min内失去90%的水;其储能模量增加了3～4倍,相转变行为变弱,而最低临界溶解温度(LCST)提高了1.4℃.     

端羟基聚丁二烯型聚氨酯/聚苯乙烯(或聚甲基丙烯酸甲酯)互穿网络的形态和玻璃化转变

The morphology structure and glass transition behavior of polybutadiene-based polyuretha-ne/polystyrene (or polymethyl methacrylate) interpenetrating polymer network (PU(HTPB)/ PSt-IPN, PU(HTPB)/PMMA-IPN) were investigated by TEM and DSC. TEM showed that the phase inversion of PU(HTPB)/PSt-IPN occurred in the concentration of 25% PU(HTPB), and the size of dispersed phase domains of the IPN formed was smaller in the concentration about 50% PU(HTPB). Increasing DVB content or proportion of NCO to OH enhanced in-terpenetration of two components. All of IPN samples exhibited special cellular structure. According to the fact that PU(HTPB) was formed first,a formation mechanism of the struc-ture was proposed.     

端羟基聚丁二烯型聚氨酯/聚苯乙烯(或聚甲基丙烯酸甲酯)互穿网络的形态和玻璃化转变

互穿聚合物网络(IPN'S)已经成为高聚物共混改性,高聚物间相容性的一个重要研究领域,IPN材料的宏观性能与其微观形态有着密切的关系,如能通过改变结构、组成、交联密度及合成条件等因素来控制IPN的形态,则就可以入为地制备各种性能优良的材料。本文用透射电镜和差示扫描量热仪对同步法合成的端羟基聚丁二烯型聚氨