芳氧基钇配合物催化合成以杯芳烃为核的星形聚己内酯

合成了两种杯芳烃的衍生物(2a,2b),并作为大分子引发剂在三(2,6-二叔丁基-4-甲基-苯氧基)钇[Y(DBMP)3]的催化下,引发己内酯的可控开环聚合,制备了一系列以杯芳烃为核的星形聚己内酯.1H-NMR和SEC研究表明,在一定分子量范围内,以对叔丁基杯[4]芳烃衍生物(2a)为核的星形聚己内酯是四臂且分子量可控的较窄分布星形聚合物,而以对叔丁基杯[6]芳烃衍生物(2b)为核的星形聚己内酯为结构不够明确的星形聚合物.DSC分析表明星形聚己内酯的熔点、结晶温度和结晶度随分子量的增加而增加,且低于相近分子量的线形聚己内酯.POM观察聚己内酯的等温结晶形态,发现星形聚己内酯和相近分子量的线形聚己内酯相比,前者具有不规则的球晶形态和较慢的结晶速度,而后者表现出较快的结晶速度和规则的球晶形态.     

聚ε-己内酯薄膜的受限结晶行为研究

利用原子力显微镜(AFM)系统地研究了聚ε-己内酯(PCL)在物理受限空间,即在薄膜、超薄膜中的结晶行为.结果表明,PCL的结晶形态与薄膜的厚度有关.当薄膜的厚度大于2Rg(Rg为回转半径)时,高分子结晶形态呈现球晶;当厚度介于Rg~2Rg之间时,高分子结晶生成枝蔓或树枝状结构;当厚度小于Rg时,其结晶形态为“岛”状结构.讨论了结晶温度、分子量与基底等对高分子结晶形态的影响.PCL在薄膜中的结晶是一个扩散控制的动力学过程,其生长机理可以用有限扩散凝聚(DLA)来解释.     

AFM研究PCL薄膜的结晶形态

利用原子力显微镜 (AFM)详细研究了聚己内酯 (PCL)超薄膜及其在特殊限制环境下的结晶形态 .AFM的观察表明 ,PCL在石英基板上的结晶形态呈现典型的球晶及比较少见的树枝状晶两种形态 .认为主要是超薄膜结晶过程中由于几何受限及基板吸附导致分子链扩散移动速度大大降低 ,由此形成的扩散控制结晶过程从而导致最终形成树枝状的分形结构 .将聚合物限制在间距为 10 μm的凹槽内 ,发现PCL的结晶有比较规整的排列 ,而且沿着凹槽的方向结晶排列取向优先 .当在凹槽两侧铝条上施加强电场后 ,发现在静电场作用下 ,PCL的结晶取向生长方向发生改变 ,沿着电场方向排列生长的结晶增多     

树枝状嵌段聚合物D-PCL-b-PS在不对称末端受限条件下的结晶行为

研究了树枝状嵌段聚合物聚(ε-b-己内酯)-b-聚苯乙烯(D-PCL-b-PS)的分子结构对PCL链段受限结晶行为的影响.首先,通过活性正离子开环聚合(ROP)合成了树枝状的嵌段聚合物D-PCL.在此基础上用原子转移自由基聚合(ATRP)的方法,合成了树枝状的嵌段聚合物D-PCL-b-PS,在结晶的PCL链段的两个末端...     

非晶高聚物对聚(ε-己内酯)在其与苯乙烯-丙烯腈共聚物相容共混物中球晶生长速率的影响

本文研究了聚(ε-己内酯)(PCL)在其与苯乙烯-丙烯腈共聚物(SAN)的相容共混物中球晶生长速率与共混组成和结晶温度的关系.发现聚己内酯的球晶生长速率随着SAN的含量增加而下降.由于PCL与SAN是相容共混物,因此在用二次成核动力学方程描述PCL球晶生长速率时,我们引进了相互作用参数X.结果由共混体系的结晶动力学方程计算到的X值与由平衡熔点下降方法计算到的X_(23)值是相同的;而PCL晶体的折叠表面自由能则随着SAN含量的增加而下降.这些结果说明非晶高聚物SAN有碍于PCL球晶的生长.     

非晶高聚物对聚(ε-己内酯)在其与苯乙烯-丙烯腈共聚物相容共混物中球晶生长速率的影响

 本文研究了聚(ε-己内酯)(PCL)在其与苯乙烯-丙烯腈共聚物(SAN)的相容共混物中球晶生长速率与共混组成和结晶温度的关系.发现聚己内酯的球晶生长速率随着SAN的含量增加而下降.由于PCL与SAN是相容共混物,因此在用二次成核动力学方程描述PCL球晶生长速率时,我们引进了相互作用参数X.结果由共混体系的结晶动力学方程计算到的X值与由平衡熔点下降方法计算到的X₂₃值是相同的;而PCL晶体的折叠表面自由能则随着SAN含量的增加而下降.这些结果说明非晶高聚物SAN有碍于PCL球晶的生长.     

聚(ε-己内酯)薄膜结晶形貌及分子取向研究

用匀胶机通过溶液铸膜方法在硅片和铝箔基板上分别制备具有不同厚度的聚(ε-己内酯)(PCL)薄膜. 通过原子力显微镜(AFM)和偏光衰减全反射傅里叶红外光谱(ATR-FTIR)对薄膜中PCL的结晶形貌、 片晶生长方式及分子链取向进行了研究. AFM结果表明, 在200 nm或更厚的薄膜中, PCL主要以侧立(edge-on)片晶的方式生长; 对于厚度小于200 nm的薄膜, PCL片晶更倾向于以平躺(flat-on)的方式生长. 这种片晶生长方式的改变在硅片和铝箔基板上都表现出同样的倾向. 此外, 在15 nm或更薄的薄膜中, PCL结晶由通常的球晶结构变为树枝状晶体. 偏光ATR-FTIR结果表明, 当膜厚小于200 nm时, 薄膜结晶中PCL分子链沿垂直于基板表面方向取向, 并且膜越薄, 取向程度越高, 与AFM的观测结果一致.     

聚ε-己内酯/聚氯乙烯球晶表面的XPS研究

聚合物薄膜在微电子领域中的应用日益增加.聚ε-己内酯/聚氯乙烯（PCL/PVC）是研究得最广泛的聚合物共混薄膜之一.PCL与PVC以一定比例混合时,可以形成环带球晶；同时,体系分为结晶PCL相及PCL/PVC非晶混溶相.用XPS和成象XPS分析技术,对PCL/PVC膜的表面化学组成和元素分布情况进行了研究.观察到PCL在薄膜表面富集.此外,成象XPS表明,PVC在球晶边界处富集,且球晶边界宽度约15 μm.     

聚己内酯-聚铵盐抗菌材料的制备

通过开环聚合(ROP)和原子转移自由基聚合(ATRP)制备了一类聚己内酯-聚阳离子酯嵌段共聚物(LPCL-b-PJDMA).聚合物的制备通过四步反应合成:(1)月桂醇引发开环引发ε-己内酯合成LPCL;(2)以2-溴异丁酰溴(BIBB)封端LPCL制备大分子引发剂;(3)用氯乙酸甲酯对甲基丙烯酸二甲氨基乙酯(DMA)进行季铵化反应制备阳离子小分子(命名为JDMA);(4)用五甲基二乙基三胺(PMDETA)/溴化亚铜为催化剂,催化不同链段数的LPCL与JDMA发生ATRP反应制得LPCL-b-PJDMA.通过核磁氢谱(1H-NMR)对聚合物的化学结构进行表征,确认合成目标产物.利用示差扫描量热仪(DSC)对其热性进行研究,并用水接触角的方法测量聚合物膜亲水性,最后通过测试细菌在聚合物膜上的存活率的方法测定其抗菌性能.结果表明,LPCL与PJDMA共聚后,随着PCL重复单元数增加,共聚物结晶温度相对于纯PCL出现明显的先降低后升高趋势.LPCL-b-PJDMA的亲水性都比纯PCL好,且与LPCL/PJDMA的比例有关.所有的LPCL-b-PJDMA膜对革兰氏阴性菌和革兰氏阳性菌都具有抗菌能力.     

三(2,6-二叔丁基-4-甲基苯氧基)镧配合物催化合成星形聚己内酯

分别以三乙醇胺和四乙醇乙二胺为引发剂,用三(2,6-二叔丁基-4-甲基苯氧基)镧(La(DBMP)3)作催化剂,催化ε-己内酯开环聚合,制备了三臂和四臂星形聚己内酯.通过1HNMR表征了聚合物的星形结构以及分子量.研究表明,每一个催化剂分子可与多个引发剂分子作用,当三乙醇胺与La(DBMP)3的摩尔比值为1.7～6.4时,均可制得纯净的三臂星形聚己内酯.通过调节ε-己内酯与多元醇的摩尔比值,可以改变星形聚己内酯的分子量,实现聚合产物分子量可控.     

Influence of hyperbranched against linear architecture on crystallization behavior of poly(ε‐caprolactone)s in binary blends with poly(vinyl chloride)

Nonisothermal and isothermal crystallization behaviors of the hyperbranched poly(ε‐caprolactone) (HPCL)/poly(vinyl chloride) (PVC) and linear poly(ε‐caprolactone) (LPCL)/(PVC) blends were characterized with various blend composition such as 100/0, 95/5, 90/10, and 80/20, respectively. HPCL was synthesized through polycondensation of AB₂ macromonomer while LPCL and PVC were commercially purchased. The architectural characterization performed on ¹H NMR spectra revealed that HPCL consisted of about 3 AB₂ units and the linear segments consisted of 25 ε‐CL units. Through the nonisothermal crystallization analyses by modified Avrami approach with DSC crystallization exotherms, it was found that the crystallization rate was retarded by the increase in the noncrystallizable component (PVC) in the blends. This is in good agreement with the results of the isothermal crystallization analyses where time resolved small angle light scattering (SALS) and polarized optical microscopy (POM) were used. The effect of molecular architectural difference between HPCL and LPCL on the crystallization of their binary blends with PVC was elucidated by comparing the crystallization kinetic parameters. Both the nonisothermal and isothermal crystallization analyses showed that the crystallization rates of HPCL/PVC blends was faster than LPCL/PVC blends at given blend compositions. The faster crystallization of the HPCL/PVC blends is ascribed to the two specific architectural characteristics of HPCL; the branched structure and the incorporated long linear segments. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 577–589, 2007     

IN SITU OBSERVATION OF MELTING AND CRYSTALLIZATION BEHAVIORS OF POLY(ε-CAPROLACTONE) ULTRA-THIN FILMS BY AFM TECHNIQUE

The melting and crystallization behaviors of poly(ε-caprolactone) (PCL) ultra-thin films with thickness from 15 nm to 8 nm were studied by AFM technique equipped with a hot-stage in real-time. It was found that melting can erase the spherulitic structure for polymer film with high thickness. However, annealing above the melting point can not completely erase the tree-like structure for the thinner polymer film. Generally, the structure formation of thin polymer films of PCL is controlled not only by melting and crystallization but also by dewetting during thermal annealing procedures, and dewetting predominates in the structure formation of ultra-thin films. However, the presence of tree-like morphology at 75 °C may be due to the strong interaction between PCL and mica surface, which may stick the PCL chains onto the mica surface during thermal annealing process. Moreover, the growth of the dendrites was investigated and it was found that crystallization is followed from a dewetted sample, and the branches did not grow with the stems. The crystallization of polymer in the ultra-thin films is a diffusion-controlled process. Both melting and crystallization behaviors of PCL in thin films are influenced by film thickness.     

Effect of film thickness on morphological evolution in dewetting and crystallization of polystyrene/poly(ε-caprolactone) blend films

In this Article, the morphological evolution in the blend thin film of polystyrene (PS)/poly(ε-caprolactone) (PCL) was investigated via mainly AFM. It was found that an enriched two-layer structure with PS at the upper layer and PCL at the bottom layer was formed during spinning coating. By changing the solution concentration, different kinds of crystal morphologies, such as finger-like, dendritic, and spherulitic-like, could be obtained at the bottom PCL layer. These different initial states led to the morphological evolution processes to be quite different from each other, so the phase separation, dewetting, and crystalline morphology of PS/PCL blend films as a function of time were studied. It was interesting to find that the morphological evolution of PS at the upper layer was largely dependent on the film thickness. For the ultrathin (15 nm) blend film, a liquid-solid/liquid-liquid dewetting-wetting process was observed, forming ribbons that rupture into discrete circular PS islands on voronoi finger-like PCL crystal. For the thick (30 nm) blend film, the liquid-liquid dewetting of the upper PS layer from the underlying adsorbed PCL layer was found, forming interconnected rim structures that rupture into discrete circular PS islands embedded in the single lamellar PCL dendritic crystal due to Rayleigh instability. For the thicker (60 nm) blend film, a two-step liquid-liquid dewetting process with regular holes decorated with dendritic PCL crystal at early annealing stage and small holes decorated with spherulite-like PCL crystal among the early dewetting holes at later annealing stage was observed. The mechanism of this unusual morphological evolution process was discussed on the basis of the entropy effect and annealing-induced phase separation.     

Crystalline morphology evolution in PCL thin films

The transition of crystalline morphology is revealed in poly(?‐caprolactone) (PCL) thin films as the polymer film thickness changes from hundreds of nanometers to several nanometers. The PCL can crystallize into spherulites, dense‐branching morphology (DBM), or dendrites, depending on the polymer film thickness. It was found that when the polymer film thickness approaches 2Rg (radius of gyration of polymer), there is a remarkable change in crystalline morphology. Under this condition, the polymer crystallization is a diffusion‐controlled process. When the value of polymer film thickness closes to Rg, PCL cannot crystallize, and a dewetting phenomenon will take place. Moreover, polymer morphology can be controlled by varying supercooling. The effect of molecular weight on polymer morphology has been investigated. The main factors that affected pattern formation in nonequilibrium crystallization are also discussed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1303–1309, 2005     

Surface phase separation, dewetting feature size, and crystal morphology in thin films of polystyrene/poly(ε-caprolactone) blend

Thin films of polystyrene (PS)/poly(ε-caprolactone) (PCL) blends were prepared by spin-coating and characterized by tapping mode force microscopy (AFM). Effects of the relative concentration of PS in polymer solution on the surface phase separation and dewetting feature size of the blend films were systematically studied. Due to the coupling of phase separation, dewetting, and crystallization of the blend films with the evaporation of solvent during spin-coating, different size of PS islands decorated with various PCL crystal structures including spherulite-like, flat-on individual lamellae, and flat-on dendritic crystal were obtained in the blend films by changing the film composition. The average distance of PS islands was shown to increase with the relative concentration of PS in casting solution. For a given ratio of PS/PCL, the feature size of PS appeared to increase linearly with the square of PS concentration while the PCL concentration only determined the crystal morphology of the blend films with no influence on the upper PS domain features. This is explained in terms of vertical phase separation and spinodal dewetting of the PS rich layer from the underlying PCL rich layer, leading to the upper PS dewetting process and the underlying PCL crystalline process to be mutually independent.     

Ringed spherulites in ternary polymer blends of poly(<Emphasis Type="Italic">ε</Emphasis>-caprolactone), poly(styrene-<Emphasis Type="Italic">co</Emphasis>-acrylonitrile), and polymethacrylate

The relationship between ringed spherulite morphology, crystallization regimes/kinetics, and molecular interactions in miscible ternary blends of poly(-caprolactone) (PCL), poly(benzyl methacrylate) (PBzMA), and poly(styrene-co-acrylonitrile) (SAN) was investigated by using differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). The interactions resulted in the deviation of both experimental and calculated T_gs and formation of the specific morphology of the spherulitic structure. Ring-banded spherulites were observed in the PCL/PBzMA/SAN ternary blends. The width of ring bands changed with the blend ratio and the crystallization temperature. Additionally, both composition and wt% of AN in the SAN copolymer had an apparent effect on the morphology of PCL spherulites. Both the crystallization structure of lamellae and molecular interactions greatly influenced the ring bands of PCL spherulites. Furthermore, by using the Flory–Huggins approximation, the depression of the melting point showed that interactions in the PCL/PBzMA/SAN-17 blend were greater than in the PCL/PBzMA/SAN-25 blend. In the ternary blends, the great molecular interactions between amorphous and crystalline polymer resulted in better homogeneity and a larger band period of the extinction rings in the PCL spherulites.     

Interfacial structure in thin water layers formed by forced dewetting on self-assembled monolayers of omega-terminated alkanethiols on Ag

A method for the spectroscopic characterization of interfacial fluid molecular structure near solid substrates is reported. The thickness and interfacial molecular structure of residual ultrathin D20 films remaining after forced dewetting on alkanethiolate self-assembled monolayers (SAMs) of 11 1-mercaptoundecanoic acid (11-MUA), 11-mercaptoundecanol (11-MUD), and undecanethiol (UDT) on Ag are investigated using ellipsometry and surface Raman spectroscopy. The residual film thickness left after withdrawal is greater on hydrophilic SAMs than on hydrophobic SAMs. This behavior is rationalized on the basis of differing degrees of fluid slip within the interfacial region due to different interfacial molecular structure. The v(O-D) regions of surface Raman spectra clearly indicate unique interfacial molecular properties within these films that differ from bulk D20. Although the residual films are created by shear forces and Marangoni flow at the three-phase line during the forced dewetting process, the nature of the films sampled optically must also be considered from the standpoint of thin film stability after dewetting. Thus, the resulting D20 films exist in vastly different morphologies depending on the nature of the water-SAM interactions. Residual D20 is proposed to exist as small nanodroplets on UDT surfaces due tospontaneous rupture of the film after dewetting. In contrast, on 11-MUD and 11-MUA surfaces, these films exist in a metastable state that retains their conformal nature on the underlying modified surface. Analysis of the peak intensity ratios of the so-called "ice-like" to "liquid-like" v(O-D) modes suggests more ice-like D20 character near 11-MUD surfaces, but more liquid-like character near 11-MUA and UDT surfaces. The creation of residual ultrathin films by forced dewetting is thus demonstrated to be a powerful method for characterizing interfacial molecular structure of fluids near a solid substrate under ambient conditions of temperature and pressure.     

Morphology and properties of polycaprolactone-poly(dimethyl siloxane)-polycaprolactone triblock copolymers

The molecular structure, crystallization, solid-state morphology, thermal properties, and phase behavior of two copolymers consisting of a poly(dimethylsiloxane) (PDMS) mid-block coupled to polycaprolactone (PCL) end-blocks were investigated. Both copolymers (which differ only in the molecular lengths of the PCL end-blocks) were found to be lamellar systems, whose core consists of PCL chains having the same crystal structure as PCL homopolymer, and whose amorphous interlayers contain the PDMS blocks and the PCL noncrystalline segments. From x-ray and electron-microscopy results, it is expected that the PCL blocks may be folded once in the longer copolymer and not at all in the shorter. As a result of their differing PCL lengths, the former crystallizes as regular PCL spherulites (at a growth rate reduced with respect to PCL homopolymer), whereas the latter yields only defective, immature axialites of low overall crystallinity. Electron diffraction showed that these spherulites grow preferentially along b crystallographic axis and that the PCL crystalline stems are arranged perpendicularly to their lamellae. © 1993 John Wiley & Sons, Inc.