13C及29Si核磁共振研究苯乙烯-二甲基硅氧烷嵌段共聚物的弛豫及分子运动

用¹³C及²⁹Si核磁共振研究了苯乙烯(S)及二甲基硅氧烷(Si)嵌段共聚物中硅氧烷软段的固体及溶液谱的自旋-晶格弛豫时间T₁。固态嵌段共聚物主链²⁹Si及侧甲基¹³C的T₁都与均聚物的T₁相近,但在CdCl₃溶液中各种嵌段共聚物的T₁与均聚硅氧烷相差颇大。用偶极-偶极相互作用来解释高聚物的自旋-晶格弛豫。苯乙烯-二甲基硅氧烷嵌段共聚物具两相结构,所以嵌段共聚物中软段及硬段微区中链段的运动与在均聚物分子中链段的运动模式基本相同。而CdCl₃对聚苯乙烯或聚硅氧烷都是良溶剂,软段硬段之间有相互影响。所以其链段运动与均聚物不同,从而导致链段运动的相关时间τ_c变短和T₁的增长。     

一种侧链共轭噻吩共聚物增强的三阶非线性光学特性

侧链共轭的聚噻吩衍生物具有拓宽的共轭程度,有望成为一类性能优良的三阶非线性光学材料.合成了一种侧链共轭的噻吩共聚物:聚 -噻吩(POTVTh-Th),该聚合物与其均聚物相比,吸收光谱发生了明显的红移,禁带宽度为1.72eV.采用Z扫描技术在800nm下用飞秒激光器研究了该聚合物溶液和薄膜的三阶非线性光学特性,结果表明该共聚物四氢呋喃溶液中的三阶非线性极化率为8.84×10^-10esu,聚合物薄膜的三阶非线性极化率为7.25×10^-9esu,分别是其 关键词： 侧链共轭 噻吩共聚物 三阶非线性极化率 非线性吸收     

嵌段共聚物受限于软孔内的自组装

利用自洽场方法研究两嵌段共聚物受限于接枝均聚物链(聚合物刷)圆孔中的自组装相形貌.研究表明,当圆孔内径一定时,嵌段比f和聚合物刷C的体积分数φ_C是调控嵌段共聚物相形貌的主要因素,聚合物刷的弹性熵也起着重要作用.当f＝0.7时,在聚合物刷的浸润下,贴近刷表面处AB嵌段共聚物构成环层状结构,随着φ_C的减小这种结构会周而复始地出现.当f处于0. 关键词： 嵌段共聚物 圆孔受限 聚合物刷 自洽场     

红外光谱法测定聚(乳酸-苯丙氨酸)共聚物的含量

分别以苯丙氨酸和乳酸为原料合成了3-苯甲基-2,5-吗啉二酮(PMD)与丙交酯(LA),以PMD和LA作为聚合单体经开环聚合分别得到PMD均聚物(PPMD)、丙交酯均聚物(PLA)及聚(乳酸-苯丙氨酸)共聚物。对合成的均聚物进行红外分析,确定1 671.53和870.82 cm-1处的吸收峰分别为PPMD和PLA的特征峰。根据以上两种特征吸收峰并以朗伯-比耳定律为理论依据,建立了利用红外光谱法测定聚(乳酸-苯丙氨酸)共聚物含量的方法。实验测定的标准工作曲线为y=0.055 67x+0.1091,r=0.999 3。利用该标准工作曲线定量测定了共聚物组分含量,其结果与1H NMR测定值一致,相对误差在2％以内,证明红外光谱法可方便、快捷地测定聚(乳酸-苯丙氨酸)共聚物组分含量,且适用于其他聚(乳酸-氨基酸)共聚物的含量测定,具有一定的实用性及推广性。     

一维共聚物链的色散关系研究

研究了一维共聚物链的晶格振动，得到了不同均聚物构型的色散关系，并分析了其振动模的结构特点.调整界面耦合，得到了界面模，其频率位于声频与光频或光频之间的带隙中.从晶格振动的角度分析了共聚物的量子阱或超晶格特征. 关键词： 共聚物 界面耦合 晶格振动     

准一维共聚物的电子结构研究

在紧束缚近似下,建立了共聚物 (- PPP_x )—( PA_y)- 的物理模型,研究了组成共聚物的均聚物单体对体系晶格结构、能带结构等的影响,发现共聚物的带隙可通过改变均聚物的配比或均聚物之间的相互作用来加以调制. 关键词： 共聚物 界面耦合 带隙     

聚对苯二甲酸丁二醇酯/聚(对苯二甲酸丁二醇酯-e-己内酯)二元结晶共混体系的相容性和结晶行为

聚对苯二甲酸丁二醇酯(PBT)/聚(对苯二甲酸丁二醇酯-e-己内酯)(PBT-PCl)是一个新制备的具有分子间排斥相互作用的A/AxB1?x型两元结晶共混体系. 根据两元平均场模型,报道对苯二甲酸丁二醇酯(BT)与"-己内酯(CL)结构单元的相互作用参数为0.305. DSC研究发现,此共混物呈现了与典型的共聚物/均聚物共混物不同的结晶特征. PBT-PCL影响PBT链的活动力和晶片堆积;同时PBT-PCL的结晶受到先期结晶的PBT晶粒的阻滞. 尽管拥有相同的BT单元,共混的两组分在组成变化范围内仍没有形     

苯乙烯和马来酸酐共聚物的13C NMR谱解析和分子链结构表征

通过比较高温110 ℃下特定苯乙烯-马来酸酐共聚物H10和常温紫外辐照特定共聚合的苯乙烯-马来酸酐共聚物UV4的¹³C质子去偶谱和DEPT135谱，总结给出共聚
物链中马来酸酐环中酸酐基的取代效应参数（α=13.5、β=2.5、γ=-2）及引用苯基取代参数：α=16、β=6、γ=-2，对共聚物主链碳的化学位移进行了经验计算，对所有碳，尤其是主链碳在三单元组或四单元组水平上进行了链序列结构归属. 在进行峰面积积分的基础上，对共聚物分子链两种组份摩尔比或摩尔含量、交替度、链嵌段长度、马来酸酐环残基中顺反异构体比和共聚物数均分子量等进行了表征. 共聚物UV4比H10的交替度高许多，表明聚合温度对苯乙烯和马来酸酐共聚合交替链结构的形成有重要影响.     

木薯淀粉改性絮凝剂的光谱研究

采用氧化还原引发体系引发木薯淀粉与丙烯酰胺接枝共聚制备出天然木薯淀粉改性絮凝剂,用紫外-可见吸收光谱(UV-Vis)、红外光谱(FTIR)和拉曼光谱(RS)详细对比研究了木薯淀粉、丙烯酰胺和接枝共聚物三者的光谱特征,并据此讨论了接枝共聚机理.     

红外光谱监测聚富马酸二羟丙酯及其共聚物的合成研究

聚富马酸二羟丙酯(PPF)是一种可生物降解的线形不饱和聚合物,其分子链上的双键在适当引发剂的作用下可以与其他烯类单体进行交联,生成具有三维网络结构的交联体,对组织起到支撑作用。先合成了中间体低聚物-富马酸二羟丙酯(PFP),然后采用熔融缩聚的方法通过低聚物PFP合成了聚合物PPF,并且在此基础上采用类似的方法合成了癸二酸二羟丙酯(PSP),再使PFP和PSP进行缩聚反应,生成包含癸二酸二羟丙酯链段的新的聚富马酸二羟丙酯的共聚物——聚(富马酸二羟丙酯共聚癸二酸二羟丙酯)P(PF-co-PS)。在合成的过程中用FTIR对中间体富马酸二丙二醇酯、癸二酸二羟丙酯以及PPF和P(PF-co-PS)的结构进行了表征。结果表明,随着聚合反应的进行,低聚物逐渐转化为聚合物PPF或P(PF-co-PS)。     

Light-induced orientation of the molecules of nematic liquid crystals doped with comb-shaped polymers with different spatial distributions of chromophores

The orienting effect of light on nematic liquid crystals (NLCs) doped with comb-shaped polymers with different spatial distributions of side absorbing azobenzene fragments, i.e., a homopolymer (containing only azofragments), a block copolymer (containing additionally a block of non-absorbing fragments), and a statistical copolymer (containing randomly arranged absorbing and non-absorbing fragments) is experimentally studied. The light-induced Freedericksz transition threshold for the block copolymer is two times lower than that for the homopolymer. For NLC with statistical copolymer dopant, the first-order orientation transition with an extremely wide optical bistability region is observed.     

Exact results for the adsorption of a semiflexible copolymer chain in three dimensions

Lattice model of directed self-avoiding walk has been solved analytically to investigate adsorption–desorption phase transition behaviour of a semiflexible sequential copolymer chain on a two-dimensional impenetrable surface perpendicular to the preferred direction of the walk of the copolymer chain in three dimensions. The stiffness of the chain has been accounted by introducing an energy barrier for each bend in the walk of the copolymer chain. Exact value of adsorption–desorption transition points have been determined using the generating function method for the cases in which one type of monomer is having interaction with the surface, namely (i) no interaction (ii) attractive interaction and (iii) repulsive interaction. Results obtained in each of the case show that for stiffer copolymer chain adsorption transition occurs at a smaller value of monomer surface attraction than a flexible copolymer chain. These features are similar to that of a semiflexible homopolymer chain adsorption.     

Effect of Interfacial Structure on Crystallization Behavior of Polypropylene/Polyolefin Elastomer/Barium Sulfate Ternary Composites

In this paper, interfacial structure induced development of crystallization behavior of polypropylene (PP)/polyolefin elastomer (POE)/barium sulfate (BaSO₄) ternary composites was studied by DSC. Two kinds of PP (copolymer and homopolymer) were used. The compatibility between PP and POE had a distinct influence on nucleation and crystal growth of PP in PP/POE binary composites. The crystallization rate of PP homopolymer increased because of the heterogeneous nucleation by POE, while the crystallinity of PP homopolymer decreased because of an inhibition effect of the hexane side chains in POE. BaSO₄ particles acted as heterogeneous nucleating agents of PP in ternary composites. The dispersion of BaSO₄, controlled by interfacial design, had a distinct influence on the nucleation activity of BaSO₄ in ternary composites. Interfacial structure had the same effect on nucleation activity of BaSO₄ particles and crystallization rate of PP matrix in PP copolymer ternary composites as those in PP homopolymer ternary composites.     

Binary-component micelle and vesicle: Free energy and asymmetric distributions of amphiphiles between monolayers of vesicle

The real-space two-dimensional self-consistent field theory (SCFT) is employed to study the free energies of micelles and vesicles constituted by binary amphiphilic diblock copolymer AB in homopolymer A. With increasing volume fraction of copolymer AB, there are morphological transitions from the circle micelles to oblate circle-like micelles, to compound structure with inverted micelles in the inner center and micelles outer layer, and to vesicles. Special attentions are paid to the role of the copolymer AB in controlling free energies of the micelles and vesicles, by examining the effect of length ratio of A/B with the fixed whole chain length of AB copolymer, the length effect of A or B block with the corresponding fixed length of B or A block, for one component of copolymer, and the effect of different amphiphile compositions for binary-component copolymer system. The quantity η is provided to describe the asymmetric density distribution of amphiphiles between the inner and outer monolayers of vesicles, and to quantify the relative asymmetric extent of the density distribution between two species of copolymers in binary component vesicles.     

Adsorption of a Gaussian random copolymer chain at an interface

We consider the adsorption of an isolated, Gaussian, random, and quenched copolymer chain at an interface. We first propose a simple analytical method to obtain the adsorption/depletion transition, by averaging over the disorder the partition function instead of the free energy. The adsorption thresholds obtained by previous authors at a solid/liquid and at a liquid/liquid interface for multicopolymer chains can be rederived using this method. We also compare the adsorption thresholds obtained for bimodal and for Gaussian disorder; they only agree for small disorder. We focus on the specific case of an ideally flat asymmetric liquid/liquid interface, and consider the situation where the chain is composed of monomers of two different chemical species A and B. The replica method is developed for this case. We show that the Hartree approximation, coupled to a replica symmetry assumption, leads to the same adsorption thresholds as obtained from our general method. In order to describe the properties of the adsorbed (or depleted) chain, we develop a new approximation for long chains, within the framework of the replica theory. In most cases, the behavior of a random copolymer chain can be mapped onto that of a homopolymer chain at an asymmetric attractive interface. The values of the effective adsorption energy are different for a random and a periodic copolymer chain. Finally, we consider the case of uncorrelated annealed disorder. The behavior of an annealed chain can be mapped onto that of a homopolymer chain at an asymmetric non attractive interface; hence, an annealed chain cannot adsorb at an asymmetric interface. Received 21 January 1999     

The Nature of Trapping Centers in Amorphous Biphenyl-Containing Polymer

Study of optical properties of methyl methacrylate and 4-vinylbiphenyl copolymers in a rigid amorphous polymer allowed establishing the non-excimer nature of energy traps in a polymer chain. These traps are probably related to possibility of collective states formed by macromolecule’s chromophore groups. The shortening of the trap states decay time in 4-vinylbiphenyl homopolymer comparing to copolymer is observed.     

抗冲共聚聚丙烯中二甲苯可溶物的链结构与性能研究

抗冲共聚聚丙烯(IPC)是聚丙烯与乙烯-α-烯烃共聚产物在反应釜内形成的原位共混物,乙烯-α-烯烃无规共聚物(橡胶相)作为聚丙烯增韧剂,增韧能力受其组成、玻璃化转变温度(T_g)的影响很大。目前工业界主要采用二甲苯可溶物来表征IPC中橡胶相的含量。该研究采用红外光谱(FTIR)、核磁共振(NMR)和热分析(DSC)等方法对两种不同催化剂制备的IPC的二甲苯可溶物,进行了组成、链结构及热性能对比研究,结果显示二甲苯可溶物中除了乙烯-丙烯无规共聚物外,还含有少量的具有可结晶乙烯序列的乙烯-丙烯多嵌段共聚物,且两个样品中的乙烯-丙烯多嵌段共聚物中可结晶乙烯序列长度存在差别;两个样品中乙烯、丙烯单元在分子链上无规分布的程度比较接近;丙烯序列PPP的含量相对低且乙烯共聚单元含量高的样品具有更低的Tg,这将有利于其对聚丙烯抗冲击韧性的提高。     

Preparation and Characterization of Poly (Acrylonitrile-co-1-Acryloylpyrrolidine- 2-Carboxylic Acid) with High Molecular Weight

1-acryloylpyrrolidine-2-carboxylic acid (APCA) monomer was copolymerized with acrylonitrile (AN) by aqueous suspension polymerization. High molecular weight (HMW) copolymers of AN and APCA [poly(AN-co-APCA)] with different copolymer composition were successfully prepared by employing azobisisobutyronitrile (AIBN) as initiator and polyvinyl alcohol (PVA) as dispersant in a H₂O/N,N-dimethylformamide (DMF) mixture at 60°C. The PAN homopolymer and copolymers were characterized by elemental analysis (EA), nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). The EA results indicated that the content of oxygen increased significantly in PAN copolymers with increasing APCA content. The APCA copolymer composition calculated from the EA was higher than that from ¹H NMR spectra. The FTIR spectra of PAN and poly(AN-co-APCA) with different monomer ratios confirmed that the contents of APCA units in the copolymer chains increased with increasing APCA content in the feed. The DSC exotherms revealed that copolymerization with APCA could slow the rate of the exothermic reactions during the heat-treatment processes. The XRD results indicated that the PAN homopolymer and copolymers poorly crystallized and the crystallinity decreased with increasing APCA contents.