The Composition,Sequence Analysis,and Crystallization Characterization of Poly(Trimethylene‐co‐Butylene Terephthalate) Copolymer

A series of poly(trimethylene‐co‐butylene terephthalate) (PTBT) copolymers were prepared by direct esterification followed by polycondensation. The composition and sequence distribution of the copolymers were investigated by nuclear magnetic resonance (NMR). The results demonstrate that the synthesized PTBT copolymers are block copolymers and the content of poly(butylene terephthalate) (PBT) units incorporated into the copolymers is always less than that in the polymerization feed. The 1,4‐butanediol consumption by a side reaction leads to a relatively lower content of PBT units in the resultant copolymers. At the same time, the PBT and poly(trimethylene terephthalate) (PTT) sequence length distributions in the copolymers are different. The PBT segments favor a longer sequence length than do the PTT segments in their corresponding enriched copolymers. The crystallization rate of the copolymers becomes lower than the homopolymers, especially for PTT‐enriched copolymers. Compared with the PTT segment, the presence of PBT segments in the copolymers seems to accelerate crystallization. A wide‐angle X‐ray diffraction (WAXD) analysis indicates PTT and PBT units do not co‐crystallize. The reduced melting temperatures of the copolymers may be attributed to a smaller lamellar thickness and lateral size due to short sequence lengths.     

三嵌段共聚物的电子结构及态密度特征

采用紧束缚近似计算方法,针对小带隙的聚乙炔(polyacetylene,(PA))和大带隙的聚对苯撑(poly(p-phenylene),(PPP)组成的三嵌段共聚物(triblock copolymer)-(PA)x-(PPP)n-(PA)y-和-(PPP)x-(PA)n-(PPP)y-性质进行了研究,发现它们具有典型的量子阱特征.对均聚物PPP和PA以及三嵌段共聚物的态密度(density of states, (DOS))进行了计算分析,发现共聚物的态密度与均聚物的态密度有着显著的区别,共聚物的带隙的大小介于大带隙的PPP和小带隙的PA之间,在共聚物中与PPP的导带和价带的子带隙以及共聚物的导带底和价带顶中,所存在的能态密度只能由PA来提供,而在共聚物的价带底和导带顶的能态密度则取决于PPP的态密度.     

Thermal studies on ethylene–vinylcyclohexane copolymers prepared with bis-indenyl type metallocene catalyst systems

Ethylene–vinylcyclohexane copolymers (EVCH) were synthesized with unsubstituted and substituted bis-indenyl type metallocene catalysts and their thermal and dynamic mechanical behavior was studied and compared to a series of metallocene catalyzed ethylene-1-hexene (EH) and ethylene-1-hexadecene (EHD) copolymers. Increasing comonomer incorporation in the chain decreased the melting point, the level of crystallinity, and the density of all copolymers, but the bulky size of the vinylcyclohexane (VCH) group made this decrease very insignificant for the EVCH copolymers. The influence of the VCH group was also noticed in the loss tangent curves by dynamic mechanical analysis as a very insignificant shift of the β-transition to lower temperatures at increasing comonomer content, a behavior quite opposite to the behavior of the EH and EHD copolymers. The storage modulus curves explained that the stiffness properties of the EVCH copolymers are as good or better than those of the EH and EHD copolymers at the same comonomer level. The intensities of the maximum in the loss tangent curves indicate that EVCH copolymers may have good impact properties. Fractionation studies by differential scanning calorimetry (DSC) using a self-nucleation/annealing (SSA) procedure confirmed a broadening of the lamellar thickness distribution as the amount of comonomer increased. Self-nucleation/annealing curves of highly branched EVCH and EH copolymers exhibited big similarities suggesting similar random comonomer distributions.     

Designing and Characterization of Poly(L-Lactide)/Poly(ϵ-Caprolactone) Multiblock Copolymers

A series of poly(L-lactide)/poly(?-caprolactone) (PLA/PCL) biodegradable multiblock copolymers was synthesized by a two-step process and characterized. Ring-opening polymerization was used to prepare a series of HO-PLA-PCL-PLA-OH copolymers initiated by hydroxyl-terminated PCL. Then the triblock copolymers and 1,6-hexamethylene diisocyanate (HDI) were reacted with different copolymer/HDI weight ratios. Consequently, a series of PLA/PCL multiblock copolymers with designed molecular chain structure was obtained. Gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, and ¹H NMR were used to characterize these copolymers and the results showed that the designed PLA/PCL copolymers had been synthesized. Dynamic mechanical analysis (DMA) was applied to characterize their thermal properties. Stress–strain curves showed that a PLA/PCL copolymer with adjustable mechanical properties had been achieved.     

Study of photooxidation of styrene-butadiene copolymers by surface pressure measurements at the air-water interface

Block and random copolymers of butadiene and styrene as well as polybutadiene and polystyrene homopolymers have been investigated with respect to their monolayer properties and photooxidation behavior. Whereas polystyrene and block copolymers of styrene and butadiene form stable monolayers, polybutadienes and random copolymers do not interact with the aqueous subphase. The monolayer properties of block copolymers with different styrene content indicate that polybutadiene also contributes to the surface pressure. Photo-oxidation of random and block copolymers of styrene and butadiene leads to a significant enhancement in surface pressure of the monolayers due to the generation of groups which can effectively interact with the aqueous surface. FTIR spectral studies show the formation of carbonyl, hydroxyl, and hydroperoxyl groups in the polymers on photooxidation. A comparison of the pressure-area isotherms of random and block copolymers oxidized in solution indicates that there is an energy transfer from butadiene to styrene units in the case of random copolymers, resulting in a protective effect of butadiene units from oxidation. In addition, in the monolayers of oxidized block copolymers, a phase transition occurs which is attributed to the extrusion of polystyrene blocks from the monolayer. The surface pressure-area isotherms and the rates of photooxidation are strongly dependent on the microstructure of polybutadiene as well as on whether oxidation is performed in solution or at the oxygen-water interface.     

Photoluminescence properties of new PPV derivatives

We investigate the emission properties of two copolymers by steady-state and time-resolved photoluminescence measurements. The copolymers are derived from poly-phenylene-vinylene (PPV) to which a non-conjugated ether group was added. The difference between the two copolymers is the group attached on the phenyl rings. Their fluorescence spectra present bathochromic and hypsochromic shift with respect to pristine PPV, well explained by their chemical properties. Additionally, we observe an enhancement of their quantum yield compared to that of PPV. Photoluminescence decays are bi-exponential for the two copolymers and their lifetime are longer than that of PPV. Finally, differences in emission properties between the two copolymers put in evidence the importance of their conformational structures in the luminescence processes.     

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     

Exploring Microstructures and Interphase Properties of Surface- Grafted Diblock Copolymers in a Homopolymer Melt by Self-Consistent Field Theory Simulations

Polymeric self-consistent field theory is used to investigate microstructures and interphase properties of diblock copolymers grafted onto solid surfaces in a homopolymer melt. The calculations show that the grafted diblock copolymers can self-assemble into hemispherical microstructures at low grafting densities of the diblock copolymers. The morphology transforms into hemicylinder-like and sandwich-like lamellar microstructures with an increase in the chain-grafting density. The effective thickness of the grafted block layer and the interphase width between the homopolymer melt and the grafted copolymers strongly depend on the physicochemical parameters of the system, such as the composition of the grafted copolymer, the chemical incompatibility between the different components, the length ratio of grafted copolymer to homopolymer, and the grafting density of the diblock copolymers. In addition, the above computational results of microphase-separated structures and interphase properties are qualitatively compared with our previous experimental observations. The comparison indicates that our theoretical results not only reproduce the general feature of the experimental observations, but also elucidate the internal structural information and complement the findings in the region of high grafting densities of diblock copolymers.     

Weak segregation theory and non-conventional morphologies in the ternary ABC triblock copolymers

The statistical theory of microphase separation in the ternary ABC triblock copolymers is presented and the corresponding phase diagrams are built both for the linear and miktoarm copolymers. For this purpose the Leibler weak segregation theory in molten diblock copolymers is generalized to multi-component monodisperse block copolymers with due regard for the 2nd shell harmonics contributions defined in the paper. The Hildebrand approximation for the χ-parameters is used. The physical meaning of this and alternative choices for the χ-parameters is discussed. The symmetric A_fB_1-2fC_f copolymers with the middle block non-selective with respect to the side ones are shown to undergo the continuous ODT not only into the lamellar phase but also, instead, into various non-conventional cubic phases (depending on the middle block composition it could be the simple cubic, face-centered cubic or non-centrosymmetric phase, which reveals the symmetry of I4₁ 32 space group No. 214 first predicted to appear in molten block copolymers). For asymmetric linear ABC copolymers a region of compositions is found where the weakly segregated gyroid (double gyroid) phase exists between the planar hexagonal and lamellar or one of the non-conventional cubic phases up to the very critical point. In contrast, the miktoarm (star) ABC block copolymers with one of its arm non-selective with respect to the two others are shown to reveal a pronounced tendency towards strong segregation, which is preceded by increase of stability of the conventional BCC phase and a peculiar weakly segregated BCC phase (BCC₃), where the dominant harmonics belong to the 3rd coordination sphere of the reciprocal lattice. The validity region of the developed theory is discussed and outlined in the composition triangles both for linear and miktoarm copolymers. We present also the list of the 2nd shell harmonics (SAXS reflections) allowed and prohibited in some of the non-conventional morphologies due to the weak segregation considerations and comparison of our results with the preceding SCFT treatment of the ABC copolymers by Matsen.     

Designing pattern-recognition surfaces for selective adsorption of copolymer sequences using lattice monte carlo simulation

We describe a simulation method to design surfaces for recognizing specific monomer sequences in copolymers. We fix the monomer sequence statistics of the AB copolymers on a surface containing two types of sites and allow the simulation to iterate towards an optimal surface pattern that can recognize and selectively adsorb the sequence in the copolymer. During the simulation the surface pattern is designed by switching identities of two randomly picked sites. For copolymers with less blocky sequences the designed surfaces recognize the correct sequence well when the segment-surface interactions dominate over the intersegment interactions. For copolymers with more blocky sequences recognition is good when the segment-surface interactions are only slightly stronger than the intersegment interactions.     

Ultrasonic degradation of poly (styrene-co-alkyl methacrylate) copolymers

The ultrasonic degradation of poly (styrene-co-methyl methacrylate) (SMMA), poly (styrene-co-ethyl methacrylate) (SEMA) and poly (styrene-co-butyl methacrylate) (SBMA) copolymers of different compositions was studied. The copolymers were synthesized and NMR spectroscopy was used to determine the composition, and the glass transition temperatures were determined by DSC. The reactivity ratios were determined by the Kelen–Tudos method and it indicated that the copolymers were random. The effect of solvent, temperature and copolymer composition on the ultrasonic degradation rate of these copolymers was investigated. A model based on continuous distribution kinetics was employed to study the degradation kinetics. The degradation rate coefficients of the copolymers decreased with an increase in the styrene content in the copolymer. At any particular copolymer composition the rate of degradation follows the order: SBMA > SEMA > SMMA. Thermogravimetric analysis (TGA) of the copolymers was carried in order to assess their thermal stability. The same order of degradation was observed for the thermal degradation of the copolymers as that observed for ultrasonic degradation.     

Investigation of registration properties of some fluoropolymers

Investigation of heavy ion radiolysis of polyvinylidenfluoride and its copolymers has shown that registration properties of materials depend on quantity of hydrogenous fragments in the polymer chain which produce lightly oxidizing double bonds in the chain under irradiation. Therefore, polyvinylidenfluoride has the lowest registration threshold. The mechanical properties of copolymers are better than those of PVDF. Moreover, the copolymers have significantly higher etching selectivity that improves pore shape in track membranes.     

Phase behavior of binary blends of symmetric polystyrene-polybutadiene diblock copolymers studied using SANS

Binary blends of compositionally symmetric diblock copolymers are investigated using small-angle neutron scattering. The study focuses on the miscibility of blends of polystyrene-polybutadiene diblock copolymers as a function of chain length ratio and blend composition, and the results are related to the theoretical phase diagram put forward by M.W. Matsen (J. Chem. Phys. 103, 3268 (1995)). Three different low molar mass copolymers were blended with a high molar mass copolymer. We find very good coincidence with the theoretical phase diagram obtained. Only for blends having a chain length ratio of 0.06, theory predicts that a larger amount of short copolymers can be dissolved in the matrix of long copolymers, and vice versa. With the latter blends and volume fractions of short chains between 0.11 and 0.70, the second-order Bragg-peaks do not vanish, which indicates that the lamellae are asymmetric. Received: 9 February 1998 / Revised: 20 April 1998 / Accepted: 24 April 1998     

Self-assembly of block copolymers grafted onto a flat substrate:Recent progress in theory and simulations

Block copolymers are a class of soft matter that self-assemble to form ordered morphologies on the scale of nanometers, making them ideal materials for various applications. These applications directly depend on the shape and size of the self-assembled morphologies, and hence, a high degree of control over the self-assembly is desired. Grafting block copolymer chains onto a substrate to form copolymer brushes is a versatile method to fabricate functional surfaces. Such surfaces demonstrate a response to their environment, i.e., they change their surface topography in response to different external conditions. Furthermore, such surfaces may possess nanoscale patterns, which are important for some applications; however, such patterns may not form with spun-cast films under the same condition. In this review, we summarize the recent progress of the self-assembly of block copolymers grafted onto a flat substrate. We mainly concentrate on the self-assembled morphologies of end-grafted AB diblock copolymers, junction point-grafted AB diblock copolymers(i.e.,Y-shaped brushes), and end-grafted ABA triblock copolymers. Special emphasis is placed on theoretical and simulation progress.     

Electrochemical,morphological, and spectroscopic study of poly(aniline-co-<Emphasis Type="Italic">o</Emphasis>-bromoaniline) (PA-co-<Emphasis Type="Italic">o</Emphasis>-BrA) conducting copolymer

A series of moderately conducting and soluble copolymers of poly(aniline-co-o-bromoaniline) (PA-co-o-BrA) having different compositions was obtained by in the situ copolymerization method using different concentrations of monomer units of aniline and o-bromoaniline in the feed. The physio-chemical properties of the copolymers have been studied with sophisticated instrumental techniques. The electrochemical study of the copolymers was conducted by cyclic voltammetry. The band gap of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the copolymers was evaluated by UV-vis spectroscopy. The morphological study was conducted by scanning electron microscopy and transmission electron microscopy at high magnification which shows non-uniform tubular to globular morphology of the copolymers. Surface profiles of the polymers were studied by AFM analyses, and it has confirmed the smooth surface of the copolymers while the homopolymers possesses non-uniform surfaces. The particle size distribution curve indicates that the particle sizes vary in the range of 5 to 9000 nm, and a small fraction of particles possess a size in the range of 5–10 nm.     

Development of copolymer of CR-39 with high sensitivity to low let particles

Several types of copolymers of CR-39 were prepared to find its usefulness as a nuclear track detector of high sensitivity. Track responses of these copolymers were investigated by irradiating energetic ions from proton through Ar. The copolymer of CR-39 monomer with N-isopropylacrylamide (NIPAAm) shows higher sensitivity than that of pure CR-39 for low LET particles such as protons. Preliminary results are reported for the track responses of copolymers (CR-39/NIPAAm) with various contents of NIPAAm as well as the etching properties.     

E—DAM共聚物序列结构的^13CNMR研究

本文用COM和APT~(13)C NMR方法研究了三种乙烯(E)和甲基丙烯酸N,N—二甲胺乙酯(DAM)共聚物(E—DAM),找到了一组化学位移屏蔽参数,并用这种参数进一步研究了E—DAM共聚物序列结构.     

Electronic and Optical Properties of Some Polysulfone-Polydimethylsiloxane Copolymers in Thin Films

Polysulfone (PSF)-polydimethylsiloxane (PDMS) block copolymers (PSF-b-PDMS) with various compositions were prepared by condensing chloro-terminated polysulfone oligomers with α, ω -dihydrogensilyl-polydimethylsiloxane in refluxing chlorobenzene solution in the presence of urea as a hydrogen chloride acceptor. The temperature dependences of the electrical conductivity and thermoelectric power (Seebeck coefficient) of copolymers were studied using thin films deposited from a dimethylformamide solution (spin coating method) onto glass substrates. It was established that the various copolymers showed typical semiconducting properties. Some correlations between these properties (activation energy, ratio of carrier mobilities, etc) and molecular structure of the copolymers were found. A model based on band gap representation was found to be suitable for explanation of the electronic transport mechanism through the studied copolymers in thin films. The study of the transmission and absorption spectra (in the spectral range from 300 nm to 1400 nm) evidenced that the indirect allowed optical transitions were predominant. The values of the optical energy band gap (ranged between 1.50 eV and 1.70 eV) are in agreement with values of width of the forbidden band calculated from the temperature dependence of the electrical conductivity.     

Thermal behavior of vinylidene chloride—methyl acrylate copolymers

The thermal behavior of random copolymers of vinylidene chloride-methyl acrylate (VDC-MA) was monitored with differential scanning calorimetry. The effects of composition, annealing, and heating rate on the copolymer melting process were studied. Increasing levels of comonomer decreased the crystalline melting point and percent crystallinity of the copolymers. A combination of information obtained from heating rate and small-angle x-ray scattering studies led to a model of the melting behavior of PVDC and its copolymers. Apparently a simultaneous melting/recrystallization phenomenon occurs in these materials during heating.