Phase Behavior and dewetting for polymer blend films studied by in situ AFM and XPS: From thin to ultrathin films

In this work, the film thickness (l(0)) effect on the phase and dewetting behaviors of the blend film of poly(methyl methacrylate)/poly (styrene-ran-acrylonitrile) (PMMA/SAN) has been studied by in situ atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The thinner film shows the more compatibility of the blend, and the phase separation of the film occurs at l(0) > 5R(g) (radius of gyration). An initially time-independent q*, the characteristic wavenumber of the phase image, which is in good agreement of Cahn's linearized theory for the early stage of spinodal decomposition, has been obtained in real space and discussed in detail. For 5R(g) > l(0) > 3R(g), a "pseudo-dewetting/(phase separation + wetting)" behavior occurs, where the pseudo-wetting is driven by the concentration fluctuation mechanism. For 10 < 3R(g), a "real dewetting/(phase separation + wetting)" behavior occurs.

Sugars-grafted aliphatic biodegradable poly(L-lactide-co-carbonate)s by click reaction and their specific interaction with lectin molecules

A novel biodegradable aliphatic poly(L-lactide-co-carbonate) bearing pendant acetylene groups was successfully prepared by ring-opening copolymerization of L-lactide (LA) with 5-methyl-5-propargyloxycarbonyl-1,3-dioxan-2-one (PC) in the presence of benzyl alcohol as initiator with ZnEt2 as catalyst in bulk at 100 degrees C and subsequently used for grafting 2-azidoethyl beta-D-glucopyranoside and 2-azidoethyl beta-lactoside by the typical "click reaction," that is Cu(I)-catalyzed cycloaddition of azide and alkyne. The density of acetylene groups in the copolymer can be tailored by the molar ratio of PC to LA during the copolymerization. The aliphatic copolymers grafted with sugars showed low cytotoxicity to L929 cells, improved hydrophilic properties and specific recognition and binding ability with lectins, that is Concanavalin A (Con A) and Ricinus communis agglutinin (RCA). Therefore, this kind of sugar-grafted copolymer could be a good candidate in variety of biomedical applications.

Dewetting and phase behaviors for ultrathin films of polymer blend

Dynamics of dewetting and phase separation in ultrathin films (thickness is ca. one radius of gyration, approximate to 1 R-g) of poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN) blends on Si substrate has been studied by in situ atomic force microscopy (AFM). In the miscible region, a "spinodal-like" dewetting driven by a composition fluctuation recently predicted by Wensink and Jerome (Langmuir 2002, 18, 413) occurs. In the two-phase region, the dewetting of the whole film is followed by phase separation in the droplets, coupling with the wetting of the substrate by the PMMA extracted by the strong attractive interaction between them.

Surface phase separations of PMMA/SAN blends investigated by atomic force microscopy

The thin films of poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (SAN) and their blends were prepared by means of spin-coating their corresponding solutions onto silicon wafers, followed by being annealed at different temperatures. The surface phase separations of PMMA/SAN blends were characterized by virtue of atomic force microscopy (AFM). By comparing the tapping mode AFM (TM-AFM) phase images of the pure components and their blends, surface phase separation mechanisms of the blends could be identified as the nucleation and growth mechanism or the spinodal decomposition mechanism. Therefore, the phase diagram of the PMMA/SAN system could be obtained by means of TM-AFM. Contact mode AFM was also used to study the surface morphologies of all the samples and the phase separations of the blends occurred by the spinodal decomposition mechanism could be ascertained. Moreover, X-ray photoelectron spectroscopy was used to characterize the chemical compositions on the surfaces of the samples and the miscibility principle of the PMMA/SAN system was discussed.

ABS树脂合成中影响PB-g-SAN接枝共聚物接枝率的因素

采用种子乳液聚合方式 ,以 K2 S2 O8为引发剂引发聚合 ,合成了一系列 PB- g- SAN接枝共聚物。考察了引发剂用量、分子量调节剂 (TDDM)用量和橡胶 (PB)含量对 PB- g- SAN接枝共聚物接枝率的影响。并将 K2 S2 O8引发剂与氧化 -还原引发体系做了比较。结果表明 ,随着引发剂 K2 S2 O8用量逐渐增加 ,PB- g- SAN接枝共聚物的接枝率逐渐降低。引发剂用量太少时 ,不能满足聚合要求 ,PB- g- SAN接枝共聚物的接枝率也会降低。随着分子量调节剂 (TDDM)用量的增加 ,PB- g- SAN接枝共聚物的接枝率逐渐降低。随胶含量的增加 ,PB- g- SAN接枝共聚物的接枝率逐渐降低。采用氧化 -还原引发体系引发聚合有利于接枝反应的进行 ,在 PB含量相同时 ,采用氧化 -还原引发体系合成的 PB- g- SAN接枝共聚物的接枝率比采用 K2 S2 O8合成的接枝共聚物接枝率高。

PMMA/SAN共混体系的热膨胀系数和等温压缩系数测定

通过溶液共混制得不同组成的聚甲基丙烯酸甲酯 (PMMA)和苯乙烯 -丙烯腈共聚物 (SAN,其中AN的含量约为 30 % (质量 ) )的共混物。利用压力 -体积 -温度 (p VT)膨胀仪对 PMMA、SAN纯组分样品及各共混物分别进行了测量 ,得到了它们的比容 Vsp随温度 T和压力 p变化的关系 (p VT数据 ) ,计算出它们的热膨胀系数 α随温度变化的关系以及等温压缩系数 β随压力变化的关系。在此基础上 ,拟合出共混物的 α和 β分别随组成变化的关系式。此外 ,应用 Tait方程对所有样品的 p VT数据进行了拟合

Functionalization of isotactic polypropylene with maleic anhydride by reactive extrusion: mechanism of melt grafting

In this work, chemical structures and molecular parameters of grafted materials of PP-g-MAH prepared by melt reactive extrusion were studied by using electrospray ionization-mass spectrometer and gel permeation chromatography. It was found that the initial radicals, due to homolitic scission of dicumyl peroxide could be combined with maleic anhydride (MAH) monomers as well as polypropylene (PP) molecular chains. The homopolymerization of MAH cannot occur and the MAH radicals undergo a dismutational reaction under the processing condition (180-190 degreesC). A modified mechanism of melt grafting MAH onto PP has been proposed tentatively on the basis of our experimental results and other experimental findings published in the literature. (C) 2001 Elsevier Science Ltd. All rights reserved.

SAN树脂的相对分子质量对ABS树脂力学性能的影响

通过将三种不同相对分子质量的SAN树脂与同一种ABS接枝粉料进行熔融共混 ,测试共混物的力学性能 ,比较了三种SAN各自的增韧特性。实验结果表明 :SAN树脂的相对分子质量越高 ,制得的ABS树脂的冲击强度和断裂伸长率越高。SAN树脂的相对分子质量对ABS树脂的拉伸强度没有影响。SAN树脂的低聚物和挥发成分对拉伸强度影响较大。将高相对分子质量SAN和低相对分子质量SAN按不同比例混合后 ,再与ABS接枝粉料以 18份橡胶共混 ,考察了高相对分子质量SAN的加入对共混物冲击强度和熔体流动速率的影响。在SAN树脂中加入高相对分子质量SAN树脂后 ,可以提高ABS树脂的冲击强度 ,显著降低加工流动性

EAA增容LLDPE/SAN共混物的形态及力学性能

采用SEM及力学性能测试等方法，研究了乙烯－丙烯酸共聚物（EAA）含量对其增容线性低密度聚乙烯（LLDPE）／苯乙烯－丙烯腈共聚物（SAN）共混物形态及性能的影响．发现少量的EAA可使共混物中SAN相的相尺寸减小，共混物模量、拉伸强度及断裂伸长率提高．当EAA的含量增加至11．7％时，它在共混物中两相界而的分布达到饱和，即增容剂饱和浓度Cs=11．7％；此时，共混物形态及性能的变化趋势出现明显转折．明显过量的EAA主要起增韧作用．EAA的增容机理为，它与LLDPE组分的非晶区可部分相容，同时又与SAN相存在着分子间特殊作用.

Photoluminesence and electroluminescence of the blue emission of devices based on poly(p-phenylenevinylene) copolymers

Bright blue polymer light-emitting diodes have been fabricated by using the poly(p-phenylenevinylene)-based copolymers with 10 C long aliphatic chains as the electroluminescent layers, PBD in PMMA and Alq(3) as the electron-transporting layers, and aluminum as the cathode. The multilayer structure devices show 190 cd/m(2) light-emitting brightness at 460 nm, 15 V turn-on vol- tage. It is found that the intensities of photoluminescence and electroluminescence (EL) increase with increasing aliphatic chain length, the EL intensity and operation stability of these polymer light-emitting diodes can be improved by reasonable design of the structure.

CRYSTALLIZATION KINETICS OF MIXTURES OF POLY(EPSILON-CAPROLACTONE) AND POLY(STYRENE-CO-ACRYLONITRILE)

The crystallization kinetics in mixtures of poly(epsilon-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) has been investigated as the function of composition and crystallization temperature. The isothermal growth rates of PCL spherulites decrease with increasing concentration of SAN. Because of the miscibility of PCL/SAN mixtures, the radial growth rates of the spherulites are described by a kinetic equation including the interaction parameter and the free energy for the formation of crystal nuclei. The interaction parameter obtained from the fitting of the kinetic equation with experimental data is in good agreement with that obtained from melting point depression. Folding surface free energies decrease with the increase of SAN concentration. In light of these results, it is suggested that, for the PCL/SAN mixtures, the noncrystallizable SAN polymer reduces the mobility of crystallizable PCL polymer so that the growth rates decrease with the increase of noncrystallizable component fraction.

Clay mineral distributions in the southern Yellow Sea and their significance

To better understand the characteristics of the clay minerals in the southern Yellow Sea, the X-ray quantitative determinations have been carried out for the surface samples obtained from the Yellow Sea. With newly compiled clay mineral synoptic maps, the depositional processes were described for four main clay minerals (illite, chlorite, kaolinite and smectite). The analysis shows that most clay minerals are of terrigenous source with the Huanghe River acting as the major sediment supplier. Besides, the source of muddy sediments in the Yellow Sea was also discussed. As for the central Yellow Sea mud (CYSM), the sediments in its northern part mainly come from the Huanghe River, and those in the rest are of multi-origin. Very similarly, a large amount of sediments in the northern part of the southeastern Yellow Sea Mud (SEYSM) derive from the Keum River and Yeong-san River, while those in the southern part are of multi-origin.

Sesquiterpenes from Laurencia similis

One new sesquiterpene, (4E)-1-bromo-5-[(1'S*, 3'R*)-3'-bromo-2',2'-dimethyl-6'-methylenecyclohexyl]-3-methylpent-4-ene-2,3-diol (1), and fifteen known sesquiterpenes, isopalisol (2), luzonensol (3), palisadin B (4), aplysistatin (5), palisadin A (6), 4-hydroxyl-palisudin C (7), 5-acetoxypalisadin B (8), 10-hydroxyaristolan-9-one (9), aristol-8-en-1-one (10), aristolan-9-en-1-one (11), aristolan-1(10)-en-9-one (12), aristolan-1( 10)-en-9-ol (13), aristolan-1(10), 8-diene (14), aristolan-1,9-diene (15) and aristofone (16), were isolated from a sample of marine red alga Laurencia similis. Their structures were established by detailed NMR spectroscopic analysis and comparison with literature data. Compounds 2-9, and 16 were isolated for the first time from this species. All these metabolites were submitted for a cytotoxicity assay against the tumor cell line BEL7402 (human liver adenocarcinoma), but all of them were found inactive (IC50 > 10 mu g/mL).

The antitumor effect of bromophenol derivatives in vitro and Leathesia nana extract in vivo

To investigate the antitumor effect of bromophenol derivatives in vitro and Leathesia nana extract in vivo, six bromophenol derivatives 6-(2,3-dibromo-4,5-dihydroxybenzyl)-2,3-dibromo-4,5-dihydroxy benzyl methyl ether (1), (+)-3-(2,3-dibromo-4,5-dihydroxyphenyl)-4-bromo-5,6-dihydroxy-1,3-dihydroisobenzofuran (2), 3-bromo-4-(2,3-dibromo-4,5-dihydroxybenzyl)-5-methoxymethyl-pyrocatechol (3), 2,2',3,3'-tetrabromo-4,4',5,5'-tetrahydroxy-diphenylmethane (4), bis(2,3-dibromo-4,5-dihydroxybenzyl) ether (5), 2,2',3-tribromo-3',4,4',5-tetrahydroxy-6'-ethyloxymethyldiphenylmethane (6) were isolated from brown alga Leathesia nana, and their cytotoxicity were tested by MTT assays in human cancer cell lines A549, BGC-823, MCF-7, B16-BL6, HT-1080, A2780, Bel7402 and HCT-8. Their inhibitory activity against protein tyrosine kinase (PTK) with over-expression of c-kit was analyzed also by ELISA. The antitumor activity of ethanolic extraction of Leathesia nana (EELN) was evaluated on S-180-bearing mice. All compounds showed very potent cytotoxicity against all of the eight cancer cell lines with IC50 below 10 mu g/mL. In PTK inhibition study, all bromophenol derivatives showed moderate inhibitory activity and compounds 2, 5 and 6 showed significant bioactivity with the inhibition ratio of 77.5%, 80.1% and 71.4%, respectively. Pharmacological studies reveal that EELN could inhibit the growth of Sarcoma 180 tumor and increase the indices of thymus and spleen to improve the immune system remarkably in vivo. Results indicated that the bromophenol derivatives and EELN can be used as potent antitumor agents for PTK over-expression of c-kit and considered in a new therapeutic strategy for treatment of cancer.

Sesquiterpenes from the Marine Red Alga Laurencia saitoi

Together with five known sesquiterpenes, EtOH extraction of Laurencia saitoi yielded four new compounds, including three sesquiterpenes and one norsesquiterpene derivative. Their structures and relative configurations were elucidated by spectroscopic methods, including 1D- and 2D-NMR (H-1,H-1-COSY, HMQC, HMBC, and NOESY), as well as low- and high-resolution mass-spectrometric analyses.