Modification and Characterization of Chitosan Films Using 3-trimethoxyl Silyl Propylmethacrylate

The biodegradable flexible chitosan film was prepared by solution casting. The physico-mechanical properties, polymer loading (PL), gel content and water uptake of the chitosan film were studied. The tensile strength (TS) and % elongation at break (Eb) of the uncured chitosan film were 7.0 (MPa) and 8%, respectively. Four formulations were developed using 3-trimethoxyl silyl propylmethacrylate (TSPMA) (varied from 10–80% by weight) in methanol along with photoinitator (Darocur-1664). The raw chitosan films were then soaked in the prepared formulations and cured under UV radiation at different intensities to improve the physico-mechanical properties of the films. TS for the photocured chitosan film was 28.0 (MPa) which was 4 times higher compared to the uncured chitosan film. This TS was obtained for the formulation containing 30% silane (TSPMA) at 24th UV pass for 4 min soaking time. The maximum PL of 45.1% was obtained for the same formulation at 24th UV pass for 4 min soaking time. The water uptake and gel content of the photocured chitosan films were also studied. The scanning electron micrographs of the photocured chitosan film showed smooth surface, compact and homogeneous structure.     

Hierarchical dual-sized film surface morphologies self-generated from fluorinated binary latex blends boost hydrophobicity and lipophobicity

Latex films with controlled dual-level nanorough surfaces were obtained by casting from binary blends of fluorinated copolymer particles with a nanostructured core-shell morphology, narrow size dispersity and large size ratios. For this purpose, particles with different size, a common unfluorinated acrylic core copolymer of the self-crosslinking trimethoxysilylpropyl methacrylate (TSPMA) and a hard shell copolymer of either 2,2,2-trifluoroethyl methacrylate (TFEMA) or 1H,1H,2H,2H-heptadecafluorodecyl methacrylate (FMA) were synthesized by multistage emulsion polymerization. The FMA-based particles showed patchy morphologies dictated by the type of β-cyclodextrin used as FMA phase carrier in their synthesis. Four series of binary blends of either TFEMA or FMA copolymer particles with large (3-4 diameters) size ratios were cast into latex films with controlled hydrophobicity and lipophobicity. AFM and electron microscopy results indicate that addition of the small particles disrupts the hexagonal compact packed 3D organization of the large particles, resulting in dual-level nanorough surfaces and high water contact angles (up to θ(w)=127° in the as cast films, and θ(w)=135° upon aging or thermal annealing causing surface restructuring and TSPMA sol-gel condensation) with respect to the parent single component films. The proposed approach provides a straightforward route for the fabrication of robust coatings and films with tunable lipophobic and highly hydrophobic surfaces.     

快速响应的温敏性聚(N-异丙基丙烯酰胺)水凝胶 Ⅱ.热力学行为及水的状态研究

对使用CaCO3为成孔剂合成的快速响应的温敏性聚 (N 异丙基丙烯酰胺 ) (PNIPA)水凝胶进行了热力学行为和水的状态研究 .热力学研究表明 ,多孔结构的PNIPA水凝胶的平衡膨胀比随着反应物中CaCO3含量的增加而增加 ,随着交联剂浓度的增加而显著减小 ,但相转变温度均不受影响 .在水溶液中加入NaCl则使PNIPA水凝胶的相转变温度 (LCST)线性减小 .利用DSC分析了水凝胶中水的存在状态 ,证明了上述多孔PNIPA水凝胶中存在三种不同状态的水 ,研究了不同CaCO3粒子含量和离子强度对三种不同状态水的影响     

阳离子型温敏水凝胶的合成与性质

阳离子型温敏水凝胶的合成与性质王昌华卢英先曹维孝（北京大学化学与分子工程学院北京１００８７１）关键词热缩温敏水凝胶，Ｎ 异丙基丙烯酰胺，Ｎ 乙烯基吡啶氟硼酸盐，Ｎ 甲基 ４ 乙烯基吡啶硫酸甲酯盐水凝胶可看作是水溶或亲水高分子的一种亲水网络．多数...     

硫酸铜含量对硫酸铜与丁腈橡胶之间配位交联反应的影响

利用丁腈橡胶(NBR)的可配位侧基——腈基(—CN)与金属盐硫酸铜(CuSO4)的铜离子(Cu2+)之间的配位反应制备了一种配位交联CuSO4/NBR.影响该配位交联反应的因素众多,如热压温度、热压时间、增塑剂等等,考察了CuSO4含量对其的影响.通过X射线光电子能谱(XPS)、动态力学分析(DMA)、差示扫描量热分析(DSC)等手段对CuSO4与NBR之间的配位交联反应进行了分析,并对所得配位交联的CuSO4/NBR进行了交联密度及力学性能的测试.结果发现,随CuSO4含量的不断增加,CuSO4与NBR的配位交联程度逐渐增强,且所得配位交联CuSO4/NBR显示出从典型橡胶到韧性塑料再到脆性塑料的力学转变特性.另外,通过扫描电子显微镜(SEM)及X射线能谱仪(EDX)对材料的微观结构进行了分析,发现CuSO4在聚合物基体中不仅充当交联剂的角色,而且还起着增强填料的作用.     

丙烯酸酯系水乳漆的螯合固化

本文研究了含螯合单体2-AAEMA的丙烯酸酯共聚物乳漆的窒温螯合交联,用~1H-NMR测定了共聚物中2-AAEMA的含量,IR研究了螯合交联物的结构;比较了五种金属盐(M~(2 ))和不同2-AAEMA含量的共聚物乳液的实际交联效果,并测定了固化产物的交联程度、漆膜耐水性、硬度和力学性能。     

电化学阻抗谱研究聚合物凝胶电解质对染料敏化太阳能电池性能的影响

用甲基丙烯酸β-羟乙酯(HEMA)与N-乙烯基吡咯烷酮(NVP)共聚物P(HEMA-NVP)、甲基丙烯酸甲酯(MMA)与N-乙烯基吡咯烷酮共聚物P(MMA-NVP)为原料制备了聚合物凝胶电解质, 用电化学阻抗谱(EIS)研究了聚合物凝胶电解质中聚合物基质的结构与组成对准固态染料敏化太阳能电池(DSSCs)光伏性能的影响. 不同交联剂用量、不同HEMA用量的P(HEMA-NVP)共聚物及不同MMA用量的P(MMA-NVP)吸收液态电解质后分别形成HGelI、HGelII、MGel凝胶电解质. 结果发现, 随共聚物P(HEMA-NVP)中交联剂由0.1%(w, 下同)增大到0.6%时, 形成的HGelI 组装的DSSCs的光电转化效率(η)先增大后降低, 交联剂用量为0.4%时, DSSCs的η为最大, 为5.54%(光强100 mW·cm^-2). 同时, 比较HGelII 系列和MGel 系列DSSCs的光电性能参数发现, 含有羟基的HGel 系列的η要高于MGel 系列, 而后者的开路电压(V_oc)值高于前者. 在HGelII 系列中, HEMA含量为60%(w)时, DSSCs的η最高. 电化学阻抗谱分析表明共聚物中交联结构的不同影响了电池内部的界面阻抗及离子的传输, 引入羟基有利于降低界面阻抗. 通过调整共聚物中交联剂用量和羟基含量可改善DSSCs的光伏性能.     

制备氯甲基化聚苯乙烯交联微球的新方法

使用Lewis酸催化剂, 用自制的氯甲基化试剂1,4-二氯甲氧基丁烷(BCMB), 在室温下对聚苯乙烯交联微球(白球)进行氯甲基化反应, 制得了氯含量接近17%的氯甲基化聚苯乙烯交联微球(氯球); 通过红外光谱法与佛尔哈德分析法表征了产物的化学结构与组成; 考察了各种因素对氯甲基化反应过程的影响规律. 结果表明, 各种因素对白球氯甲基化过程的影响表现在两个方面: (1) 影响白球的氯甲基化程度; (2) 抑制或促进分子链之间通过Friedel-Crafts反应进一步交联, 影响微球的强度.     

Accelerated water tree aging of crosslinked polyethylene with different degrees of crosslinking

The effect of crosslinking degree on accelerated water tree aging in crosslinked polyethylene (XLPE) was investigated. The peroxide-crosslinking process was adopted to make XLPE specimens with different degrees of crosslinking by controlling the doping content of dicumyl peroxide (DCP) in low-density polyethylene (LDPE). The water blade electrode method was applied to accelerate water-tree aging of LDPE and XLPE specimens (hereafter referred to as the specimens), and their morphologies were observed using an optical microscope. The variation of crystalline morphology and anti-cracking performance of the amorphous region in the specimens were analyzed by differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and an electronic universal testing machine. Based on the experimental results, it was found that XLPE has great anti-water-treeing performance compared to LDPE. In addition, the higher the crosslinking degree, the better the anti-water-treeing performance. Although crystal growth is inhibited due to the crosslinking reaction, the density of tie molecular chains greatly increases in the amorphous region and exhibits significantly tighter lamellar stacking, which is the reason that water tree growth is restrained with increasing crosslinking degree.     

High Solid Acrylic–Melamine Latexes with Tunable Crosslinking Capability

Miniemulsion polymerization is employed to produce high solid content (50%) acrylic/melamine latexes with varied crosslinking capability, for their potential application as waterborne crosslinkable coatings. This synthesis strategy allows the efficient incorporation of a hydrophobic crosslinker, iso‐butylated melamine (iBMF), into polymer particles, and to obtain latexes with different iBMF concentrations and acrylic polymer with varied content of hydroxylic groups (OH–). The involved crosslinking mechanisms and the physical transformations during film thermosetting of acrylic/iBMF nanocomposite are exhaustively investigated by combining thermal, spectroscopic, and thermo‐mechanical analyses. The influence of reactive groups concentration (iBMF and OH– content in the acrylic polymer) on the rate of curing, the crosslinking degree, and consequently onto the sensitive properties of cured films are discussed here.     

(NBR/PVC)/CuSO_4复合材料中配位交联反应的研究

采用差示扫描量热法(DSC)和傅立叶转换红外光谱(FT-IR)对丁腈橡胶/聚氯乙烯合金/无水硫酸铜((NBR/PVC)/CuSO4)混合物的配位交联反应进行了研究.结果表明,(NBR/PVC)/CuSO4共混物在升温过程中出现两个放热峰,分别归因于腈基(—CN)和CuSO4之间的配位交联反应和体系中NBR/PVC的自交联反应.通过对共混物配位交联反应动力学参数的计算发现,混合物中CuSO4含量的多少并未对体系配位交联反应的进行产生影响.同时共混物中PVC的存在促进了配位交联反应的进行,降低了铜离子(Cu2+)与—CN之间配位交联反应的表观活化能Ea.     

不同交联剂对甲基丙烯酸-β-羟乙酯/E-51双甲基丙烯酸酯聚合物水凝胶性能的影响

以水溶性单体甲基丙烯酸-β-羟乙酯(HEMA)与大分子交联剂E-51双甲基丙烯酸酯(E-51-DMA)(质量比HEMA/E-51-DMA=90/10)为主要原料,分别引入了5种小分子交联剂:N,N′-亚甲基双丙烯酰胺(MBA)、二乙烯基苯(DVB)、双甲基丙烯酸乙二醇酯(EDMA)、1,1,1-三(丙烯酰氧甲基)丙烷(TAP)和2,2,2-三(丙烯酰氧甲基)乙醇(TAE),采用本体聚合方法合成了5个系列的聚合物水凝胶.研究了小分子交联剂的类型及用量对水凝胶溶胀性能、杨氏模量以及有效交联密度ve和聚合物-水相互作用参数χ的影响,并比较了不同交联剂的交联效率.结果表明,随着小分子交联剂用量的增大,水凝胶平衡含水量EWC逐渐降低,聚合物体积分数2逐渐增大,反映聚合物网络结构的有效交联密度ve以及热力学参数聚合物-水相互作用参数χ值也随之增大.通过理论交联密度和有效交联密度的线性拟合,得到所选用的5种小分子交联剂在E-51-DMA10/HEMA90水凝胶体系中的交联效率,其顺序为DVB>EDMA>TAE>MBA≈TAP.     

Foamed crosslinked LDPE/PP blends made by hot mold injection molding

Foamed and crosslinked blends of LDPE and i-PP were investigated. The specimens were made by hot mold injection molding process at the temperature of the mold of 210°C. Azodicarbonamide as foaming agent and 2,5-dimethyl-2,5-di(tert.-butylperoxy)hexane as crosslinked agent were used. The chemical changes as a result of the crosslinking were determined by gel content. Thermal behavior of the blends was studied by DSC. The difference of influence of crosslinking agent on chemical changes of both polymers was established. An improvement of the mechanical properties due to crosslinking between PE and PP on their interface was observed. The interaction on the PE/PP interface was confirmed by phase transition parameters determined on the basis of DSC-curves.     

甲基丙烯酸镁增强氢化丁腈橡胶的结构与形态和性能

用不同份量的甲基丙烯酸镁(MgMA)作增强剂,过氧化二异丙苯(DCP)作硫化剂,通过混炼和硫化过程的原位聚合制备了氢化丁腈橡胶/聚甲基丙烯酸镁(HNBR/PMgMA)纳米复合材料,用XRD、FTIR1、3C-NMR、SEM、TEM、DMA和交联密度分析等方法研究了其结构、形态和性能,并阐述了MgMA改性HNBR的相关机理.结果表明,MgMA在混炼过程中粒径明显变小,部分达到纳米级.硫化过程中发生原位自由基聚合,并部分接枝到HNBR分子链上,HNBR硫化胶和PMgMA有可能形成接枝互穿聚合物网络(接枝IPN).随着MgMA用量的增加,纳米复合材料硫化胶的定伸应力、拉伸强度、扯断伸长率、撕裂强度和热氧老化性能逐渐提高.当MgMA含量为30份时,体系的拉伸强度和扯断伸长率分别为38.5MPa和545%,并具有优异的热空气老化性能.MgMA能明显增加HNBR复合材料的储能模量,并降低其损耗因子.随着MgMA用量的增加,纳米复合材料硫化胶的总交联密度(Ve)和离子键交联密度(Ve2)增加,而共价键交联密度(Ve1)下降,表明离子键对HNBR/PMgMA纳米复合材料的力学性能起重要作用.     

Kinetics of photocrosslinking reactions of a DCPA/EA matrix in the presence of thiols and acrylates

The crosslinking efficiency and kinetics of a solid acrylic copolymer DCPA/EA (dicyclopentenyl acrylate/ethyl acrylate) matrix were investigated in the presence of pentaerythritol tetrakis (2-mercaptoacetate) (PETMP) or pentaerythritol tri- and tetraacrylates used as multifunctional crosslinking agents. The reaction of thiol and acrylate addition was sensitized by benzophenone (BP). The crosslinking efficiency of the DCPA/EA—BP—PETMP copolymer system, illuminated at high wavelengths (λ > 310 nm), was compared with that of the DCPA/EA matrix alone and the 2-component system copolymer DCPA/EA–BP. The concentrations of photosensitizer and crosslinking agent were varied from 1 to 10 mass %. The kinetics of tetrafunctional thiol addition and cyclopentene (pendant group of the DCPA/EA matrix) disappearance was followed through Fourier transform infrared (FTIR) and by determining the gel content. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2333–2345, 1997     

New trend of radiation application to polymer modification — irradiation in oxygen free atmosphere and at elevated temperature

Polycarbosilane (PCS) fiber as a precursor for ceramic fiber of silicon carbide was cured by electron beam (EB) irradiation under oxygen free atmosphere. Oxygen content in the cured PCS fiber was scarce and the obtained silicon carbide (SiC) fiber with low oxygen content showed high heat resistance up to 1973 K and tensile strength of 3 GPa. Also, the EB cured PCS fiber with very low oxygen content could be converted to silicon nitride (Si₃N₄) fiber by the pyrolysis in NH₃ gas atmosphere, which was the new processing to produce Si₃N₄ fiber. The process of SiC fiber synthesis was developed to the commercial plant.

The other application was the crosslinking of polytetrafluoroethylene (PTFE). PTFE, which had been recognized to be a typical chain scission polymer, could be induced to crosslinking by irradiation at the molten state in oxygen free atmosphere. The physical properties such as crystallinity, mechanical properties, etc. changed much by crosslinking, and the radiation resistance was much improved.     

Use of the successive self-nucleation and annealing technique to characterize <Superscript>60</Superscript>Co gamma irradiated HDPEs

The application of the Successive Self-nucleation and Annealing (SSA) thermal fractionation technique can yield detailed information of the structural changes induced in linear polyethylene by irradiation. The production of tertiary carbons during the crosslinking reactions can be equivalent to the structural heterogeneity present in branched polyethylenes since in both cases interruption of the linear crystallizable sequences occurs, and these are structural differences that can be easily detected by thermal fractionation. We demonstrate how correlations between melting point and short chain branching content employed for branched polymers can be useful to characterize the distribution of chain heterogeneity produced by crosslinking. As the radiation dose is increased and the crosslinking content also increases, the distribution of chain heterogeneity gets broader as detected by SSA. When the results are coupled with morphological observations made by transmission electron microscopy, valuable information on the morphological changes produced by crosslinking can also be ascertained, since the distribution of lamellar thicknesses substantially broadens with crosslinking. Such a broad distribution can also be predicted from SSA by simple calculations performed employing a modified version of the Gibbs–Thomson equation and is expected on the basis of random crosslinking reactions.     

THE PHYSICAL PROPERTIES OF POLY(2-HYDROXYETHYL METHACRYLATE) COPOLYMER HYDROGELS USED AS INTRAVAGINAL RINGS

Poly(2-hydroxyethyl methacrylate)(PHEMA)and poly(2-hydroxyethyl methacrylate-co-sodium methacrylate) [P(HEMA-co-SMA)]hydrogels with different compositions were prepared to be used as intravaginal rings,and their gelation time,water content,mechanical properties and morphology were investigated.The water content of PHEMA and P(HEMA-co-SMA) hydrogels decreased as the concentration of the monomer and the degree of crosslinking increased,while the water content significantly increased as the content of SMA,t...     

Radiation preparation of nano-powdered styrene-butadiene rubber (SBR) and its toughening effect for polystyrene and high-impact polystyrene

Nano-powdered styrene-butadiene rubber (NPSBR) was synthesized based on the styrene-butadiene rubber (SBR) latex via gamma radiation crosslinking followed by spray drying. Two functional monomers, 2-ethyl hexyl acrylate (2-EHA) and trimethylolpropane triacrylate (TMPTA) were used as crosslinking agents. It was found that both 2-EHA and TMPTA can improve the radiation crosslinking of SBR latex. Transmission electron microscope (TEM) and scanning electron microscope (SEM) revealed that the NPSBR has a particle size similar to that of SBR latex with a diameter of 100 nm due to the high degree of crosslinking of SBR. Mechanical testing results showed that NPSBR could toughen polystyrene (PS) and high-impact polystyrene (HIPS) effectively. In addition, NPSBR is more suitable to toughen HIPS than PS at low rubber content.     

结晶水对硫酸铜与丁腈橡胶之间配位交联反应的影响

利用动态力学分析(DMA)、差示扫描量热分析(DSC)、扫描电子显微镜(SEM)、平衡溶胀法、力学性能测试等分析手段, 通过研究五水硫酸铜(CuSO4·5H2O)填充的NBR考察了结晶水对CuSO4与NBR之间配位交联反应的影响. 结果表明, 结晶水的存在可以促进该配位交联反应.