Effect of Irradiation on Crystallinity and Mechanical Properties of Ultrahigh-Molecular-Weight Polyethylene

Ultrahigh-molecular-weight polyethylene(UtlMWPE) has been irradiated (0-40 Mrad) with a Co^(60) source at room temperature under vacuum. Their crystallinity has been investigated by DSC and SAXS A significant increase of heat of fusion can be seen at low irradiation doses, which is attributed to crystallization caused by chain scission during the process of irradiation. It is also observed that thickness of lamellae changes with irradiation dose. Young's modulus has been improved significantly after irradiation at low doses.

PREPARATION OF HIGH DENSITY POLYETHYLENE/POLYETHYLENE-BLOCK-POLY(ETHYLENE GLYCOL)COPOLYMER BLEND POROUS MEMBRANES VIA THERMALLY INDUCED PHASE SEPARATION PROCESS AND THEIR PROPERTIES

High density polyethylene （HDPE）/polyethylene-block-poly（ethylene glycol） （PE-b-PEG） blend porous membranes were prepared via thermally induced phase separation （TIPS） process using diphenyl ether （DPE） as diluent. The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry （DSC）. By varying the content of PE-b-PEG, the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy （SEM） and wide angle X-ray diffraction （WAXD）. The chemical compositions of whole membranes and surface layers were characterized by elementary analysis, Fourier transform infrared spectroscopy-attenuated total reflection （FTIR-ATR） and X-ray photoelectron spectroscopy （XPS）. Water contact angle, static protein adsorption and water flux experiments were used to evaluate the hydrophilicity, antifouling and water permeation properties of the membranes. It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes. In the investigated range of PE-b-PEG content, the PEG blocks could not aggregate into obviously separated domains in membrane matrix. More importantly, PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation, but also enrich at the membrane surface layer. Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity, protein absorption resistance and water permeation properties, which would be substantially beneficial to HDPE membranes for water treatment application.

PHASE EQUILIBRIUM FOR THE TERNARY SYSTEM VINYL CHLORIDE-CHLORINATED POLYETHYLENE-POLY(VINYL CHLORIDE)

Swelling capacity of vinyl chloride (VC) in chlorinated polyethylene (CPE) with 25—40 wt% Cl at temperature 30—57℃ was studied and their relationships were correlated with Langmuir and Freundlich adsorption equations. A ternary phase diagram for VC-CPE-PVC was also established. In-situ polymerization conditions of CPE-g-VC were proposed and CPE content control was analyzed for the manufacturing process of CPE-g-VC graft product based on results of phase equilibrium study.

Uniform to Accelerated Crystal Twisting Transition in Deuterate Polyethylene/Poly(ethylene-alt-propylene) Blend Films

A uniform to accelerated crystal twisting transition is observed in deuterate polyethylene/poly（ethylene-alt- propylene） （d-PE/PEP） blend films. And the band period is a function of initial d-PE concentration, quench depth and annealing time of phase separation. As Keith and Padden suggested, twisting of lamella is due to the unbalanced stress on its both sides, which can supply a satisfying explanation to banded spherulites formed in homogeneous systems. When it comes to d-PE/PEP blend system, in homogeneous 99% d-PE/PEP （weight fraction of d-PE） blend film, the formation of banded spherulite is observed as a result of uniform twisting of ribbon like d-PE lamellae along the radial direction. With the amorphous PEP piling up, it transfers into accelerated edge-on to fiat-on twisting due to crystallization assisted phase separation. The mechanism can be interpreted as following： d-PE molecules must inter-diffuse to the twisting growth front to continue the secondary nucleation and growth process. Meanwhile, the amorphous PEP molecules are rejected and accumulated at the twisting growth front. Once the d-PE lamella begins to twist because of unbalanced stress on both sides, the accumulated rubber phase at the growth front strengthens the unbalance and accelerates the edge-on to flat-on twisting. The concentration wave propagates further away with constant speed, and leads to concentric ring pattern with periodic nonuniform twisting along the radial direction. Since this is a kinetic effect, the band period can be controlled through initial d-PE concentration, quench depth and annealing time of phase separation. Our result shows that crystallization assisted phase separation can modify lamella growth kinetic pathway, thereby assisting concentric ring pattern formation.

Preparation and Thermo-Responsive Properties of Poly(Oligo(Ethylene Glycol)Methacrylate)Copolymers with Hydroxy-Terminated Side Chain

Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate(P(EO2-co-EG4/5))are synthesized via atom transfer radical polymerization(ATRP).The successful synthesis and the narrow polydispersity index(PDI)of two copolymers are indicated by 1H nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)analyses.The transition behaviors of polymers in the aqueous solution are demonstrated by changes in turbidity and particle sizes.The transition behavior of P(EO2-co-EG4/5)is found to be milder than that of P(EO2-co-EO4/5).Moreover,the presence of hydrogen bonds without thermo-responsive properties established by hydroxyl groups in the end-side chain of P(EO_(2)-co-EG_(4/5))hinders the dehydration at the transition temperature(TT).Attenuated total reflection Fourier transform infrared spectrometry(ATR-FTIR)analysis along with contact angle measurements reveals that both P(EO_(2)-co-EO_(4/5))and P(EO_(2)-co-EG_(4/5))films undergo phase transitions from hydrophilicity to hydrophobicity above TT.By examining the swelling and collapse behaviors of the polymer films during phase transitions,it can be concluded that the end hydroxyl groups may establish hydrogen bonds with neighboring ether groups within the films,which remain intact throughout the phase transition process due to their strong bonding interactions.This leads to an increase in steric hindrance within swollen films thereby impeding dehydration processes and inducing hysteresis during phase transitions.

基于废弃PET的环氧超支化聚酯扩链剂应用性能

以废弃聚对苯二甲酸乙二酯(PET)的降解产物为核心,制备了环氧超支化聚酯扩链剂(EHBP),探究了该扩链剂对聚对苯二甲酸-己二酸丁二酯/聚乳酸/碳酸钙(PBAT/PLA/CaCO_(3))三元复合材料微观结构、热性能、力学性能的影响。结果表明,以PET降解产物制备的EHBP对复合材料有明显的增容作用。扩链剂中的高活性环氧基团能够与PBAT和PLA上的端羧基、端羟基发生开环加成反应,形成扩链大分子以增强PBAT和PLA之间的界面相互作用。当EHBP添加量达到0.6份时,可以明显观察到两相间变得模糊、孔洞减少。缺口冲击强度由6.48 kJ/m^(2)增加到43.02 kJ/m^(2),拉伸强度由10.15 MPa增加到24.59 MPa,断裂伸长率由11.8%增加到56.72%。

星型PLLA-PEG嵌段共聚物纤维膜的制备及其亲水性能

星型结构相比较于线型结构具有更稳定的形态和更优异的力学性能。选用季戊四醇(PET)为引发剂,辛酸亚锡(Sn(Oct)_(2))为催化剂,通过L-丙交酯(L-LA)的开环聚合(ROP)制备星型端羟基聚(L-丙交酯)(s-PLLA),并与聚乙二醇(PEG,相对分子质量为1000)缩合制备四臂星型聚(L-丙交酯)-聚乙二醇共聚物(s-PLLA-PEG)。采用^(1)H-核磁共振、^(13)C-核磁共振、傅里叶变换红外光谱、超高效聚合物色谱仪对产物进行表征,并用静电纺丝技术制备s-PLLA-PEG纤维膜进行亲水性能测试。结果表明:s-PLLA-PEG共聚物被成功合成;相对于s-PLLA,s-PLLA-PEG的熔体温度和玻璃化转变温度降低,柔韧性得到改善,韧性增强;s-PLLA-PEG纤维膜对水的接触角是84.10°,随着时间的推移,接触角逐渐减小,最终水被纤维膜完全吸收,相比较s-PLLA纤维膜具有更强的亲水性。该研究表明,PEG嵌段的引入可以有效改善s-PLLA纤维膜的亲水性,展现出静电纺s-PLLA-PEG纤维膜在医用敷料领域的应用前景。

Irradiation and flame retardant effect of poly[bis(phenoxyphosphazene)] and magnesium hydroxide in LDPE composites

Poly[bis(phenoxyphosphazene)](PBPP) and magnesium hydroxide(MH) are used as a flame retardant blend with low-density polyethylene(LDPE) for the nuclear cable. This study aims to investigate the effects of PBPP in MH-LDPE blend composites on flame retardance and electron beam irradiation. The structure, morphology,and properties of the blend composites irradiated by an electron beam to different absorbed doses were characterized. The results indicated that PBPP provides lubrication during processing. As the PBPP content in the blend increases the melt flow rate at 20 phr MH, meaning the material is easier to process. The higher the PBPP content, the higher the limiting-oxygen index. The elongation at the break of the PBPP containing composites(at 50 phr MH) was evidently higher than the non-PBPP ones at different absorbed doses by electron beam irradiation. The thermogravimetric analysis results indicated that the improved mechanical property, resulting from electron-beam irradiation, could be attributed to the consumption of PBPP.

Comparison of different cationic polymers efficacy in fabrication of alginate multilayer microcapsules

In past decades, alginate-based multilayer microcapsules have been given important attention in various pharmaceutical investigations. Alginate-poly l lysine-alginate(APA) is studied the most. Due to the similarity between the structure of polyethyleneimine(PEI) and poly-L-lysine(PLL) and also lower price of PEI than PLL, this study was conducted to compare the efficacy of linear(LPEI) and branch(BPEI) forms of PEI with PLL as covering layers in fabrication of microcapsules. The microcapsules were fabricated using electrostatic bead generator and their shape/size, surface roughness, mechanical strength, and interlayer interactions were also investigated using optical microscopy, AFM, explosion test and FTIR, respectively. Furthermore, cytotoxicity was evaluated by comparing the two anionic final covering layers alginate(Alg) and sodium cellulose sulphate(NCS) using MTT test. BPEI was excluded from the rest of the study due to its less capacity to strengthen the microcapsules and also the aggregation of the resultant alginate-BPEI-alginate microcapsules, while LPEI showed properties similar to PLL. MTT test also showed that NCS has no superiority over Alg as final covering layer. Therefore, it is concluded that, LPEI could be considered as a more cost effective alternative to PLL and a promising subject for future studies.

Effect of poly(ethylene glycol) molecular weight on CO_2/N_2 separation performance of poly(amide-12-b-ethylene oxide)/poly(ethylene glycol) blend membranes

Membranes from block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074) and its blends with different molecular weight poly(ethylene glycol)(PEG)(200, 400, 600, 1500, 4600 and 8000) were prepared. The thermal properties and structures of Pebax1074/PEG blend membranes were characterized by DSC and SEM, and the gas permeation properties of CO_2 and N_2 were also investigated at different temperatures. For Pebax1074/PEG blend membranes with low molecular weight PEG(MW≤ 600), higher gas permeabilities than Pebax1074 were achieved. The permeability increased with the increase of PEG molecular weight. The addition of low molecular weight PEG resulted in decrease in activation energy of permeation. For Pebax1074/PEG blend membranes with high molecular weight PEG(MW≥ 1500), due to the melt of PEO phase crystals, the gas permeation properties of blend membranes were temperaturedependent, which could be divided into crystalline region, transition region and amorphous region according to two different transition temperatures. PEG molecular weight and operation temperature determined different gas permeation properties of Pebax1074/PEG blend membranes in three regions. The activation energies of permeation in crystalline region were larger than those in amorphous region.

Chemical Oxidative Synthesis and Conductivity of Poly(3,4-ethylenedioxythiophene)

[Objective] This paper was to introduce the chemical oxidative synthesis process, properties and test methods of 3,4-ethylenedioxythiophene(EDOT). [Method] The poor water solubility of EDOT was solved by using polyethylene glycol 20000(PEG) as the surfactant. The monomer was polymerized by chemical oxidative synthesis. The product was analyzed and verified by infrared spectrum, X-ray diffraction, ultraviolet-visible absorption spectra.[Result] The conductivity of the product was the best when the mass ratio of PEG and EDOT was 1∶1. The effects of oxidant dose and reaction time on the conductivity and yield of the product showed certain regularity. [Conclusion] EDOT could be polymerized by PEG and FeCl3, and the polymerization product was PEDOT.

Synthesis and Characterization of Thermoplastic Poly(Ester Amide)s Elastomer (TPEaE) Obtained from Recycled PET

A series of thermoplastic polyester elastomer (TPEE) and thermoplastic poly(ester amide)s elastomer (TPEaE)copolymers were obtained by depolymerizing PET (polyethylene terephthalate) by which the waste PET canbe efficiently recovered and recycled into value-added products from a practical and economical point of view.The structure of TPEE and TPEaE was identified using nuclear magnetic resonance (NMR) and Fourier transforminfrared spectroscopy (FT-IR). Differential scanning calorimetry (DSC) data showed that the melting temperature(Tm) decreased with the amide content increased. The glass transition temperature (Tg) was increased as introducingthe amide group, and the formation of amide-ester and amide-amide hydrogen bonds increased the intermolecularchain force. The intrinsic viscosity (η) showed the tendency of increment from TPEE (0.53 dL g^(−1)) to TPEaE-5%(0.72 dL g^(−1)) due to the reinforcement of hydrogen bond and chain entanglement.

Combretastatin A4/poly(L-glutamic acid)-graft-PEG conjugates self-assembled to nanoparticles

Combretastatin A4(CA4) possesses varying ability to cause vascular disruption in tumors,while the short half-life, low water solubility and deactivation of many CA4 analogs during storage limited its antitumor efficacy and drug stability. A novel macromolecular conjugate of CA4(CA4-PL) was synthesized by covalent bonding of CA4 onto poly(L-glutamic acid)-graft-polyethylene glycol(PLG-g-PEG) via Yamaguchi reaction. The obtained CA4-PL was characterized by ~1H NMR, GPC, and UV methods, and the properties of the nanoparticles composed of CA4-PL, including critical aggregation concentration, size and size distribution, and morphology, were investigated. CA4-PL can self-assemble to form micelle-like nanoparticles of 80～120 nm in diameter, which may have potential to improve the blood circulation period as well as the targetability of CA4, and find applications to treat various tumors when combined with traditional chemotherapy or radio therapy.

Characterization and separation of DNA complexes containing poly-L-lysine with or without the modification of PEG by capillary electrophoresis

The characterization of complexes is particularly critical for quality control and development of gene delivery systems. Here, the method of capillary zone electrophoresis （CZE） for the characterization of DNA and polyoL-lysine （MW 28 500） or DNA and poly-L-lysine modified with polyethylene glycol （MW10 000） complexes at various charge ratios in phosphate buffer is described firstly. During the characterization, DNA complexes can be separated into various components with different charge-to-mass ratio, i.e, components with single physicochemical property. And also the size and zeta potential of complexes were characterized by using photon correlation spectroscopy. This method is useful to characterize various complexes formed by DNA and polycations, and has the potential to separate complexes into homogeneous component for better transfection efficiency in vitro and in vivo in future.

PLA/PBS/PEG共混体系非等温热分解动力学

为了探究聚乳酸/聚丁二酸丁二醇酯/聚乙二醇(PLA/PBS/PEG)共混体系的热分解行为,通过熔融开炼共混法制备了PLA/PBS/PEG共混体系,利用同步热分析仪考察了不同加热速率下复合材料的热解行为。使用无模型方法Kissinger方程和Ozawa方程计算出了平均活化能,运用模型方法Coats-Redfern方程,将不同的热解机理函数带入其中,计算出活化能,将两个活化能进行对比,以明确最合适的反应模型。结果表明,该复合材料的热解机理函数为G(α)=[1-(1-α)^(-3)]/(-3),即随机成核随后生长。

环境中的微塑料污染及降解

由于塑料制品的过度使用并且难以进行回收,导致大部分塑料进入自然环境中。在生物和非生物因素共同作用下其理化性质发生变化,对大气、水体、土壤造成严重的微塑料(MPs)污染,甚至对人体产生了一定程度的负面影响。随着环保意识的提高,寻求一种高效绿色的塑料降解方式显得尤为重要。生物降解因绿色环保、无二次污染等优点引起了人们的广泛关注。本文首先概括了大气、水体、土壤中的MPs污染的来源及危害,其次进一步总结了塑料的生物降解与非生物降解与不同类型塑料的酶降解机制,最后,对MPs的生物降解未来的研究方向进行了展望。

柱[5]芳烃共价偶联聚乙二醇聚拟轮烷滑环材料的合成与流变性质

通过柱[5]芳烃与高分子量聚乙二醇共价交联构筑了系列互穿交联聚合物,经过退火制备了柱芳烃-聚乙二醇互穿滑环材料.核磁滴定实验、模型分子互穿实验以及高分子量聚乙二醇互穿等研究结果表明,在该聚合物中柱[5]芳烃与聚乙二醇发生晶态络合并达到互穿平衡. X射线粉末衍射及差示扫描量热-热重分析实验结果证实该互穿滑轮聚合物具有良好的晶型结构、热性能及热稳定性,由分子量为1×106的聚乙二醇合成的固态聚拟轮烷表现出较好的滑环效应,其流变行为受到链长度、滑环数量和滑环运动等因素影响.在引入滑环分子柱[5]芳烃后,该固体滑环材料表现出较好的热稳定性、柔性以及弹性机制响应性.

酰胺化反应制备聚(对苯二甲酰十二碳二元胺-共-对苯二甲酸乙二醇酯)共聚物

文中以十二碳二元胺(DDMD)和聚对苯二甲酸乙二醇酯(PET)为原料,环丁砜为溶剂,制备了聚(对苯二甲酰十二碳二元胺-共-对苯二甲酸乙二醇酯)(Poly(12T-co-ET))共聚物。考察了反应温度、投料比和溶剂用量对产物相对黏度和转化率的影响,确定其最佳工艺条件为,反应温度为210°C、DDMD与PET的投料摩尔比为1.1:1、PET与溶剂的质量比为1:10,得到产物的相对黏度为1.37、转化率为82.1%。通过傅里叶变换红外光谱和核磁共振氢谱确认了产物的结构。差示扫描量热分析和热失重分析结果表明,产物的熔点为234°C、结晶温度为201°C,初始热分解温度为357°C。拉伸强度为37.0 MPa、断裂伸长率为9.32%、弯曲强度为49.2 MPa、缺口冲击强度为1.5 kJ/m^(2)。动态力学热分析结果显示其玻璃化转变温度(T_(g))为91°C。尽管共聚物的综合性能较差,但仍可以作为基体树脂进行共混改性使用,同时,该聚合方法对PET的回收和环境保护具有一定的实用价值。

INDUCED CRYSTALLIZATION BEHAVIOR OF POLY(ETHYLENE ADIPATE) BY HIGHLY ORIENTED POLYETHYLENE

The crystallization behavior of poly（ethylene adipate） （PEA） on highly oriented high-density polyethylene （PE） substrate both from solution and isotropic melt was studied by means of optical microscopy, differential scanning calorimetry, atomic force microscopy and electron diffraction. The results show that the PE influences the crystallization of PEA strongly, which results in an epitaxial growth of PEA with well ordered structure. At the boundary of the PE substrate, a transcrystalline PEA layer is observed. Fine structural observation illustrates that the PEA grows on the PE substrate in edge- on lamellae with fixed orientation. Electron diffraction demonstrates that the epitaxial organization of PEA on PE occurs with both polymer chains parallel, which leads to the （00l） PEA diffractions inclined ±23.5° to the chain direction of PE crystals. Combining the real space morphological observation and electron diffraction results, it is concluded that the epitaxial PEA edge-on lamellae are folded in the {00l} lattice planes.