LARGELY IMPROVED BLOOD COMPATIBILITY OF POLYURETHANE BY BLENDING WITH FLUORINATED PHOSPHATIDYLCHOLINE POLYURETHANE

The improvement of biocompatibility of polyurethanes was investigated.The results demonstrate that the blood compatibility of polyurethanes can be further improved by just simply mixing with the fluorinated phosphatidylcholine poly(carbonate urethane)s(FPCPCUs).The solution blending was done by mixing poly(ether urethane)(PEU)with FPCPCU in different compositions.An increased blood compatibility of the blend films was observed with the increase of FPCPCU content,and when FPCPCU content reached to 40 wt%(40F...

SELF-ASSEMBLED MICRO-DOMAINS ON THE UPPERMOST SURFACE OF FLUORINATED POLY(CARBONATE URETHANE)S WITH FLUORINATED SIDE CHAIN ATTACHED ON HARD SEGMENTS

The surface phase separated structure of polyurethanes is always desired due to the advantage of better biocompatibility, compared with the homogeneous one. The key issue is how to control and characterize the surface morphology. In this work, we report the uppermost surface morphology of fluorinated poly(carbonate urethane)s with fluorinated side chains attached to hard segments as studied by AFM, XPS and contact angle measurement. A self-assembled micro-domain with the fluorinated side chain standing up on the uppermost surface has been proposed for polyurethane with higher fluorinated content, based on the result obtained.

Sulfonated fluorinated multi-block copolymer hybrid containing sulfonated(poly ether ether ketone) and graphene oxide: A ternary hybrid membrane architecture for electrolyte applications in proton exchange membrane fuel cells

A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer （SFMC）, sulfonated （poly ether ether ketone） （SPEEK） and I or 5 wt% graphene oxide （GO） was fabricated through a facile solution casting approach. The simple, but effective monomer sulfonation was performed for SFMC to create compact and rigid hydrophobic backbone structures, while conventional random sulfonation was carried-out for SPEEK. Hydrophilic-hydrophobic-hydrophilic structure of SFMC enhances the compatibility with SPEEK and GO and allows for an unprecedented approach to alter me- chanical strength and proton conductivity of ternary hybrid membrane, as verified from universal test machine （UTM） curves and alternating current （AC） impedance plots. The impact of GO integration on the morphology and roughness of hybrid membrane was scrutinized using field emission scanning electron microscope （FE-SEM） and atomic force microscope （AFM）. Ternary hybrid showed uniform intercalation of GO nanosheets throughout the entire surface of membrane with an increased surface roughness of 8.91 nm. The constructed ternary hybrid membrane revealed excellent water absorption, ion exchange capacity and gas barrier properties, while retaining reasonable dimensional stability. The well-optimized ternary hybrid membrane containing 5 wt% GO revealed a maximum proton conductivity of 111.9 mS/cm, which is higher by a factor of two-fold with respect to that of bare SFMC membrane. The maximum PEMFC power density of 528.07mW/cm2 was yielded by ternary hybrid membrane at a load current density of 1321.1 mA/cm2 when operating the cell at 70 ℃ under 100% relative humidity （RH）. In comparison, a maximum power density of only 182.06 mW/cm2 was exhibited by the bare SFMC membrane at a load current density of 455.56 mA/cm2 under same operating conditions.

Fluorinated polymer with high thermal stability for fabrication of 32-channel arrayed waveguide grating multiplexer on silicon

A cross-linkable fluorinated poly (ether ether ketone) (FPEEK) was synthesized for the fabrication of arrayed waveguide grating (AWG) multiplexer. The results of thermal gravimetric analysis (TGA) and near-infrared absorption spectrum show that the materials have high thermal stability and high optical transparency in the infrared communication region. The refractive index of FPEEK can be controlled easily by changing the fluorine content of the materials. The 32-channel AWG multiplexer is fabricated using the FPEEK and oxygen reactive ion etching technology. The AWG multiplexer exhibits that the insertion loss is from 12.8 to 17.8 dB and the channel crosstalk is less than-20 dB. The wavelength channel spacing and the center wavelength are 0.8nm and 1548nm, respectively.

Determining the degree of grafting for poly(vinylidene fluoride) graft-copolymers using fluorine elemental analysis

Acrylic acid (AAc) and styrene (St) were grafted onto poly(vinylidene fluoride) (PVDF) powder or membrane samples by pre-irradiation graft copolymerization.The grafted chains were proved by FT-IR spectroscopy analysis.The degree of grafting (DG) of the grafted PVDF was determined by fluorine elemental analysis (FEA) method,and was compared with the DGs determined by weighing method,acid-base back titration method and quantitative FT-IR method.The results show that the FEA method is accurate,convenient and universal,especially for the grafted polymer powders.

The Effect of Direct Gas Fluorination on Medical Grade Poly(methyl methacrylate)

Medical-grade poly(methyl methacrylate) (PMMA) is extensively employed in the fabrication of a variety of medical implants, including intraocular lenses (IOLs). However, a postoperative complication that leads to the failure of the implanted intraocular lenses has been recently identified. This process, termed calcification, occurs when calcium-containing deposits accumulate on the surface of the IOL. In this study direct gas fluorination was used to modify the surface of PMMA in an attempt to increase the service lifetime of the material in optical applications. PMMA discs exposed to a 20% fluorine/nitrogen gas mixture for 24 h were compared with untreated PMMA discs serving as control samples. Over time, both surface-fluorinated and untreated PMMA samples immersed in a simulated aqueous humour solution (SAHS) (pH 7.4, 35°C) were used to carry out in vitro studies. Attenuated total refractive Infrared spectroscopy (ATR-IR) Scanning electron microscopy (SEM), coupled with Energy dispersive X-ray analysis (EDX), showed that calcium-containing surface deposits were less abundant on surface-fluorinated PMMA compared with the control samples, indicating that the fluorinated surface was acting as a barrier to the deposits. Gravimetric analysis data showed that the decreased rate of diffusion compared with that of a control sample was due to the fluorinated surface.

新型含氟聚酰胺酰亚胺的合成与性能

由于芳香族聚酰胺酰亚胺(PAI)的溶解性较低,限制了其在溶液加工方法中的应用。为了提高PAI的溶液加工性、降低溶剂使用成本并提高热性能,研究了三苯环结构和氟取代对PAI的性能影响,以苯甲醛和对三氟甲基苯甲醛与2,6-二甲基苯胺为原料,合成了新的二胺化合物4-[(4-氨基-3,5-二甲基苯基)苯基甲基]-2,6-二甲基苯胺(ADPD)、4-[(4-氨基-3,5-二甲基苯基)[4-(三氟甲基)苯基]甲基]-2,6-二甲基苯胺(ADFPD),再与偏苯三酸酐酰氯合成了含新结构的PAI。通过傅里叶变换红外光谱、核磁共振氢谱等对单体和聚合物进行表征,通过分析证明成功合成新型PAI;采用差示扫描量热分析、热重分析、水接触角、溶解性能测试对PAI性能进行了表征。结果表明,制备的聚合物均具有良好的热稳定性能和溶解性,玻璃化转变温度大于300℃,在氮气的环境下5%热失重温度在430℃及以上,最大热失重温度在600℃以上;在类似化学结构上,对比未引入—CF_(3)的PAI-1和引入—CF_(3)的PAI-2的测试结果,发现PAI-2在溶解性和热性能上均优于PAI-1,并且能够明显降低聚合物的表面能,表明—CF_(3)能够有效提高PAI的部分性能。

端炔基含氟聚(酰亚胺-硅氧烷)的合成及其性能研究

为改善聚酰亚胺(PI)的溶解性和可融性,合成了两种含三氟甲基的芳香二胺单体,并以3,3′,4,4′-二苯甲酮四羧酸二酐(BTDA)作为二酐单体,选用端氨丙基聚二甲基硅氧烷(APPS)作为柔性链单元,间氨基苯乙炔(APA)作为活性封端剂,制备得到一系列加成型热固性含氟聚(酰亚胺-硅氧烷)共聚树脂(ABIS)。用核磁共振氢谱和红外表征ABIS的结构,并研究其溶解性、流变特性和固化后的热稳定性。用溶液成膜法制备了ABIS薄膜,研究了薄膜的物理特性。用热压法以T300碳布作为增强体制备了ABIS树脂基复合材料(T300CF/ABIS),并对其力学性能进行了探究。结果表明:硅氧烷链段和三氟甲基的引入可以显著提升PI树脂体系的流动性和溶解性。引入含氟芳香二胺后虽然ABIS固化树脂的5%热失重温度(T_(d5))有所降低,但仍超过425℃,800℃下的残留率(Y_(r800℃))达到26%。ABIS薄膜的拉伸强度和断裂伸长率分别高达15.8 MPa和65.3%,在40~107 Hz下的介电常数(ε)和介质损耗因数(tanδ)分别约为3.21和0.01且基本不变,超纯水在ABIS膜表面的接触角为94°。T300CF/ABIS复合材料的弯曲强度和层间剪切强度(ILSS)分别高达137.6 MPa和16.6 MPa。本研究制备的ABIS树脂有望在微电子器件和柔性防热复合材料中获得应用。

“Polymer-in-ceramic” based poly(ε-caprolactone)/ceramic composite electrolyte for all-solid-state batteries

Inspired by the concept of "polymer-in-ceramic",a composite poly(ε-caprolactone)(PCL)/ceramic containing LiTFSI is prepared and investigated as a solid electrolyte for all-solid-state batteries.The composite with the optimum concentration of 45 wt% LiTFSI and 75 wt% Li1.5Al0.5Ge1.5(PO4)3(LAGP,NASICON-type structure) exhibits a high ionic conductivity(σi=0.17 mS cm-1) at 30℃,a transference number of 0.30,and is stable up to 5.0 V.The composite electrolyte is a flexible and self-standing membrane.Solid-state LiFePO4//Li batteries with this composite electrolyte demonstrate excellent cycling stability with high discharge capacity of 157 mA h g-1,high capacity retention of 96% and coulombic efficiency of 98.5% after 130 cycles at 30℃ and 0.1 C rate.These electrochemical properties are better than other PCL-based allsolid-lithium batteries,and validate the concept of "polymer-in-ceramic" by avoiding the drawback of lower conductivity in prior "polymer-in-ceramic" electrolyte at high concentration of the ceramic.

气相色谱-质谱法测定纺织品中10种挥发性全氟及多氟化合物

建立了测定纺织品中10种全氟及多氟化合物(4种全氟烷基乙醇、4种全氟烷基丙烯酸酯和2种全氟辛酸酯)的气相色谱-质谱法(GC-MS)。比较了提取方式、提取溶剂、提取温度和提取时间对提取效率的影响,最终确定用叔丁基甲醚为提取溶剂,50℃超声提取40 min,萃取液经氮吹浓缩后过滤,目标物经DB-35ms毛细管柱(30 m×0.25 mm×0.25μm)程序升温分离,GC-MS SIM模式检测,外标法定量。结果表明:10种挥发性全氟及多氟化合物在10~200μg/L范围内线性关系良好,相关系数(r)均不低于0.9990,检出限(LOD)为0.002~0.030 mg/kg,定量限(LOQ)为0.007~0.090 mg/kg;不同材质纺织基体中,10种挥发性全氟及多氟化合物的高、中、低3个添加水平下的回收率为90.1%~108.5%,相对标准偏差(RSD)为1.2%~9.5%(n=6)。该方法可有效用于纺织品中10种全氟及多氟化合物的同时检测。

磷酸掺杂磺化聚(氟化亚芳基醚)-聚(环氧乙烷)共混膜的制备研究

为提高聚合物电解质膜燃料电池(PEMFC)的高温性能(150℃以上),采用磺化的聚芳基醚(SDF-F)和聚环氧乙烷(PEO)合成了新的共混膜,并使用磷酸掺杂;对新的共混膜进行了表征,并通过测量拉伸强度确定了酸掺杂共混膜的机械强度。结果表明,SDF-F和PEO成功共聚成共混膜且2种聚合物均匀混合,共混膜的磷酸掺杂水平随着PEO含量的增加而增加,当PEO的质量分数为60%时,掺杂的磷酸质量分数可达784%;共混膜的机械强度随着PEO含量的增加而下降,但即便PEO的质量分数为60%时,共混膜的拉伸强度仍有17 MPa。新共混膜能够完全满足高温聚合物电解质膜燃料电池的要求。

磷酸掺杂磺化聚(氟化亚芳基醚)-聚(环氧乙烷)共混膜的电化学性能研究

研究磷酸掺杂的磺化聚(氟化亚芳基醚)(SDF-F)和聚环氧乙烷(PEO)的共混膜的电化学性能。电化学阻抗谱分析EIS测量结果显示,其电导率与温度无关。根据不同质量比的混合膜在不同温度下的单电池性能测试结果,随着PEO含量越高,电池性能越稳定,SDF-F和PEO的质量比为6/4的混合膜的磷酸掺杂水平最低。由此可以推断,SDF-F/PEO混合膜的电池性能与磷酸水平的关系比与高温下的热稳定性关系更大。且在一定温度范围内,随着温度的升高,电极的性能会得到改善,其主要原因是由于温度升高会提高电极反应速率。然而,因为长时间稳定性测试结果表明其耐用性较低,故在高温PEM-FC中的应用的共混膜还需进一步改性。

氟化工园区周边玉米中全氟/多氟化合物的污染特征

食源性植物中全氟/多氟化合物(Per-and poly-fluorinated substances,PFASs)的污染问题已经引起人们的广泛关注。为研究典型氟化工园区周边玉米中PFASs的污染特征,在辽宁阜新氟化工园区周边的农用土壤中采集19个玉米样品,分析了根、茎、叶及果实中17种PFASs单体的含量与组成,并结合相关性分析及Arc Gis软件阐明了玉米中PFASs的富集规律及空间分布特征。结果表明,(1)氟化工园区周边农用地中玉米植株内总PFASs含量(∑PFASs)水平为15.88-620.7 ng·g^(-1),主要检出物质为短链(C≤6)PFASs、PFOA(perfluorooctanoic acid,全氟辛酸)和PFOS(perfluorooctane sulfonate,全氟辛烷磺酸)。(2)叶片是最具富集能力的器官。PFASs在叶片中总含量远高于其在根、茎及果实中含量。此外,碳链长度及官能团结构会影响玉米体内PFASs的含量。(3)PFOA与PFOS倾向富集在根部,而短链PFASs易在玉米植株内迁移。Spearman相关性分析表明,PFASs在根系中的总含量与其在茎(r=0.772,P=0.001)及叶片(r=0.400,P=0.046)中具有显著的正相关性。随着与氟化工园区距离的增加,玉米作物∑PFASs呈明显下降趋势。与氟化工园区周边1-2 km范围内玉米中PFASs含量相比,当玉米与氟化工园区的距离超过4 km时,其体内PFASs含量约减少了71.6%,表明当地氟化工生产可能是重要的点污染源。临近氟化工园区的土壤更容易受到工业废水和废渣的污染,玉米根系易从受污染的土壤中摄入PFASs,从而在体内发生富集作用;大气和灰尘摄入被认为是玉米叶片中高含量PFASs的另一来源。该研究分析了氟化工园区周边玉米中PFASs的含量与组成,为特征点污染源周边植物中PFASs的污染防治与治理提供了帮助。

煤矸石制备聚硅酸铝铁絮凝剂处理氟化工废水

以煤矸石为原料,采用“加碱焙烧—酸浸—聚合”工艺制备了聚硅酸铝铁(PAFS)絮凝剂,探究了碳酸钠添加量、焙烧时间、焙烧温度、酸浸固液比、酸浸温度、酸浸时间及聚合pH对PAFS絮凝效果的影响,并对制得的PAFS进行了表征。实验结果表明,PAFS的最佳制备条件为碳酸钠添加量40%(w)、焙烧时间2.0 h、焙烧温度800℃、酸浸固液比(g/mL)1∶6、酸浸温度60℃、酸浸时间2.0 h、聚合pH 3.6,此条件下,PAFS对氟化工废水的去浊率达96.94%,絮凝效果优于3种市售絮凝剂。表征结果显示,所制备的PAFS是聚硅酸与Al、Fe等金属离子络合后形成的无定型产物,为网状结构,具有良好的电中和能力及吸附架桥和网捕卷扫能力。

Synthesis of poly(pyridine-imide)s and their electronic memory performances

In this paper,poly(pyridine-imide)s,PI-Ph and PI-Naphth,were successfully synthesised and fabricated for use as memory devices.The Al/PI-Ph/indium tin oxide(ITO)device showed dynamic random access memory characteristics,whereas Al/PI-Naphth/ITO showed rewritable(FLASH)memory characteristics.Characterisation of their UV,cyclic voltammograms,and density functional theory,were used to illustrate the different memory behaviours.The results show that the stability of electric-field-induced-charge-transfer complexes can affect memory performance.

Anion Exchange Membranes Based on Chloromethylation of Fluorinated Poly（arylene ether）s

This report details the properties of fluorine-containing anion exchange membranes（AEMs） synthesized by chloromethylation and quaternization of fluorinated poly（arylene ether）s（FPAEs） based on decafluorobiphenyl and bisphenol A. Meanwhile, we compared their properties with those of their non-fluorinated counterparts, Udel-based AEMs. The reactivity of the chloromethylation of fluorinated poly（arylene ether）s was lowered by the strong elec- tron-withdrawing group, per-fluorinated biphenyl residue. Therefore higher temperature, more chloromethylation reagent, and longer reaction time were needed in the chloromethylation of FPAEs. Because of the hydrophobicity of fluorine, the swelling of FPAEs was depressed. In the FPAE-based AEMs, the water uptake of FPAE-1 membrane（F-1） was just 30%. There is a strong correlation between water uptake and conductivity for both Udel- and FPAE-based AEMs. Among all the membranes, the water uptake and the conductivity of FPAE-3 membrane（F-3） could reach up to 100% and 13.47 mS/cm respectively at 30 ℃. The mechanical properties of FPAE-based AEMs at room tempera- ture were worse than those of Udel-based ones because of the weak intermolecular interaction caused by the low po- larizability of fluorine. However, their high temperature mechanical properties are better, which can be explained in terms of low swelling.

新型含氟聚芳醚酮的合成与表征

A kind of highly fluorinated bisphenol monomer was synthesized. It was characterized by FTIR, 1H NMR and MS. 6F PEEK and 6F PEEKK were prepared via aromatic nucleophilic substitution, based on [3,5 di(trifluoromethyl)] phenylhydroquinone and difluoro monomers. The T gs of 6F PEEK and 6F PEEKK are 423 and 436 K, respectively. The 6F polymers exhibit a high thermal stability and good solubility. The flexible, creasable and transparent thin films were easily obtained by compression moulding and solution casting.

可交联含氟聚醚醚酮的合成

A novel crosslinkable fluorinated poly(ether ether ketone) with acetylenylbenzene end groups was prepared by solution condensation. The chemical structure of such polymer was confirmed by FTIR and 1H NMR. The crosslinking behavior and thermal stability were investigated by DSC and TGA respectively. The DSC thermogram for the first heating run shows a glass transition of 6F-PEEK at about 395 K and a exothermic peak correspongding to the self-crosslinking reaction of fluorinated poly(ether ether ketong) at about 700 K. For the second heating run, the exothermic peak disappered and the glass transition shifted to a higher temperature. The crosslinked polymer shown excelent thermal stability and solvent-resistence. The temperature for 5% weight loss was 774 K and the self-crosslinked polymer was no more disolved by polar solvents, which disolved in before crosslinking, such as DMF, DMAc and NMP. This kind of polymer may be a potential material used as electro-optical devices.

苯乙炔封端的可交联含氟聚芳醚的合成及性能

The crosslinkable trifluoromethylated poly(aryl ethers) terminated with phenylethynyl moieties(11F-PAE-PEP)s were prepared in two step syntheses. The structure of 11F-PAE-PEP was confirmed by FTIR and 1H NMR. The crosslinking behavior was studied by DSC. There is a remarkable increase of T g after crosslinking of the poly(aryl ethers). The T g values of crosslinked polymers were 437 and 446 K, respectively. The crosslinked polymers could not be soluble in common organic solvents, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, chloroform, and tetrahydrofuran. The temperatures at a 5% mass loss of the crosslinked polymers in air were above 789 K. They showed a good optical property, too. This kind of polymers will be the promising materials used as the microelectronics and optical waveguide devices.

低介电常数含氟聚芳醚的合成

A kind of high Fluorine-containing poly(aryl ether) without side reaction was synthesized in a two-step synthesis. Its structure was confirmed by FTIR, 1H NMR and 19F NMR. The polymer shows an excellent thermal stability, good solubility, low water absorption, low dielectric constant and low refractive index. Flexible and transparant thin film can be easily obtained by compression moulding or solution casting. The polymer would be a promising material used for microelectronics and waveguide devices.