原硅酸钠改性的聚偏氟乙烯接枝苯乙烯磺化膜的制备与性能

以过氧化苯甲酰(BPO)作引发剂,通过溶液接枝聚合法把苯乙烯接枝到原硅酸钠改性的聚偏氟乙烯(PVDF)膜上,磺化后得到聚偏氟乙烯接枝苯乙烯磺酸(PVDF-g-PSSA)电解质膜。采用多功能材料实验机表征了膜的力学强度,使用交流阻抗谱和气相色谱仪研究了原硅酸钠含量对PVDF-g-PSSA膜的质子导电性能和阻醇性能的影响。结果表明,原硅酸钠加入后,随着原硅酸钠含量的提高,PVDF-g-PSSA膜的质子电导率σ随原硅酸钠含量的提高而升高,力学性能得到改善,甲醇透过系数逐渐增大。     

原硅酸钠改性的聚偏氟乙烯接枝苯乙烯磺化膜接枝率的影响因素

以过氧化苯甲酰(BPO)作引发剂,通过溶液接枝聚合法把苯乙烯接枝到原硅酸钠改性的聚偏氟乙烯(PVDF)膜上,磺化后得到聚偏氟乙烯接枝苯乙烯磺酸(PVDF-g-PSSA)电解质膜。讨论了原硅酸钠的用量、接枝反应时间、反应温度、BPO浓度、苯乙烯单体浓度等对PVDF-g-PSSA膜接枝率的影响。结果表明,原硅酸钠用量为10%(质量分数,下同)、BPO浓度为0.016mol/L反应液、苯乙烯与四氢呋喃的比例为4∶1、在75℃水浴中,氮气保护下反应10h,可得到接枝率为16.1%、电导率为1.6×10-2S/cm的PVDF-g-PSSA电解质膜。     

改性聚偏氟乙烯接枝苯乙烯/丙烯酸磺酸电解质膜及其在CO传感器中的应用

以过氧化苯甲酰(BPO)作引发剂,通过溶液接枝聚合法把苯乙烯/丙烯酸同时接枝到原硅酸钠改性的聚偏氟乙烯(PVDF)膜上,磺化后得到聚偏氟乙烯接枝苯乙烯/丙烯酸磺酸(PVDF-g-PS/ PASA)膜.FTIR分析表明:苯乙烯和丙烯酸接枝到PVDF膜上;环境的相对湿度在20%～80%范围内,对PVDF-g-PS/ PASA膜电导率的影响基本不变,并达到0.0198S·cm-1,40℃保水率达99%.将膜应用于CO传感器中,传感器电流响应信号与CO气体浓度具有较好的线性关系.     

臭氧引发接枝制备聚偏氟乙烯亲水膜

利用臭氧的强氧化性,对溶解在N-甲基吡咯烷酮中的聚偏氟乙烯进行处理引入过氧基团,然后通过热引发接枝聚合亲水性聚乙二醇甲基丙烯酸酯(PEGMA),通过相转变法(phase inversion)制备具备亲水特性的PVDF分离膜.通过红外光谱、热重分析和接触角测试对接枝改性后的聚偏氟乙烯的结构和性能进行表征.红外光谱显示在1 734 cm-1处出现PEGMA的特征吸收峰,表明已成功接枝上PEGMA.接枝后的PVDF膜接触角降低到42°,表现出很好的亲水性;同时研究了接枝条件对改性膜亲水性的影响,随接枝单体浓度增加其亲水性增大;改性前后的聚偏氟乙烯膜的表面形貌通过扫描电子显微镜(SEM)分析表明,在相同成膜条件下改性后分离膜表面形貌发生很大变化,改性后制备的分离膜有较大的膜孔出现;水通量测试和牛血清蛋白吸附实验进一步表明,接枝改性可以明显改善PVDF分离膜的亲水性和抗污染性能.     

TMAH改性PVDF一步接枝PSSA质子交换膜的制备及性能

针对商业化Nafion系列全氟磺酸质子交换膜的甲醇渗透率高的问题,利用四甲基氢氧化铵(TMAH)液相改性聚偏氟乙烯(PVDF),以过氧化苯甲酰(BPO)为引发剂,一步将苯乙烯磺酸(SSA)接枝到改性的PVDF上,制备了用于替代Nafion膜的聚偏氟乙烯接枝聚苯乙烯磺酸(PVDF-g-PSSA)质子交换膜。研究了不同质量分数的TMAH甲醇溶液对PVDF-g-PSSA膜电导率和甲醇渗透率的影响。同时,利用傅立叶变换红外光谱(FTIR)和能谱扫描电镜(SEM-EDX)分析了膜的结构、形貌及硫元素分布情况。结果表明,TMAH使PVDF脱去部分HF产生碳碳双键且PSSA成功接枝到改性的PVDF骨架上,硫元素在膜内外分布均匀;PVDF-g-PSSA膜的电导率和甲醇渗透率随TMAH在甲醇中质量分数的增多而增大,TMAH质量分数为20%的膜的质子电导率在20℃下达到0.0890S/cm、常温下的甲醇渗透率为5.07×10-7 cm2/s;热重分析(TGA)表明,膜的热稳定性良好,耐热温度高达190℃。该膜作为电解质材料的直接甲醇燃料电池(DMFC)最大功率密度可达到17.085mW/cm2,且工艺简单、成本低,有望在实际中应用。     

低温等离子体接枝改性PVDF膜

采用低温等离子体接枝技术改性聚偏氟乙烯膜(PVDF),在PVDF膜表面引入疏水性单体苯乙烯,达到改变膜表面孔径的大小和孔径分布的目的.通过傅立叶红外光谱仪(FTIR-ATR)对改性前后的PVDF膜表面进行了结构分析,考察了PVDF膜接枝前后官能团的变化.采用示差扫描量热仪(DSC)分析了PVDF改性前后膜的孔径分布,考察了改性条件对膜孔径大小和分布的影响.通过扫描电子显微镜(SEM)和原子力显微镜(AFM)观测了PVDF膜改性前后表面形貌的变化.研究了接枝温度、接枝时间等接枝条件对PVDF改性膜纯水通量的影响.结果表明,随着照射时间和接枝时间的延长,PVDF改性膜的孔径分布变窄,纯水通量下降,接枝率提高.     

两性离子聚合物表面改性的聚偏氟乙烯抗污染膜的制备及性能

提高聚偏氟乙烯(PVDF)抗污染性能是改善PVDF应用效果的重要途径。文中通过自由基聚合的方法将抗污染材料——两性离子类化合物磺酸甜菜碱(DMAPS)接枝到碱处理过的PVDF膜表面。研究了接枝DMAPS后,PVDF膜表面的结构与性能变化,并初步探讨了改性后的PVDF膜对牛血清蛋白的吸附性能。结果表明,在PVDF膜表面接枝DMAPS后,膜表面孔洞减小,亲水性提高。虽然改性后的PVDF膜通量有所下降,但通过牛血清蛋白(BSA)的振荡吸附实验发现,两性离子改性膜表现出良好的抗蛋白质吸附性能。与PVDF原膜相比,改性膜在BSA溶液中通量下降率小,用水清洗后膜通量恢复率高。     

聚偏氟乙烯超滤膜的辐照接枝改性研究

聚偏氟乙烯超滤膜经Co-60辐照,接枝乙烯基单体,再经磺化,成为磺化聚偏氟乙烯超滤膜.研究了辐照剂量、接枝时间对接枝率的影响和磺化反应的条件等.试验表明,改性后膜的亲水性和抗污染性增强.此外,还讨论了膜改性的机理.     

聚两性电解质修饰聚偏氟乙烯膜的制备及抗污染性能

膜污染是膜分离技术广泛应用的瓶颈之一。文中通过自由基接枝聚合法将2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和甲基丙烯酰氧乙基三甲基氯化铵(DMC)接枝到聚偏氟乙烯(PVDF)膜上构建聚两性电解质化膜表面。研究了改性前后膜表面结构和抗污染性能的变化。随着单体投料量增加,聚两性电解质的接枝率逐渐增加;接枝聚两性电解质后,膜亲水性逐渐增强,膜表面孔尺寸减小。与纯PVDF膜相比,改性膜具有较低的蛋白质吸附量;在牛血清蛋白(BSA)溶液渗透过程中,膜的不可逆污染向可逆污染转化。由于可逆污染可通过简单的纯水清洗得到抑制,改性膜具有较高的通量恢复率。这个结果证明了聚两性电解质的引入赋予PVDF膜良好的抗污染性能。     

四乙基氢氧化铵改性聚偏氟乙烯接枝二氧化硅油水分离膜的研制EI北大核心CSCD

利用四乙基氢氧化铵(TEAH)和酸性高锰酸钾对聚偏氟乙烯(PVDF)粉体进行改性,得到含有羟基改性的PVDF,再将四氯化硅(Si Cl4)水解后的原硅酸通过分子内脱水缩合的方法接枝到改性PVDF骨架上,通过浸没沉淀相转移法制得聚偏氟乙烯接枝二氧化硅(PVDF-g-SiO_2)油水分离膜。研究了TEAH含量对PVDF粉体接枝二氧化硅(SiO_2)的接枝率和油水分离膜性能的影响,同时采用傅里叶变换红外光谱、扫描电镜-X射线能谱和视频光学接触角测量仪测试了膜的结构和表面接触角。结果表明,TEAH使PVDF脱去部分氟化氢(HF)产生碳碳双键,双键经酸性高锰酸钾(KMnO_4)氧化生成羟基,SiO_2接枝到改性的PVDF粉体,硅元素均匀地分散在分离膜中。PVDF粉体接枝SiO_2的接枝率随着TEAH的含量增加而升高,分离膜的水通量随接枝率的升高先增加后降低。TEAH质量分数为1.4%,分离膜的接触角降低到62.8°,膜中SiO_2的接枝率和水通量分别为6.25%、889.5 L/(m2·h),截留率和水通量恢复率分别达到94.3%和90.4%,衰减率为9.6%。     

Adsorption and recognizing ability of molecular imprinted polymer MIP-PEI/SiO(2) towards phenol

Firstly, functional macromolecule polyethyleneimine (PEI) was grafted onto the surfaces of silica gel particles via the coupling grafting method, the adsorption material PEI/SiO(2) was formed. Secondly, the molecular imprinting was carried out towards the macromolecule PEI grafted on the surface of silica particles using phenol as a template and diepoxyalkyl (669) as a crosslinking agent. Finally, imprinted polymer MIP-PEI/SiO(2) with high affinity, specific recognition ability and excellent selectivity for phenol was prepared. The adsorption and recognition ability of MIP-PEI/SiO(2) for phenol were researched by static methods. The experimental results show that MIP-PEI/SiO(2) possesses very strong adsorption and recognition ability for phenol. The saturated adsorption capacity could reach to 46.6 mg g(-1). The selectivity coefficients relative to resorcin and p-nitrophenol are 35.41 and 37.40, respectively. The empirical Freundlich isotherm was found to describe well the equilibrium adsorption data. pH and temperature have great influence on the adsorption capacity. Diluted hydrochloric acid solution is used as eluent, and the adsorbed phenol is eluted easily from MIP-PEI/SiO(2).     

新型室温酯化法制备纳米SiO2引发剂和原位引发聚合

提出了一种在室温、潮湿和大气环境等温和条件下,通过酯化反应在纳米SiO2微球表面接枝偶氮分子,合成纳米SiO2引发剂的新方法.使用这种纳米SiO2引发剂原位引发单体苯乙烯和甲基丙烯酸甲酯进行自由基聚合,在SiO2表面接枝聚苯乙烯或聚甲基丙烯酸甲酯.结果表明:用合成的纳米SiO2引发剂原位引发单体聚合后,在纳米SiO2表...     

Preparation and antibacterial characteristic of water-insoluble antibacterial material QPEI/SiO<Subscript>2</Subscript>

Polyethyleneimine (PEI) was grafted onto micron-sized silica gel particles via the coupling action of gamma-chloropropyl trimethoxy silane, and grafting particles PEI/SiO(2) was prepared. Then, polymeric reactions of two steps, tertiary amination reaction and quaterisation, were conducted for the grafted PEI. After quaterisation of the grafted polyethyleneimine, a composite particle, QPEI/SiO(2), was obtained. QPEI/SiO(2) is a water-insoluble antibacterial material. In this work, the antibacterial characteristic of QPEI/SiO(2) was mainly investigated using Escherichia coli (E. coli) as a disease-leading bacterium and adopting a colony count method. The effects of quaterisation degree of PEI and pH of the medium on the antibacterial ability of QPEI/SiO(2) were examined. The antibacterial mechanism of QPEI/SiO(2) was explored profoundly by using two enzyme activity determination methods, beta-D-galactosidase activity determination and TTC-dehydrogenase activity determination. The experimental results indicates that the water-insoluble antibacterial material QPEI/SiO(2) possesses strong antibacterial ability, for the bacterial suspension with a concentration of 10(9) CFU/ml, the antibacterial ratio of QPEI/SiO(2) can reach about 100% only with a dosage of 15 g/l and only for a contact time of 10 min. The main factors influencing the antibacterial ratio of QPEI/SiO(2) are the quaterisation degree of the grafted PEI and pH value of the medium. QPEI/SiO(2) with higher quaterisation degree has stronger antibacterial ability. In a certain range of pH value, the higher the pH value of the medium is, the stronger the antibacterial ability of QPEI/SiO(2 )is. Enzyme activity determination results show that the antibacterial mechanism of the water-insoluble antibacterial material QPEI/SiO(2) is based on a sterilization process and not only is a bacteriostasis action.     

Adsorption of phenol on a novel adsorption material PEI/SiO2

In this paper, functional macromolecule polyethyleneimine (PEI) was grafted onto the surfaces of silica gel particles via the coupling effect of gamma-chloropropyl trimethoxysilane (CP), and the novel adsorption material PEI/SiO2 with strong adsorption ability for phenol was prepared. The adsorption properties of PEI/SiO2 for phenol were researched by both static and dynamic methods. The experimental results show that PEI/SiO2 possesses very strong adsorption ability for phenol, and the saturated adsorption amount could reach to 160 mg g(-1). The empirical Freundlich isotherm was found to describe well the equilibrium adsorption data. pH and grafting amount of PEI have great influence on the adsorption amount. Diluted sodium hydroxide solution is used as eluent, and the adsorbed phenol is eluted easily from PEI/SiO2.     

纳米SiO2/PEA复合粒子的制备和表征

在经预处理的SiO2表面上通过乳液聚合反应接枝丙烯酸乙酯,用FT-IR和XPS对制备的纳米SiO2/PEA复合粒子进行了表征,研究了由复合粒子填充的PP/POE/SiO2复合材料的力学性能、结晶性能和结构形态。结果表明:通过乳液聚合反应成功地将EA接枝到纳米SiO2的表面上;由复合粒子填充的PP/POE/SiO2复合材料,纳米SiO2在基体中的分散尺寸约为100 nm,分布较均匀,复合材料的冲击强度和断裂伸长率均得到提高,在SiO2含量4%(质量分数)时,PPβ晶峰的强度最强。     

HDPE/SiO_2杂化材料的结晶行为

通过熔融接枝反应将乙烯基三甲氧基硅烷(A-171)接枝到高密度聚乙烯(HDPE)分子链上,以四乙氧基硅烷(TEOS)为前驱体,加入接枝的HDPE中,通过溶胶-凝胶法(Sol-Gel)制备了HDPE/SiO2杂化材料。采用DSC分析,研究了SiO2对HDPE结晶行为的影响。结果表明,SiO2在HDPE中起到异相成核的作用,使HDPE的结晶温度提高、微晶尺寸分布减小。随降温速率增大,结晶峰变宽,结晶温度Tp向低温方向移动。非等温结晶动力学研究表明,在冷却速率范围5℃/min~20℃/min内,杂化材料异相成核,近似一维生长。     

低填充SiO_2/聚丙烯纳米复合材料的拉伸特性

通过对纳米 Si O2 辐照接枝聚合改性 ,结合熔融共混工艺制备了低填充 Si O2 / PP纳米复合材料。发现在一定拉伸速度和粒子含量下 ,经辐照改性的 Si O2 / PP纳米复合材料韧性得到显著提高 ,同时强度也有所增加。随拉伸速度的升高 ,纳米复合材料的模量和强度逐渐增大 ,而韧性则随之下降。断面扫描电镜观察表明 ,改性纳米粒子填充复合材料韧性提高的机理以空化和基体大面积剪切屈服为主     

Chelating adsorption properties of PEI/SiO(2) for plumbum ion

In this paper, a novel adsorption material PEI/SiO(2) with strong adsorption ability towards heavy-metal ions was prepared. In preparation of PEI/SiO(2), functional macromolecule polyethyleneimine (PEI) was grafted onto the surfaces of silica gel particles via the coupling effect of gamma-chloropropyl trimethoxysilane (CP). The adsorption properties of PEI/SiO(2) for Pb(2+) ion were studied by both static and dynamic methods. The experimental results show that PEI/SiO(2) possesses very strong adsorption ability for Pb(2+) ion, the saturated adsorption amount could reach to 17.5mgg(-1), and the empirical Langmuir isotherm was found to describe well the equilibrium adsorption data. The pH and grafting amount of PEI have great influence on the adsorption amount. The Pb(2+) ions adsorbed on PEI/SiO(2) are eluted easily by diluted hydrochloric acid solution.     

低填充SiO2/聚丙烯纳米复合材料的拉伸特性

通过对纳米SiO2辐照接枝聚合改性,结合熔融共混工艺制备了低填充SiO2/PP纳米复合材料,发现在一定拉伸速度和粒子含量下,经辐照改性的SiO2/PP纳米复合韧性得到显著提高,同时强度也有所增加,随拉伸速度的升高,纳米复合材料的模量和强度逐渐增大,而韧性则随之下降,断面扫描电镜观察表明,改性纳米粒子填充复合材料韧性提高的机理以空化和基体大面积剪切屈服为主。