One step graft copolymerization of acrylic acid and sodium styrene sulfonate onto high－density polyethylene film by preirradiation method

High-density polyethylene(HDPE)films were irradiated by ^60Co gamma ray with a dose of 100kGy in air and then immersed in aqueous solution of acrylic acid(AA) and sodium styrene sulfonate(SSS) at different temperature.The effects of grafting conditions such as temperature,reaction time ,Mohr‘s salt concentration,and total concentration of monomer on grafting yield were studied.Both grafting yield of AA and SSS onto HDPE respectively increases with total concentration of monomer on grafting yield were studied.Both grafting yield of AA and SSS onto HDPE respectively increases with total concentration of monomers.The highest grafting yield was observed at 3mol/L monomers where the grafted PE swelled to the largest extent in the monomers mixture.The grafting yield increases with reaction time and then levels off.At higher temperature,the grafting yield decreases with Mohr‘s salt concentration,but increases at low temperature when Mohr‘s salt concentration is 0.083%.Which can be interpreted that in the presence of Fe^2 diperoxides and hydroperoxides may decompose at low temperature to form radical which can initiate the grafting.The physical and chemical properties of grafting films were also investigated.     

Proton exchange membranes prepared by radiation-induced graft copolymerization from binary monomer mixtures onto poly(tetrafluoroethylene-co-hexafluoropropylene) film

Sulfonic acid proton exchange membranes based on a poly(tetrafluoroethylene-co-hexafluoropropylene) film were synthesized through the single-step graft copolymerization of sodium styrenesulfonate and acrylic acid monomers from binary monomer aqueous solutions using the electron beam pre-irradiation method in air. The effects of the various polymerization parameters (absorbed dose, reaction time, and monomer ratio) on the degree of grafting were studied.A correlation between the degree of grafting and some of the physical-chemical properties (water uptake and ion-exchange capacity) of the synthesized copolymers was established. The distribution of the sulfonic acid groups was investigated across the thickness of several membranes in order to gain a better understanding of the graft copolymerization process from binary monomer aqueous solutions onto the fluorinated film and to synthesize membranes with optimal physical-chemical properties.     

HDPE预辐照接枝SSS与AA体系的反应动力学研究

采用电子束引发预辐照接枝方法在高密度聚乙烯(HDPE)上接枝丙烯酸(AA)与对苯乙烯磺酸钠(SSS)两种单体,以制备含磺酸和羧酸基团的双功能基阳离子交换膜。研究发现,接枝速率与辐照剂量、单体总浓度及反应温度密切相关。接枝反应的活化能为22．2kJ／mol。傅立叶变换红外光谱(FTIR)测试表明,接枝膜上引入了磺酸基团和羧酸基团。     

HDPE辐照接枝AA与SSS体系阻聚剂用量对接枝率的影响

考察了预、共辐照两种接枝方法中阻聚剂硫酸铜和摩尔盐对接枝率的影响规律。发现不同接枝方法的阻聚剂硫酸铜和摩尔盐对接枝率有着不同的影响规律。共辐照接枝体系中加入相同量的阻聚剂时,摩尔盐的阻聚效果明显弱于硫酸铜。空气气氛预辐照接枝时,较高反应温度下接枝率随摩尔盐用量的增加呈下降趋势,而反应温度较低时,随着摩尔盐用量的增加接枝率先升高,出现峰值后又降低。这是因为在摩尔盐的催化下,过氧化物可以在较低的温度下分解产生烷基自由基,从而引发接枝反应。     

聚-L-乳酸辐射接枝N-乙烯基吡咯烷酮的研究

以甲醇为溶剂,采用辐射接枝法制备了聚-L-乳酸（Poly-L—lacticacid,PLLA）/N-乙烯基吡咯烷酮（N-vinyl pyrrolidone,NVP）接枝共聚物（Poly（L—lactide）-g—poly（N—vinyl pyrrolidone）,PLLA—g—PVP）。研究了不同吸收剂量对接枝率的影响,并用傅立叶变换红外光谱（Fourier transform infrared spectrometer,FT—IR）、核磁共振氢谱（Nuclear magnetic resonance,^1HNMR）、差示扫描量热法（Differential scanning calorimeter,DSC）对接枝共聚物进行了表征。结果表明,共聚物接枝率随吸收剂量的增加而增加,吸收剂量为5 kGy时,接枝率可达14．9％;NVP链段C=O吸收峰出现在1660—1671cm^-1,随吸收剂量的增加移向高波数;在^HNMR中PLLA链段甲基和次甲基峰面积比大于3：1,说明接枝反应可能发生在PLLA次甲基碳上;PLLA的结晶焓随吸收剂量的增加而增加;接枝共聚物的结晶焓随吸收剂量的增加而降低。     

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.     

SBS粉体预辐射接枝丙烯酸研究

以60Coγ射线为辐射源,对SBS粉体在空气中进行预辐照,然后将一定量粉体置于丙烯酸水溶液体系中进行接枝反应。研究了反应时间、反应温度、单体浓度和吸收剂量对接枝率的影响。傅里叶变换红外光谱(FTIR)分析结果证明了羧酸基团的成功引入,并对接枝后粉体的热重分析,结晶度和表面形貌进行了研究。     

Adsorption of methyl violet and brilliant blue onto poly(vinyl alcohol) membranes grafted with N-vinyl imidazole/acrylic acid

Poly(vinyl alcohol) films were grafted with two monomers using gamma radiation, acrylic acid and N-vinyl imidazole. The ability of these membranes to adsorb the dyes, methyl violet and brilliant blue, has been investigated. The data show that untreated or alkali treated membranes adsorb methyl violet, but they did not adsorb brilliant blue. In contrast, acidic treated membranes do adsorb brilliant blue, and did not adsorb methyl violet. This indicates that these membranes could be used for the separation of both dyes. Also it was found that the dye uptake increases with the increase in the degree of grafting.     

过氟化聚合物的苯乙烯接枝研究--辐照条件与反应条件的影响

Fuel cell is in focus as a very low exhaust new dynamo system. Especially polymer electrolyte fuel cells (PEFC) using proton exchange membranes (PEM) have attracted much attention for the electrical vehicle and other mobile applications such as cellar phone and personal computer. Conventional perfluoro-sulfonic acid membranes such as Nation() (DuPont de Nemours LTD.) have been the popular PEM used in PFEC. However, there are still several problems such as insufficient gas barrier properties, low thermal resistance, and their high costs.In this study, hawse have studied the partially fluorinated PEM for PEFC by radiation grafting onto per-fluorinated polymers such as PFA, FEP and ETFE with reactive styrene monomers using pre-irradiation grafting method in gas and in liquid phase, respectively, and successive sulfonation. Characteristic properties of the grafted and sulfonated materials have been discussed and optimized fabricating conditions were determined.Characteristic properties of the obtained materials have been measured by differential scanning calorimetry,thermogravimetric analysis and FT-IR spectroscopy, etc.In the case of irradiation in air, glass transition temperatures (Tg) of the grafted materials depend on the yields of styrene grafting onto the materials. That is higher yields of grafting give lower thermal stability. On the other hand, when the peroxy radicals were converted trapped radicals by exposure in air after irradiation under oxygen-free atmosphere, Tg of the grafted materials hardly depends on the grafting yields.Moreover, the yields of grafting in gas phase were higher than that of liquid phase. However, the sample form of grafting in gas phase has been greatly changed, whereas the sample form of grafting in liquid phase has kept its original feature.Therefore, it is suggested that the fabricating conditions for PEFC membranes were preferred to irradiation under oxygen-free atmosphere and grafting in liquid phase.Ion exchange capacities of the sulfonated-materials could be 3.0meq/g. Other properties of the obtained membranes such as chemical structure were also discussed.     

Amidoxime-based adsorbents prepared by cografting acrylic acid with acrylonitrile onto HDPE fiber for the recovery of uranium from seawater

An amidoxime-based polymeric adsorbent was prepared by pre-irradiation grafting of acrylonitrile and acrylic acid onto high-density polyethylene fibers using electron beams,followed by amidoximation.Quantitative recovery of uranium was investigated by flow-through experiment using simulated seawater and marine test in natural seawater.The maximum amount of uranium uptake was 2.51 mg/g-ads after 42 days of contact with simulated seawater and 0.13 mg/g-ads for 15 days of contact with natural seawater.A lower uranium uptake in marine test can be attributed to the short adsorption time and the contamination of marine microorganisms and iron.However,the high selectivity toward uranium against vanadium may be beneficial to harvest uranyl ion onto adsorbents and the economic feasibility for recovery of uranium from seawater.