可UV 固化粉末状超支化树脂的研究

以三羟甲基丙烷(B3)、2,2.二羟甲基丙酸(AB2)和对甲苯磺酸为原料通过准-步熔融缩聚反应合成了常温为玻璃态的不同代数脂肪族超支化聚酯.采用13C 核磁共振谱仪(Nuclear magnetic resonance,NMR)、红外光谱仪(Fourier transform infrared spectroscopy,FT-IR)、凝胶渗透色谱仪(Gel permeation chromatography,GPC)、示差扫描量热仪(Differential scanning calorimeters,DSC)等方法对其结构和性能等进行了分析与表征.以硬脂酸和甲基丙烯酸为反应试剂,对超支化聚酯进行端基改性,得到了部分端基改性超支化树脂.该树脂可作为主体树脂在UV固化粉末涂料中得到应用.     

硅橡胶膜辐射接枝中酸效应的研究——Ⅰ.与丙烯酸共辐射接枝反应

本文以硅橡胶为基材深入研究了与丙烯酸共辐射接校中的酸效应。结果表明,甲醇-丙烯酸与硅橡胶共辐射接枝体系中酸效应在不同吸收剂量范围是不同的。<5kGy时酸有敏化作用,在5—13kGy范围酸有相反的效果。在所有剂量范围内单体浓度、剂量率等因素对辐射接枝反应的酸效应无明显影响。除吸收剂量外,酸效应还与基材组成、单体与溶剂类型以及接枝方法等多种因素有关。     

含硅光固化材料的性能研究

研究了体系组成对光固化有机硅聚氨酯丙烯酸酯(Polysiloxane isophorone urethane acrylate,PSIUA)体系的耐水性、体积收缩、硬度、附着力、耐溶剂性及机械性能的影响.研究发现,含羟基及醚键的活性单体会使体系吸水率上升;随着体系交联度增加,吸水率下降.PSIUA体系体积收缩率随PSIUA含量的增加而下降,所研究的PSIUA体系的体积收缩率均小于10%.加入三官能团单体和具有刚性结构、交联度较大的的环氧丙烯酸酯有利于提高体系的硬度.加入适量的含羟基的活性单体及环氧丙烯酸酯可以提高PSIUA光固化膜的附着力.测得PSIUA体系的玻璃化转变温度为246.0℃.     

硅橡胶辐射接枝中酸效应的研究——Ⅱ.N-VP或4-VP单体与硅橡胶共辐射接枝反应

本文以硅橡胶膜为基材研究了与N-2-乙烯基吡咯烷酮(N-VP)或4-乙烯基吡啶(4-VP)共辐射接枝中的酸效应。结果表明,甲醇-N-VP与硅橡胶共辐射接枝体系中,在较大的剂量范围内酸对接枝反应有抑制作用。但酸对甲醇-4-VP体系的接枝反应却依然起敏化作用。虽然体系中酸度有上述影响,但剂量率、单体浓度的变化并不影响酸抑制或敏化接枝反应的总趋势。文中也讨论了上述接枝反应中酸效应的机理。     

混合烷烃γ辐射磺氯酰化制备烷基石油磺酸钠——Ⅱ.偶氮二异丁腈对烷烃γ辐射磺氯酰化反应的敏化作用研究

为了对以多种结构类型的混合烷烃为原料的γ辐射磺氯酰化法合成烷基石油横酸钠的反应提高产率,所以对偶氮二异丁腈(AIBN)敏化效应进行了研究,并对其敏化机理进行了探讨。以AIBN作敏化剂进行磺氯酰化反应,可使烷基磺酰氯具有较大的产率。     

Synthesis of amidoxime polymer gel to extract uranium compound from seawater by UV radiation curing

A new amidoxime polymer gel for uranium extraction from seawater was successfully prepared by photoinitiated crosslinking polymerization. It involves UV-induced radical polymerization of acrylonitrile (AN) and methacrylic acid (MAA) monomers with crosslinking agent and photoinitiator: an alternative synthesis pathway to gamma radiation. Characteristic peaks of Fourier transform infrared spectroscopy (FTIR) indicated that nitrile group was completely converted into amidoxime group. Eight hours of 60 W UV curing was enough for polymer gel formation. For the 4 to 1 ratio of AN to MAA, crosslinking agent concentration of 1 g/100 mL-monomers and photoinitiator content of 60 mL/100 mL-monomer, maximum uranium adsorption capacity of 17.02 mg/g adsorbent in seawater was achieved for sample spiked with 10 ppm uranium. For seawater sample spiked with 2,245 ppm uranium, the adsorption capacity reached 432.41 mg/g adsorbent. The amidoxime polymer gel could be regenerated for at least eight cycles while retaining about 50% of the uranium uptake capacity. Thus, the present amidoxime polymer adsorbent is a high-efficiency seawater uranium recovery agent for both high and low uranium concentrations.     

移波薄膜测量紫外光的研究

采用溶液浸泡法制备了含有移波剂PT、PPO、Bis-MSB及POPOP的聚甲基丙烯酸异丁脂薄膜,以及这几种成分混合组成的复合膜层。测量了它们的吸收、发射和激发光谱,并给出了膜层中移波剂含量的最佳范围。     

尼龙-66滤膜电子束预辐照接枝丙烯酸的研究

采用电子束预辐照接枝法,以水为溶剂,硫酸铜为阻聚剂,将丙烯酸接枝到尼龙-66滤膜上面。探讨电子束吸收剂量、丙烯酸单体浓度、接枝时间和反应温度对滤膜接枝率的影响。对不同接枝率的滤膜进行吸水性测试,并利用扫描电子显微镜和傅里叶红外光谱仪对接枝前后的滤膜进行表征。结果表明:丙烯酸成功接枝到尼龙-66滤膜表面,接枝后样品表面孔洞减少,表面粗糙度增加;接枝率随着吸收剂量、丙烯酸单体浓度、接枝时间和反应温度的增加而增大,而后渐渐趋于平缓;接枝后的滤膜吸水率有很大的提高。     

紫外辐射引发聚丙烯接枝马来酸酐-苯乙烯的研究

将紫外辐射技术应用到本体接枝改性,成功制备了聚丙烯的马来酸酐-苯乙烯接枝物(PP-g-(MAH-co-St)),并用红外光谱对接枝物进行了表征.研究了紫外光辐照时间、单体及引发剂(BP)浓度等因素对接枝率及熔体流动速率的影响.结果显示,辐照时间为30 s时,接枝效果最佳.接枝率及熔体流动速率随BP含量的增加呈现先增加后降低的趋势,分别在BP用量为0.6g/100g PP及0.4g/100g PP时达到最佳值.MAH及St浓度对接枝率及熔体流动速率的影响与BP浓度的影响相似,其最佳用量为4 g/100 g PP.St的存在对接枝反应有明显的改善作用.接枝物的热性能分析显示,接枝PP的结晶及熔融温度都有所变化,说明接枝反应对PP的晶体形貌及尺寸有显著影响.     

Study on the reaction kinetics of 99Tcm-labeled BIDP

A novel zoledronic acid derivative, 1-hydroxy-2-(2-butyl-1H-imidazole-1-yl)-ethylidene-1,1-diphosphonic acid(BIDP), was synthesized and labeled with <'99>Tc<'m>. The detailed kinetic study on the labeling reaction between BIDP and <'99>Tc<'m> was carried out. The results indicated that the reaction rote constants k were 0.0258, 0.0268,0.0305, 0.0323, 0.0351 and 0.0384 min<'-1> at 0℃, 5℃, 10℃, 15℃, 20℃ and 25℃, respectively. From the Arrhenius equation k=-A.e<'-Ea/(Rr)>, the activation energy Ea of the labeling reaction was calculated to be 10.45 kJ/mol. And the correlation between k and temperature(T) was also deduced as In k=1258.8×(1/7)+0.9531. In addition, it was found that in order to get a high radiolabeling yield(RLY)(>90%), the reaction temperature must be up to 12℃.     

水溶液中环己丁酸的伽玛射线辐射降解研究

采用^60Coγ-射线辐射降解环己丁酸,通过对辐照前后化学需氧量（CODcr）与pH值变化的分析,研究了不同环己丁酸浓度、初始pH值、H202初始浓度和吸收剂量对环己丁酸的辐射降解效果的影响。结果表明：在相同剂量条件下,环己丁酸初始浓度越高,CODcr去除率越低;酸性条件更利于溶液中CODcr的去除;H202与γ-射线辐照之间具有显著的协同效应,H202初始浓度为1mmol·L-1时,其对40mg·L-1环己丁酸的辐射降解的促进效果达到最好。环己丁酸水溶液的CODcr浓度变化服从一级反应动力学方程。     

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.     

蒙特卡罗模拟方法对EAS阵列性能分析与优化设计的研究

建立了快速计算机阵列性能分析程序，由此对阵列性能进行了快速分析，对种种阵列设计方案进行比较与优化搜寻，本文介绍其基本原理，方法，程序设计及部分计算结果。     

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。     

聚丙烯粉料固相光接枝丙烯酸的研究

为了提高聚丙烯(PP)的亲水性和染色性,以二苯甲酮(BP)为光引发剂、使用固相光接枝反应装置,采用固相紫外光接枝法在PP粒料表面接枝丙烯酸(AA)单体,并研究了单体含量、引发剂用量、辐照时间和溶胀时间对接枝率的影响规律,以及PP接枝前后力学性能的变化。结果表明,AA用量为1mL、引发剂用量为0.15g、辐照时间为30min、溶胀时间为12h时的接枝率最高。接枝率为5.2%左右,上染率为43.4%时,接枝PP的拉伸强度降了1.37MPa,但断裂伸长率从358.3%增加到396.3%,说明丙烯酸适度接枝对力学性能影响不大。