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。     

颜料/树脂界面状态对UV固化效率的影响

本工作对颜料的表面改性及其对紫外光(UV)固化效率的影响进行了研究。研究发现,除了通常认为的颜料对UV的吸收以及散射会造成UV固化效率下降外,颜料表面与树脂的界面区域残存有空气成分也可能是造成彩色光固化涂层固化速度下降的另一个重要原因。电子能谱研究结果表明,三乙醇胺改性的艳佳丽蓝颜料不仅使得颜料/树脂界面的空气成分大幅减少,而且颜料与树脂的结合处改性前后的碳、氮、氧的组成成分、结合能都发生了明显的变化,存在着明显的界面耦联现象。颜料改性后,固化速度比未改性前有明显提高(例如,膜厚为125μm的涂料通过三乙醇胺对蓝色颜料改性,固化时间从45s减少到14s)。显然这与颜料/树脂界面的状态有关,说明通过颜料的改性来促进UV固化是可行的。研究结果对光固化彩色涂料的研究开发乃至光固化体系填料的使用等都具有积极意义。     

水性丙烯酸树脂的合成和UV固化研究

合成了一种新型的、可射线固化的水性丙烯酸树脂,采用该树脂和各种辅助成分配制成水性涂料。研究了在合成过程中异氰酸酯基含量（ＮＣＯ％）的变化以及该树脂的水稀释曲线。同时研究了辐照时间、距离,光引发剂的种类,光敏助剂以及活性稀释剂对交联程度的影响,得到了性能优良的涂膜。     

叔胺结构对有机硅改性聚丙烯酸酯树脂UV固化的影响

UV-radiation curing has become a well-accepted technology because of its distinct advantages mainly as environmental benign, efficiency, less energy consumption and mild curing condition. The free radical photopolymerizations have been based mainly on acrylate systems, which polymerize rapidly and can be adjusted with ease to modify materials with different properties for different applications. The primary limiting factor of the approaches, however, is that the reactions would be inhibited by oxygen. A main method to tackle the problem is to add tertiary amine. Nevertheless, this causes new problems in the curing products, which turn yellow easily and their deposited period becomes short.In this work we have synthesized silicone modified polyacrylate (SPA) resins from bis[3-(trimethoxysilyl)propyl]amine (A1170) and polyethylene glycol diacrylate (SR-344) through Michael addition (Fig. 1). Without adding any extra tertiary amine, the structure of the obtained prepolymers could effectively solve the problem of oxygen inhibition.The DPC curves characterizing the UV curing behavior of the prepolymers are shown in Fig.2. With the SPA, the curing reaction in ambient atmosphere reached the maximum reaction rate at almost the same time as in N2, and the reaction rate in air is a little higher than in N2. The conversion of SPA in air is also a little higher than in N2. All these may be explained as follows. Tertiary amine can suppress the oxygen inhibition and produce more radicals. Tertiary amine may offer hydrogen to peroxide free radical produced in the oxygen inhibition process, the latter further decompose into alkyl radicals and hydroxide radicals.However, chain transfer and radicals terminations tend to occur, which made the rate reduced quiekly at later stages of the curing [1].     

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.     

丙烯酸-丙烯酰胺共聚高吸水性树脂的紫外聚合及其性能研究

本论文在无交联剂条件下以丙烯酸、丙烯酰胺和氢氧化钠为原料利用高压紫外汞灯辐照引发聚合高吸水性树脂丙烯酸(AA)-丙烯酰胺(AM)共聚物。考察中和度、光照时间、单体含量、聚合物粒度等因素对共聚AM-AA吸液性能的影响。获得了最佳的试验条件,并在最佳试验条件下合成了共聚物。其吸水率(去离子水)为3062g/g,吸生理盐水(0.9%NaCl水溶液)率为241.6g/g,吸自来水率232.8g/g,吸人工尿率为76.6g/g,吸人工血率为367g/g。     

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。     

利用低能自屏蔽电子帘式加速器进行木器表面涂料辐照固化的研究

本文初步描述了利用低能自屏蔽电子帘式加速器固化木器涂料和石膏板表层涂料的生产工艺。讨论了电子束固化过程中的质量控制,诸如表层涂料的涂布技术,涂层厚度对表面性能的影响,电子束辐照场下的剂量值与剂量分布等。合成了作为EB涂料主要成分的不饱和聚酯树脂。比较了几种不同种类的EB涂料的固化条件并且对固化后涂层性能作了表述。     

UV照射对径迹蚀刻过程的影响

Truck technology depends decisively on the track structure of the material after irradiation. In order to reveal microstructures of the ion-tracks, many techniques have been applied to characterize the track. Conductometrie method is wildly used in the area as it can monitor in-situ the pore formation and growth processes that are closely related to structures of the ion track[1].In this study, polyethylterephthalate films (PET, 38 μm thick) were irradiated with Xe ions of 450 MeV, 3 × 105ions/cm2. Before etching with aqueous 0.3 M NaOH solution at 40℃, the samples were illuminated with UV light (λ＞310nm) in air for different time durations. Pore growth processes during the etching were monitored by the conductometric measurement. Fig. 1 shows the measurement results of radial etching rate of the pore growth in dGl/2/dt (Ω-1/2s-1) with the etching time.a. Without UV illumination, b. UV illuminated for 60 min, c. UV illuminated for 180 min, d. UV illuminated for 720 min As shown in Fig. 1, the etching processes changed dramatically with UV illumination time. (1) The break through time reduced with increased sensitization time, from 8× 104S of the control to about 1 × 104s of the 720 minutes UV illumination. (2) With increased UV illumination time, the shape of the pore growth rate curve changed greatly, f-mally became a shape with a peak and a vale. Formation of the peak implies that pores tended to break-through on completing the UV-light illumination, whereas the vale can be related to the slower etching rate in the track halo where most molecules had been crosslinked by the heavy ion irradiation. After etching for sufficient long time, the pore grew at a constant rate determined by the bulk etching rate.To interpret the measurements, numerical analysis and fitting were carried out, from which information related to the track structures and variations with the UV illumination was obtained.     

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.