CSC-P(AM-AA)重金属捕集絮凝剂的光谱表征及其对重金属去除研究

采用光聚合技术成功制备了羧甲基壳聚糖(CSC)、丙烯酰胺(AM)、丙烯酸(AA)的三元接枝共聚物,即壳聚糖基重金属捕集絮凝剂CSC-P(AM-AA)。为了证明接枝共聚产物的成功制备和表征其结构特征,采用红外光谱(IR)、X射线衍射(XRD)、差热-热重分析(TG-DSC)、扫描电镜(SEM)对其进行表征,结果表明成功制备出羧甲基壳聚糖的接枝共聚物CSC-P(AM-AA),且具有较好的溶解性;由于羧甲基壳聚糖的接枝改性使得CSC-P(AM-AA)具有与P(AM-AA)显著不同的结构特征。同时絮凝实验证明其具有较好的重金属螯合捕集效果,在pH为8、投加量为8 mg·L-1、转速为150 r·min-1时,CSC-P(AM-AA)对Cu2+的最佳去除率为87.0%。     

丙烯酰胺聚合物与氧化铝晶体相互作用的分子动力学模拟

将丙烯酰胺单体分别与丙烯酸(AA)、阳离子单体丙烯酰氧乙基二甲基乙基溴化铵(DMB)、疏水性单体丙烯酸十八酯(OA)共聚,分别得到阴离子聚丙烯酰胺P(AA-co-AM)、阳离子聚丙烯酰胺P(DMB-co-AM)、非离子聚丙烯酰胺P(AM)和疏水性聚丙烯酰 胺P(OA-co-AM)等四种丙烯酰胺高分子絮凝剂. 用分子动力学方法,模拟计算了四种聚丙烯酰胺絮凝剂与氧化铝晶体(012)晶面的相互作用,以获得相应的形变能,结合能及理论排序,为阐释四种高分子絮凝剂的絮凝作用机理提供理论依据. 研究结果表明：四种聚合物分子相对Al₂O₃(012)面的初始位置均已贴近Al₂O₃(012)面,且絮凝剂分子中的O原子与Al₂O₃(012)面的Al原子之间存在强烈的相互作用;与Al₂O₃(012)晶面结合的高分子絮凝剂发生扭曲变形,但形变能远小于相应的非键作用能. Al₂O₃(012)晶面结合能的大小排序为P(DMB-co-AM)>P(OA-co-AM)>P(AA-co-AM)>P(AM), 显示四种絮凝剂中P(DMB-co-AM)的絮凝性能最佳,PAM絮凝效果最差.     

马铃薯深加工工艺废液化学絮凝研究

以钙盐、铝盐、铁盐及聚丙烯酰胺为絮凝剂在不同温度、不同pH等条件下对马铃薯深加工的废液进行化学絮凝。结果发现聚丙烯酰胺加聚合氯化铝絮凝的效果最好。CODCr能由15000mg/L降到5500mg/L,沉降率60%左右。SS能由9500mg/L降到1000mg/L,沉降率为90%左右。能达到进行生物絮凝的要求。     

紫外光引发模板聚合阳离子聚丙烯酰胺及其污泥脱水应用

阳离子聚丙烯酰胺是污水和污泥处理中常用的一种絮凝剂,传统方法制备的阳离子聚丙烯酰胺因阳离子单体随机分布, 电荷过于分散, 导致其在絮凝时不能充分发挥阳离子单体的电中和作用,为此本研究尝试使用一种新型方法制备阳离子聚丙烯酰胺,即以二甲基二烯丙基氯化铵(DMDAAC)和丙烯酰胺(AM)为单体,分别以两种不同分子量的聚丙烯酸钠(PAAS)为模板,使用紫外光引发模板聚合法制得模板聚合物TPDA1和TPDA2,同时使用紫外光引发聚合法制得非模板聚合物(NTPDA)作为对比。使用红外光谱(FTIR)、氢核磁共振图谱(1H NMR)、扫描电镜(SEM)等方法对制得的聚合物进行表征,并通过污泥脱水试验研究其污泥脱水效率。波谱分析结果表明,添加模板提高了DMDAAC单体的活性,促使聚合物分子中形成DMDAAC连续分布的阳离子单体嵌段结构,从而提高了聚合物的絮凝性能,尤其是电中和作用;SEM扫描显示模板聚合物的具有较大的比表面积和分形维数;污泥脱水试验表明,模板聚合物具有较好的污泥脱水性能和较宽pH应用条件,当模板聚合物TPDA1投加量为50 mg·L-1,污泥pH为8时,其具有最佳污泥脱水效率,污泥含水率降至最低值72.5%。模板分子量对聚合物属性也存在影响,分子量较低的模板制得的聚合物具有相对较好的污泥脱水效率。     

光聚合壳聚糖基絮凝剂的光谱表征研究

由于壳聚糖的大分子键上分布着大量的氨基、羟基和N-乙酰基等活性功能基团,将其改性作为天然绿色絮凝剂越来越受到关注,但对其的接枝共聚产物的光谱学表征研究鲜有报道。因此,对壳聚糖基絮凝剂进行光谱学表征与分析研究具有重要意义。论文以壳聚糖(CS)、丙烯酰胺(AM)、二甲基二烯丙基氯化铵(DMDAAC)为接枝共聚单体,采用光聚合技术制备壳聚糖基絮凝剂CS-P(AM-DMDAAC)。采用X射线衍射(XRD)、紫外光谱(UV)、红外光谱(IR)研究其结构特征;分析了壳聚糖、丙烯酰胺、二甲基二烯丙基氯化铵及三者接枝共聚产物的X射线衍射(XRD)、紫外光谱(UV)、红外光谱(IR)的图谱特征和振动吸收峰归属。研究了壳聚糖脱乙酰度、壳聚糖浓度、阳离子度对接枝共聚产物壳聚糖基絮凝剂CS-P(AM-DMDAAC)的X射线衍射(XRD)、紫外光谱(UV)、红外光谱(IR)的影响。UV光谱和IR光谱研究结果证明CS,AM和DMDMAAC成功发生接枝共聚反应制备出CS-P(AM-DMDAAC),壳聚糖浓度增加导致其光谱对称性减弱。XRD图谱研究表明接枝共聚反应使得壳聚糖的晶型结构趋向不定型结构转变,不定型结构相比于晶型结构更易于水化,故接枝共聚产物具有更加优异的溶解性。     

DFT方法研究木质素单体及二聚体的结构与拉曼光谱

木质素是自然界中第二丰富的天然聚合物,广泛存在于各种陆地植物的木质部中,利用木质素拉曼光谱对植物种类进行快速无损鉴别具有重要的应用价值。但由于木质素大分子构型非常复杂,对其拉曼特征光谱的仿真研究一直存在困难。利用Gaussian16W中包含的B3LYP密度泛函方法结合6-311G(d, p)基组,构建出三种木质素单体及其三种同种木质素单体构成的二聚体以及三种异种木质素单体构成的二聚体,提出了一种利用木质素的三种基本结构单体及其二聚体仿真分析木质素大分子拉曼光谱特征的方法。首先计算了三种单体的基本构型、轨道能级和电子空间分布,并分析了三种木质素单体拉曼光谱和振动模式的特点。随后利用不同组合方式的β-O-4二聚体的光谱谱峰特征,解释了特征谱峰信号位置漂移的成因,提出了判断木质素大分子信号特征的主要依据。研究结果表明,1 712 cm^-1谱峰信号最强且位置稳定,振动归属为碳碳双键伸缩振动,该振动归属引起的特征峰可以作为木质素大分子最主要的信号特征;1 642 cm^-1谱峰信号振动归属为芳香环骨架振动,仅受芳香环甲基数量影响产生劈裂,该振动归属引起的...     

聚合硫酸铁絮凝剂的絮凝形态光谱研究

利用紫外-可见光谱研究了聚合硫酸铁絮凝剂的絮凝形态及其性能。研究内容包括：不同pH的聚合硫酸铁絮凝剂溶液的吸收光谱,吸收光谱中有关吸收峰对应的聚合硫酸铁絮凝剂微观形态、反应机理以及絮凝除浊、除色效果比较。研究发现：当pH值在1.0～2.5之间时,在200～1 100 nm范围内随着pH升高所有峰的吸收值均增加;当pH大于2.5时, 随着pH上升,峰的吸收值并不继续增加,有些吸收波段光谱吸收值反而下降, 甚至明显下降; 在pH值为2.0时,絮凝效果最好;在pH值为1.5～2.0之间和2.0～2.3之间也有较好的絮凝效果。在200～400 nm处, 不同pH的聚合硫酸铁絮凝剂的光谱曲线变化与絮凝效果有一定的对应关系。研究结果对于聚铁类絮凝剂的优势絮凝形态的分析和鉴定有潜在应用前景,有利于为聚铁高分子絮凝剂形态分析和鉴定提供一些简便易行的方法。     

FTIR及CLSM对转基因杨木细胞壁木质素含量及微区分布研究

通过木质素基因工程能够有效降低杨木细胞壁木质素含量,从而改善人工林杨树作为木质纤维材料的利用现状。选取C3H基因活性抑制表达的转基因杨树和其对照组杨树为实验材料,利用傅里叶红外光谱(FTIR)技术快速表征C3H基因表达活性降低后幼龄杨木细胞壁木质素的含量,并结合激光共聚焦显微镜(CLSM)和组织化学染色技术原位表征木质素含量微区分布变化规律。结果表明转基因杨树与对照组杨树红外谱图的形状和特征峰数目、位置基本一致,表明C3H基因活性降低并未改变杨木细胞壁主要化学成分及结构,但I_{1 508}/I_{1 379},I_{1 508}/I_{1 425}和I_{1 508}/I_{1 740}木质素特征峰高度比值结果表明转基因杨木木质素含量下降了8.2%～9.5%,峰强度的区别说明C3H基因活性抑制表达能够改变杨木细胞壁上木质素等化学组分含量;CLSM观察发现转基因杨木木质素微区分布含量均为纤维细胞角隅>复合胞间层>次生壁,与对照组木质素呈现相同的沉积规律,且转基因杨木细胞壁木质素浓度低于对照组杨木;组织化学染色的结果同样表明杨木S单体木质素均匀分布于纤维细胞壁上,而G单体木质素微区沉积规律为纤维细胞角隅>复合胞间层>次生壁,进一步揭示了C3H基因活性的降低并没有改变转基因杨木G和S木质素单体的沉积规律,但对其纤维和导管壁上木质素单体含量分布有一定影响。     

基于拉曼光谱快速检测亚氯酸钠法脱木素的动力学及选择性

酸性亚氯酸钠法脱木素是目前实验室最常用的脱木素方法,可最大程度地保留综纤维素,但关于木质素在逐步脱除过程中其动力学及选择性的研究却很少。拉曼光谱能快速、定性和半定量地测定亚氯酸钠法脱木素过程中残余木质素及木质素单体含量在不同细胞及形态学区域的动态变化。以阔叶材桉木、针叶材杉木、禾本科毛竹为例,通过提取亚氯酸钠法脱木素过程中不同细胞木质素(1 598 cm~(-1))及单体愈疮木基(G, 1 270 cm~(-1))、紫丁香基(S, 1 331 cm~(-1))的平均拉曼光谱,发现三种木材在各区域中木质素脱除动力学总体规律一致,即在反应初期木质素大量快速移除,随着反应的进行木质素脱除效率下降。其中,在反应前0.5 h, 1 598 cm~(-1)处平均拉曼强度降低量超过82%,而在脱木素后期(1.0～1.5 h),木质素平均拉曼强度减少仅5%～15%。特别的,竹材脱木素所需时间要明显少于木材。相同条件下,竹材纤维细胞在前10 min内1 598 cm~(-1)处拉曼强度减少就达88.65%。同时,木质素的脱除具有高度的选择性。在反应初期,射线细胞中G和S型木质素的移除率均高于导管和纤维细胞,而在导管、纤维细胞中, S型木质素的脱除比G型木质素更明显。在逐步脱除木质素过程中,导管、射线、纤维细胞间木质素相对强度关系总体不变,即导管、射线相对木质素浓度始终高于纤维细胞。总体而言,在组织水平,导管中木质素最难于脱除,射线细胞次之,纤维细胞中的木质素较容易脱除。在纤维细胞中,细胞角隅木质素脱除速率最高,其次是复合胞间层,次生壁最低。就木质素单体而言, S型木质素比G型木质素更容易脱除。研究表明拉曼光谱能简单、快速地检测不同树种中各类组织、细胞以及木质素结构单元在生物质化学预处理中残余木质素含量的动态变化,同时进一步加深对生物质亚氯酸钠法脱木素选择性及动力学的理解。     

负载硅藻土的固体聚合硫酸铁的制备及结构表征

以工业副产品七水硫酸亚铁(FeSO4·7H2O)为原料,制备液体聚合硫酸铁(PFS)絮凝剂,再与硅藻土复合,在一定的温度下,通过真空烘箱干燥制备同体PFS.通过红外光谱及扫描电镜(SEM)对其结构表征,结果表明:负载硅藻土后的PFS中很可能有新的基团键生成,在PFS之间形成了新的键桥作用;硅藻土中多种金属物质和部分PFS相互作用形成了复合型铁系聚合体,以及硅藻土中载体吸附团聚作用的结果,使絮凝剂的分子结构变大,增强了复合絮凝剂吸附架桥和卷扫的功能.通过正交实验研究其合成优化工艺条件为:FeSO4·7H2O与硅藻土的质量比为43:1,反应时间为1 h,反应温度为55℃;合成产物对生活污水的处理具有良好的絮凝性能,COD和浊度的去除率分别可达80.00%和99.98%.     

Study on Direct Grafting Maleic Anhydride onto Poly(D,L-lactide-co-glycolide) Chains

Direct graft copolymerization of maleic anhydride (MAH) onto poly(D,L-lactide-co-glycolide) (PLGA) was performed by use of benzoyl peroxide (BPO) as initiator. Fourier transform infrared spectra, nuclear magnetic resonance, titration analysis of maleation extent and water contact angle were employed to characterize the obtained MPLGA. The effects of monomer concentration, initiator concentration and reaction temperature on the degree of maleation were investigated. The MPLGA scaffold was obtained by using NaCl as the porogen. The results showed that maleic anhydride was successfully grafted onto the PLGA chains. The monomer and initiator concentrations played an important role in the graft copolymerization; the extent of maleation first increased with increasing content of MAH and BPO and then declined. The extent of maleation continuously increased with increasing temperature to 100°C, and then the rate of increase decreased. The extent of maleation could be controlled in the range from 0.15 to 0.71% by adjusting the graft copolymerization conditions. The introduction of anhydride enhanced the water contact angle of PLGA. The MPLGA scaffold showed a network of interconnected pores ranging from 50 to 300 μm.     

Preparation and Properties of Chlorinated Polyethylene-Chlorinating/Grafting-Poly (Acrylic acid) and its Sodium-Salt Ionomer

Acrylic acid (AA) was grafted onto high-density polyethylene (HDPE) by in-situ chlorination graft copolymerization (ISCGC), yielding a graft copolymer composed of chlorinated polyethylene (CPE) as backbone and poly (acrylic acid) (PAA) as branch chains. The reaction process and the preparation of its carboxylated ionomers were studied. The structure of the graft copolymer and the ionomer were characterized by FTIR, gel permeation chromatography (GPC), and degree of grafting (GD). The influence of factors related to the main and side reactions, including the monomer concentration, chlorine contents of the product, and reaction temperature were investigated. Additionally, the effects of these factors on the reaction are described. The aim of the research was to investigate how chlorinated polyethylene grafted with poly (acrylic acid) (CPE-cg-PAA) and its sodium-salt ionomer could be prepared and their relative effect on thermal and mechanical properties.     

二（2-苯并咪唑亚甲基）胺合镝的合成及其与DNA作用的光谱研究

首次微波合成二（2-苯并咪唑亚甲基）胺（L）及其稀土金属镝的配合物[DyL2（NO3）2]NO3,用红外、元素分析、核磁共振、摩尔电导对其进行表征。用紫外可见光谱、荧光光谱、粘度研究了该配合物与鲑鱼精脱氧核糖核酸（DNA）的作用规律,结果表明：配合物以部分插入和静电作用模式与DNA键合。     

Zwitterionic monomer graft copolymerization onto polyurethane surface through a PEG spacer

A new zwitterionic surface was obtained by a novel three-step grafting procedure. The zwitterionic monomer was introduced by cerium-induced graft copolymerization in the presence of N,N′-methylene bisacrylamide (MBAA) as cross-linking agent. Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) analysis confirmed the MBAA could stimulate zwitterionic monomer grafting onto the membrane surface. Surface properties were also determined by atomic force microscope (AFM) and water contact angle. The hemocompatibility of the modified PU membranes was evaluated by the activated partial thromboplastin time (APTT), thrombin time (TT) and prothrombin time (PT). The TT and APTT of PU were significantly prolonged by the zwitterion of sulfobetaine monomer grafting copolymerization. The new polyurethane membrane could have a great potential in biomedical applications.     

A Study of the Synthesis of EPDM-g-MAN and Toughness of its Blend with SAN (AEMS)

Ethylene–propylene–diene–methyl methacrylate/acrylonitrile terpolymers (EPDM-g-MAN) were synthesized by comonomers methyl methacrylate and acrylonitrile (MMA-AN) grafted on EPDM macromolecules with solution graft copolymerization. The engineering plastics of the blend of EPDM-g-MAN with SAN (AEMS) were prepared by blending EPDM-g-MAN with SAN resin. The effect of AN/MMA-AN weight percentage (f _AN) on monomer conversion ratio, grafting ratio, and grafting efficiency of the graft copolymerization and the notched Izod impact strength of AEMS were investigated. The notched Izod impact strength of AEMS, prepared by blending SAN with EPDM-g-MAN, was synthesized under our optimum S2 reaction conditions, with EPDM/MMA-AN weight proportion of 50/50 and f _AN of 10 wt%, presenting a peak with the maximum value of 61.0 kJ/m². The microstructure of AEMS prepared with S2 reaction conditions showed that when the polarity of EPDM-g-MAN was appropriate, the EPDM phase formed a pseudocontinuous phase in the SAN matrix and the interfacial adhesion was strong, which could induce shear yielding of the SAN matrix. Differential scanning calorimetry analysis showed that there was good compatibility between SAN resin and EPDM-g-MAN synthesized with f _AN of 10 wt% and a EPDM/MMA-AN weight ratio of 50/50.     

利用19F NMR与荧光光谱法检测高分子酰胺化反应

通过血红素上羧基与端氨基聚乳酸上的氨基之间进行酰胺化反应,制得了血红素-聚乳酸分子.利用六氟异丙醇与端羧基反应生成六氟异丙醇酯,结合19F NMR峰面积积分的方法测定羧基含量,以荧光胺作为荧光试剂,采用荧光光谱法测定伯胺端基.进而,采用端基分析方法计算了血红素-聚乳酸的数均分子量,检测了血红素与聚乳酸1∶1和1∶2投料...     

新型D-π-D芴配体的合成及表征

以芴、对甲氧基苯硼酸为原料,通过Friedel-Crafts烷基化、澳代、Suzuki偶联反应合成了一种新型电子给体-π-电子给体(Donor-π-Donor,简写为D-r-D)含芴功能基的有机双光子吸收材料(TPA)单体9-(4-溴代丁基)-9-丁基-2,7-二(4-甲氧基苯基)-9-氢芴(BBBBMOPF,I),其...     

Surface Modification of Poly(tetrafluoroethylene) Microporous Membranes by Acrylic Acid Liquid-Phase Graft Copolymerization

Air plasma-pretreated poly(tetrafluoroethylene) (PTFE) films were subjected to further surface modification by liquid-phase graft copolymerization with acrylic acid monomer (AAc). The surface compositions and microstructures of the modified films were characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). An exterior graft copolymerization of AAc on the PTFE fiber was indicated by the SEM photographs. The XPS results indicated that the F/C atomic ratio of the membranes were 1.837 and 1.207, and the O/C atomic ratio were 0 and 0.112 for the original and liquid-phase grafted PTFE membranes, respectively. The pore size distributions of the treated and untreated PTFE membranes, measured by the bubble-point method, were much smaller than that of the untreated membrane.     

Curing behavior and physical properties of an epoxy nanocomposite with amine-functionalized graphene nanoplatelets

Amine-functionalized graphene nanoplatelets (AGNPs) were prepared via an easy simple one-step process, treating graphite powder with 4-aminobenzoic acid in polyphosphoric acid, and then the effects of the AGNPs on the curing and physical properties of an epoxy resin were studied. The formation of the AGNPs was confirmed by scanning electronic microscopy (SEM), Fourier transform infrared spectroscopy, and thermogravimetric analyzer. Curing behavior of the epoxy/AGNPs nanocomposite was investigated by differential scanning calorimeter. The AGNPs made the epoxide curing reaction with amine groups slightly faster. The physical properties of the epoxy/AGNPs nanocomposite were investigated by dynamic mechanical analyzer, thermomechanical analyzer, and impact test. The AGNPs improved T_g by 21.4 °C, and storage modulus and impact strength of the epoxy resin 23 and 73%, respectively, much more effective than the graphite powder at the same filler loading of 1 phr. SEM images for the fracture surfaces of the epoxy/AGNPs nanocomposite showed improved interfacial bonding between the epoxy matrix and the nanofillers due to the amine functional groups of the AGNPs.