通过RAFT聚合制备SiO2/接枝共聚物纳米杂化粒子

以二氧化硅(SiO2)纳米粒子表面键接的二硫代苯甲酸酯作为可逆加成-断裂-链转移(RAFT)聚合反应的链转移剂, 在室温下引发苯乙烯和马来酸酐进行表面RAFT交替共聚反应, 制得了SiO2/苯乙烯-alt-马来酸酐杂化材料. 通过聚氧化乙烯(PEO)的羟基与马来酸酐的酯化反应, 将PEO接枝到SiO2纳米粒子的表面, 增加了硅粒子的生物相容性. 用FTIR, TGA和TEM对杂化材料的结构、组成和形貌进行了表征.     

苯乙烯/马来酸酐共聚物修饰碳纳米管的研究

利用羟基碳纳米管上的羟基与马来酸酐之间的简单反应, 在碳纳米管上引入双键, 进一步引发苯乙烯聚合, 在碳纳米管表面接枝苯乙烯马来酸酐共聚物, 同时采用羟基碳纳米管与苯乙烯马来酸酐共聚物直接反应也在碳纳米管的表面引入了苯乙烯马来酸酐共聚物. 经IR, Raman, TG和TEM测定, 证明了碳纳米管与苯乙烯马来酸酐共聚物之间为化学键连接关系.     

疏水上转换纳米晶的均相体系聚合物包覆及在发光检测中的应用

选用水解的十八碳烯-马来酸酐共聚物(PMAO)为表面修饰分子,发展了一种以疏水纳米粒子吸附表面活性剂十二烷基磺酸钠(Na YF_4-SDS)为中间体的均一液相聚合物包覆纳米粒子方法.该方法解决了油溶性纳米晶与弱极性聚合物分子难以在单一体系下均匀分散的问题,实现了在均一液相体系下对疏水纳米晶的单分散包覆以及表面羧酸官能团修饰.红外光谱与表面Zeta电位测试结果表明纳米晶已被聚合物包覆,粒子表面为强电负性的羧酸基团.电镜结果表明聚合物包覆的上转换纳米晶粒径无明显的变化,具有良好的单分散性.发射光谱表明聚合物包覆前后粒子的发射谱带无显著变化,保持了原油相粒子的发光性能.进一步的特异性识别荧光显微成像实验证实聚合物包覆后的粒子(Na YF_4-PMAO)可用于生物学检测.     

聚对亚苯基二亚甲基薄膜的表面化学改性及其肝素化反应

采用化学气相沉积聚合(CVDP)法制备聚对亚苯基二亚甲基(PPX),再通过与酸酐的化学表面反应将丁酸酰基和马来酰基引入PPX薄膜的表面,制得表面带活性取代基的PPX.改性后的薄膜表面粗糙度略有增加,但仍旧维持在10nm以内.改性后的薄膜水接触角减小,减小幅度达到十几度,表面亲水性大幅度提高.丁二酸酐表面改性后薄膜的抗化学氧化时间不变,马来酸酐表面改性后薄膜的抗氧化时间略有下降,但抗氧化时间都大于30h,仍具有优异的抗化学氧化性能.丁酸酰基和马来酰基取代PPX肝素化反应后膜中的肝素含量在7μg/cm2左右,肝素化后薄膜的抗凝血性能得到明显提高.     

非水滴定和傅立叶红外光谱在聚丙烯马来酸酐接枝物表征中的应用

采用非水滴定法中的无机碱直接滴定方法测定了马来酸酐在聚丙烯上的接枝率,并对该方法作了可行性验证,讨论了非水滴定中的两个难点：化学计量比的确定和滴定终点的判断。通过傅立叶红外光谱法(FTIR)对聚丙烯马来酸酐接枝物的纯化效果、自由基引发反应对非水滴定的影响及聚丙烯接枝马来酸酐的反应机理作了定性分析,并结合非水滴定的数据绘制了红外定量校准曲线。     

聚马来酸酐高级脂肪醇酯的合成及其对聚乙烯的表面改性研究

采用溶液聚合的方法合成聚马来酸酐，考察不同聚合条件对聚马来酸酐产率的影响。将所合成的聚马来酸酐与十八醇、十六醇和十四醇进行酯化反应合成了三种两亲性的大分子表面改性荆聚马来酸酐十八醇酯(PMAO)、聚马来酸酐十六醇酯(PMAH)和聚马来酸酐十四醇酯(PMAT)。对这三种聚马来酸酐高级醇酯／聚乙烯共混体系的表面亲水性进行了研究，采用全反射红外光谱对聚马来酸酐高级醇酯共混体系薄膜进行表征，发现聚马来酸酐高级醇酯可以在聚乙烯薄膜表面富集，接触角测量表明聚马来酸酐高级醇酯的加入可以有效降低聚乙烯薄膜的水接触角。     

天然橡胶原位接枝炭黑的分散性研究

采用原位固相接枝方法,使在高温和强剪切作用下降解的天然橡胶接枝到炭黑表面.采用透射电镜(TEM)、原子力显微镜(AFM)等方法观察了接枝前后的炭黑粒子形貌变化,发现未接枝炭黑以微米级的附聚体形式存在,而由于炭黑聚集体被强剪切力部分破坏,接枝炭黑的聚集程度明显减弱,粒子的尺寸减小.采用激光光散射粒度仪对接枝前后炭黑的粒度进行分析,接枝炭黑的体积平均粒径为164 nm,远小于测得的原炭黑的粒径797 nm.采用沉降法、透光率法及zeta电位测量研究了接枝改性对炭黑在溶剂中的分散性及分散稳定性的影响,结果表明,接枝炭黑在接枝分子的溶剂中的分散性变好,分散稳定性提高.     

硅胶修饰-表面分子印迹牛血红蛋白及其识别性能的研究

选用马来酸酐修饰的硅胶作为载体,丙烯酰胺为功能单体,N,N′-亚甲基双丙烯酰胺为交联剂,牛血红蛋白为模板分子,采用氧化还原悬浮聚合法,合成了具有选择性识别的牛血红蛋白分子印迹聚合物.并用红外光谱(IR)、扫描电子显微镜(SEM)和元素分析对聚合物进行了表征,结果表明载体表面成功地接枝了分子印迹聚合物薄层.同时选择性吸附实验表明分子印迹聚合物具有良好的识别性能,能实现水溶液中牛血红蛋白的富集.     

聚酰胺-胺树状分子接枝到方法修饰多壁碳纳米管

采用聚酰胺-胺树状分子(PAMAM)“接枝到”这一温和而简单易行的方法修饰多壁碳纳米管(MWCNTs),制备了一种树状分子/碳纳米管(MWCNTs-g-PAMAM)纳米复合材料。在水、甲醇和乙醇等极性溶剂中,该复合材料具有很好的分散性。通过傅立叶变换红外光谱(FTIR)、X-射线光电子能谱(XPS)、热重分析(TGA)和透射电子显微镜(TEM)等对MWCNTs-g-PAMAM纳米复合材料进行了表征。FTIR表明接枝修饰是PAMAM与MWCNTs的共价键结合,TGA数据表明PAMAM成功修饰于MWCNTs侧壁,且接枝到MWCNTs上PAMAM的量随其代数(G1.0～G4.0)的不同而不同,具体顺序为G2.0＞G1.0≈G3.0＞G4.0.     

聚氨酯接枝多壁碳纳米管的制备及表征

采用两步法成功地将聚氨酯分子链以共价键连接到碳纳米管表面. 首先将聚丙烯酰氯通过与强酸氧化后多壁碳纳米管表面产生的羟基及少量羧基之间的化学反应共价接枝到碳纳米管表面; 然后将接枝到碳纳米管表面的聚丙烯酰氯与端羟基聚氨酯发生酯化反应, 实现了聚氨酯对碳纳米管的表面共价接枝. 采用傅里叶变换红外光谱(FTIR)、透射电镜(TEM)、扫描电镜(SEM) 和热重分析(TGA)等对接枝后的产物进行了表征, 结果表明, 聚氨酯已共价接枝到碳纳米管表面, 被接枝的聚合物的含量接近90%.     

Preparation of micelle-encapsulated single-wall and multi-wall carbon nanotubes with amphiphilic hyperbranched polymer

The hyperbranched polyester (Boltorn^TM H20) was modified by maleic anhydride and then polystyrene (H20-MAh-PSt) to form amphiphilic micelles in water. The single-wall and multi-wall carbon nanotubes (SWCNTs and MWCNTs, respectively) were encapsulated in the formed micelles through non-covalent interactions. The formed structures were confirmed by FTIR, NMR, GPC, and XPS analysis. The dispersion and aggregation behaviors were observed by TEM and UV-vis and Raman spectroscopic analysis. The results showed that the dispersion performance of the obtained micelle-encapsulated carbon nanotubes in water was greatly improved compared to the pure carbon nanotubes. From the TEM observation, the individual SWCNT structure and the uniform polymer coating around the surface of SWCNT were seen after crosslinking. The Raman spectroscopic measurements also demonstrated that for the crosslinked samples, no effect occurred associated with concentration-dependent carbon nanotube aggregation.     

Glass bead grafting with poly(carboxylic acid) polymers and maleic anhydride copolymers

Glass beads were etched with acids and bases to increase the surface porosity and the number of silanol groups that could be used for grafting materials to the surfaces. The pretreated glass beads were functionalized using 3‐aminopropyltriethoxysilane (APS) coupling agent and then further chemically modified by reacting the carboxyl groups of carboxylic acid polymers with the amino groups of the pregrafted APS. Several carboxylic acid polymers and poly(maleic anhydride) copolymers, such as poly(acrylic acid) (PAA), poly(methacrylic acid) (PMA), poly(styrene‐alt‐maleic anhydride) (PSMA), and poly(ethylene‐alt‐maleic anhydride) (PEMA) were grafted onto the bead surface. The chemical modifications were investigated and characterized by FT‐IR spectroscopy, particle size analysis, and tensiometry for contact angle and porosity changes. The amount of APS and the different polymer grafted on the surface was determined from thermal gravimetric analysis and elemental analysis data. Spectroscopic studies and elemental analysis data showed that carboxylic acid polymers and maleic anhydride copolymers were chemically attached to the glass bead surface. The improved surface properties of surface modified glass beads were determined by measuring water and hexane penetration rates and contact angle. Contact angles increased and porosity decreased as the molecular weights of the polymer increased. The contact angles increased with the hydrophobicity of the attached polymer. The surface morphology was examined by scanning electron microscopy (SEM) and showed an increase in roughness for etched glass beads. Copyright © 2007 John Wiley & Sons, Ltd.     

Preparation and characterization of PE and PE-g-MAH/montmorillonite nanocomposites

Polyethylene (PE) was chemically modified with grafting maleic anhydride (MAH) monomer on its backbone at first. Then the melt-direct intercalation method was employed to prepare two kinds of nanocomposites, polyethylene (PE)/organic montmorillonite (Org-MMT) and maleic anhydride grafted polyethylene (PE-g-MAH)/Org-MMT nanocomposites. X-ray diffractometery (XRD) was used to investigate the intercalation effect and transmission electron microscopy (TEM) to observe the dispersion of Org-MMT interlayers in matrixes. The results show that an intercalated structure would be acquired on mixing the PE and Org-MMT; and an almost exfoliated system would be obtained by mixing the PE-g-MAH and Org-MMT. Moreover, further measurements via thermogravimetric (TGA) and differential scanning calorimetry (DSC) showed that both of the nanocomposites had a higher thermal decomposition temperature and a higher crystallization temperature when compared to the original matrix. At the same time, the thermal and crystal properties for the PE-g-MAH prepared in this experiment are also discussed.     

Synthesis and characterization of imidized poly(styrene‐maleic anhydride) nanoparticles in stable aqueous dispersion

Organic nanoparticles are synthesized by partial imidization of high‐molecular weight styrene(maleic‐anhydride) with 26 to 34 mol% maleic anhydride, in aqueous environment and presence of ammonium hydroxide. The nanoparticle dispersions have a maximum solid content of 35 wt% and good stability that critically depends on the ratio of imidized and ammonolyzed maleic anhydride moieties. The deprotonated residual maleic anhydride moieties provide dispersion stability at pH > 4, while protonation at pH < 4 causes nanoparticle sedimentation. After presentation of the synthesis conditions, the imidization reaction is characterized by FT‐IR and Raman spectroscopy, followed by thermal analysis (TGA, DSC), and morphological characterization (DLS, SEM, TEM, AFM). The reaction conditions were optimized by physical characterization of various dispersions, and finally nanoparticles could be obtained with a maximum degree of imidization of 77% in dispersed conditions, or 90 to 95% after drying that are favorable for coating applications. Copyright © 2010 John Wiley & Sons, Ltd.     

Polymers from renewable resources. II. A study in the radio chemical grafting of poly(styrene‐alt‐maleic anhydride) onto cellulose extracted from pine needles

A binary mixture of styrene and maleic anhydride has been graft copolymerized onto cellulose extracted from Pinus roxburghii needles. The reaction was initiated with gamma rays in air by the simultaneous irradiation method. Graft copolymerization was studied under optimum conditions of total dose of radiation, amount of water, and molar concentration previously worked out for grafting styrene onto cellulose. Percentage of total conversion (Pg), grafting efficiency (%), percentage of grafting (Pg), and rates of polymerization (R_p), grafting (R_g), and homopolymerization (R_h) have been determined as a function of maleic anhydride concentration. The high degree of kinetic regularity and the linear dependence of the rate of polymerization on maleic anhydride concentration, along with the low and nearly constant rate of homopolymerization suggest that the monomers first form a complexomer which then polymerizes to form grafted chains with an alternating sequence. Grafting parameters and reaction rates achieve maximum values when the molar ratio of styrene to maleic anhydride is 1 : 1. Further evidence for the alternating monomer sequence is obtained from quantitatively evaluating the composition of the grafted chains from the FT‐IR spectra, in which the ratio of anhydride absorbance to aromatic (CC) absorbance for the stretching bands assigned to the grafted monomers remained constant and independent of the feed ratio of maleic anhydride to styrene. Thermal behaviour of the graft copolymers revealed that all graft copolymers exhibit single stage decomposition with characteristic transitions at 161–165°C and 290–300°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1763–1769, 1999     

The role of interfacial compatibilization upon the microstructure and electrical conductivity threshold in polypropylene/expanded graphite nanocomposites

Attempts have been made to evaluate the effect of interface and degree of interfacial interaction upon electrical conductivity threshold in polypropylene/expanded graphite (PP/EG) nanocomposites, and dispersion state of graphite nanosheets. For this purpose, maleic anhydride grafted polypropylene (PPgMA) and maleic anhydride grafted EPDM (EPDMgMA) were used as compatibilizer. Nanocomposite samples containing 1–5 vol% of EG were prepared by melt mixing method using laboratory scale internal mixer. Characterization was carried out by using X‐ray diffraction (XRD), differential scanning calorimeter (DSC), thermo‐gravimetric analysis (TGA), scanning electron microscope (SEM), transmission electron microscope (TEM), and rheo‐mechanical spectroscopy (RMS). The conductivity measurements were carried out by using four point probe method according to ASTM D991. Results showed that the conductivity threshold is controlled by the extent of interfacial interaction between PP and EG. So, better conductivity was obtained using PPgMA as compatibilizer which causes higher level of interaction between PP and EG, and therefore better dispersion of the EG nanolayers in the polymer matrix. On the other hand, high levels of compatibilizers, especially EPDMgMA, caused formation of separated aggregates of EG shelled with the compatibilizer, which results in the reduction of conductivity of the nanocomposites. This finding has been verified by SEM, RMS, and conductivity measurements. Effects of EG nanolayers on crystalline structure and thermal decomposition temperature of the nanocomposites have also been investigated by DSC and TGA, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Grafting of maleic anhydride onto carbon black surface via ultrasonic irradiation

The grafting of maleic anhydride onto carbon black surface based on the Diels–Alder addition via ultrasonic irradiation was investigated. Fourier transform infrared spectroscopy (FT‐IR) and thermogravimetric analysis (TGA) were used to determine the chemical structure of the resulting products. The anhydride ring in the modified products can be opened into two carboxylic groups. Accordingly, the carboxylated carbon black was analyzed quantitatively through acid‐based titration to determine the concentration of anhydride ring on the modified carbon black's surface. The grafted molecules amount calculated from the concentration of the anhydride ring was consistent with the results of TGA data. Comparison of zeta potential measurement demonstrated that there were more negative charges attached to the surface of carbon black after ultrasonic modification. TEM observations showed that the conglomeration degree of modified carbon black decreased more than that of initial carbon black. Copyright © 2008 John Wiley & Sons, Ltd.     

The Localization Behavior of Different CNTs in PC/SAN Blends Containing a Reactive Component

Co-continuous blend systems of polycarbonate (PC), poly(styrene-co-acrylonitrile) (SAN), commercial non-functionalized multi-walled carbon nanotubes (MWCNTs) or various types of commercial and laboratory functionalized single-walled carbon nanotubes (SWCNTs), and a reactive component (RC, N-phenylmaleimide styrene maleic anhydride copolymer) were melt compounded in one step in a microcompounder. The blend system is immiscible, while the RC is miscible with SAN and contains maleic anhydride groups that have the potential to reactively couple with functional groups on the surface of the nanotubes. The influence of the RC on the localization of MWCNTs and SWCNTs (0.5 wt.%) was investigated by transmission electron microscopy (TEM) and energy-filtered TEM. In PC/SAN blends without RC, MWCNTs are localized in the PC component. In contrast, in PC/SAN-RC, the MWCNTs localize in the SAN-RC component, depending on the RC concentration. By adjusting the MWCNT/RC ratio, the localization of the MWCNTs can be tuned. The SWCNTs behave differently compared to the MWCNTs in PC/SAN-RC blends and their localization occurs either only in the PC or in both blend components, depending on the type of the SWCNTs. CNT defect concentration and surface functionalities seem to be responsible for the localization differences.     

Effect of Functionalized Copolymer on Titanium Dioxide Pigment Dispersion

The influence of adsorption of polymers containing different functional groups on the dispersion behavior of pigment particles has been investigated in water. The polymers chosen are styrene‐maleic anhydride copolymer modified with three different amines, tris (hydroxymethyl) amine, semicarbazide, and thiosemicarbazide of different hydrophilicity, to yield the corresponding grafted amic acids. The modified graft copolymers were characterized by Fourier transform infrared spectroscopy and ¹H‐nuclear magnetic resonance spectroscopy. Application of these amic acids as a dispersing agent to disperse titanium dioxide in water was studied. The Daniel flow method was used to assess the dispersing ability of these amic acids, and it was found that all the synthesized dispersants showed dispersion action on the pigment particles.