基于原子转移自由基聚合法制备多壁碳纳米管/Ag复合材料

在多壁碳纳米管(MWNT)表面键接可用于原子转移自由基聚合(ATRP)的引发剂,并以此引发甲基丙烯酸缩水甘油酯(GMA)在MWNT表面的ATRP.利用红外光谱(FT-IR)、核磁共振(<'1>H-NMR)和透射电镜(TEM)对接枝聚合物MWNT的结构和外观形貌进行了研究.接枝在MWNT表面的PGMA与过量的乙二胺发生开...     

利用开环聚合和原子转移自由基聚合在纳米二氧化硅表面接枝聚合物

利用硅烷偶联剂KH-550处理纳米二氧化硅(SiO_2)表面,得到氨基化的SiO_2,再通过溴异丁酸缩水甘油酯与氨基的开环反应,在SiO_2表面同时键接了开环聚合(ROP)的引发剂-OH和原子转移自由基聚合(ATRP)的引发剂-Br(SNPs-fOH/Br)。以SNPs-f-OH/Br为引发剂,分别进行ROP和ATRP,在纳米SiO_2表面接枝了聚己内酯(PCL)和聚苯乙烯(PS)混合聚合物刷(Mixed brush)。采用红外光谱、透射电镜、热失重、凝胶渗透色谱等方法对所得到的复合粒子进行了表征和测试。研究结果表明,混合聚合物刷成功接枝到了纳米SiO_2表面,通过控制聚合时间可以控制2种接枝聚合物的相对分子质量。本方法为纳米粒子表面接枝混合聚合物刷提供了一种简便的方法。     

PP/碳纳米管复合材料的结构与性能

采用原子转移自由基(ATRP)活性聚合方法在多壁碳纳米管(MWNT)表面接枝丙烯酸丁酯聚合物(PBA),并以此对聚丙烯(PP)进行改性。红外光谱(FT-IR)及透射电子显微镜(TEM)测试结果表明,采用ATRP法成功地将PBA接枝到多壁碳纳米管(MWNT)表面。采用熔融共混法制备了PP/MWNT复合材料,对其力学性能和耐热性能进行了研究,结果表明,接枝聚合物的碳纳米管提高了复合材料的拉伸强度和冲击强度,提高了PP的耐热性。MWNT-PBA和MWNT-COOH加入PP都能提高材料的性能,而MWNT-PBA比MWNT-COOH的作用更加明显。     

碳纳米管/聚甲醛复合材料的结晶形态与力学性能

在对碳纳米管(CNT)进行表面修饰后,采用活性自由基聚合法(ATRP)在其表面接枝聚甲基丙烯酸甲酯(PMMA)。再将接枝上聚合物的碳纳米管添加到聚甲醛中熔融共混制得碳纳米管/聚甲醛纳米复合材料。通过偏光显微镜观察其结晶形态,并研究了功能化碳纳米管的含量对聚甲醛缺口冲击强度的影响,结果表明,CNT-PMMA的加入使聚甲醛球晶细化,复合材料的缺口冲击强度得到提高。     

两亲性嵌段共聚物改性的多壁碳纳米管的制备

通过对碳纳米管进行表面改性制得具有引发ATRP反应活性的碳纳米管(MWNT-Br),以MWNT-Br作引发剂经过两次ATRP反应将聚乙烯基吡咯烷酮(PVP)和聚甲基丙烯酸特丁酯(PtBMA)先后接枝到多壁碳纳米管表面制得两亲性嵌段共聚物接枝的碳纳米管(MWNT-PVP-b-PtBMA),用红外光谱、热失重和透射电镜对两亲性碳纳米管进行了表征.并考察了修饰前弱亲油性的纯碳纳米管、酸化后亲水性的碳纳米管和修饰后两亲性碳纳米管这3种碳纳米管在水和氯仿形成的两相体系中的分散情况,观察到所制备的两亲性碳纳米管能够均匀分散在油水两相界面上.     

原子转移自由基聚合反应改性氧化石墨烯研究进展

原子转移自由基聚合(ATRP)是一种具有潜在应用价值的可控活性自由基聚合方法,通过ATRP反应对氧化石墨烯(GO)进行改性,可以有效控制各种接枝聚合物分子链的长度和接枝密度,赋予GO不同的功能性,如良好的溶剂分散性、环境敏感刺激响应性、生物相容性等。文中分别从GO表面固定引发剂直接引发ATRP反应和GO表面非共价键结合ATRP聚合物分子链2种途径,对ATRP反应改性GO进行综述,总结了ATRP改性反应的过程条件和研究方法,并指出了GO功能化复合材料的功能特性和应用前景。     

ATRP法在纳米硅胶粒子表面接枝聚甲基丙烯酸缩水甘油酯

将原子转移自由基聚合(ATRP)引发剂2-溴基异丁酰溴(BSB)化学键合在纳米硅胶微粒表面,以CuBr为催化剂,2,2′-联吡啶(byp)为配体,并加入少量自由(牺牲性)引发剂2-溴丙酸乙酯(BRA),在BSB-SiO2粒子表面进行了甲基丙烯酸缩水甘油酯(GMA)的接枝聚合反应。采用凝胶色谱(GPC)与热重分析(TGA)等手段对活性接枝聚合进行了确认。研究结果表明,接枝聚合反应呈现一级反应的动力学规律,接枝聚合物分子量及接枝度与单体转化率之间呈直线关系,反应过程中接枝聚合物链的密度恒定,充分显示了可控聚合的特征,成功地实现了功能单体GMA在纳米硅胶微粒表面的可控接枝聚合。     

纳米纤维素ARGET ATRP接枝PMMA改性研究

采用再生电子转移催化剂原子自由基聚合(ARGET ATRP)的方法,使甲基丙烯酸甲酯(MMA)在纳米纤维素(NCC)表面自增长,得到聚甲基丙烯酸甲酯(PMMA)接枝改性的NCC。通过傅里叶变换红外光谱(FT-IR)、X射线衍射分析(XRD)等测试方法对接枝改性前后的NCC的性能和结构进行了分析;采用凝胶渗透色谱(GPC)测定合成的PMMA的分子量及其分布。结果表明PMMA的分子量为8000左右,分子量分布较窄(Mw/Mn=1.11),说明ARGET ATRP可以有效控制NCC表面接枝PMMA聚合的均一性。     

改性多壁碳纳米管/聚氨酯形状记忆复合材料的制备及性能

利用表面引发原子转移自由基聚合(SI-ATRP)的方法在多壁碳纳米管(MWNT)表面接枝聚甲基丙烯酸甲酯(PMMA),接枝改性后的多壁碳纳米管通过原位聚合法与形状记忆聚氨酯(SMPU)合成SMPU/MWNT-PMMA复合材料。采用FTIR、SEM、TGA、DMA等方法表征材料的结构与性能,并测试其形状记忆性能。结果表明,随着MWNT-PMMA含量的增大,复合材料的力学性能显著改善,最大拉伸强度达到81.30MPa,玻璃化转变温度(Tg)增大,热稳定性增强,且复合材料具有电热双敏性,循环四次后形状固定率和形状恢复率均在95%以上,具有较好的形状记忆性能。     

碳纳米管／PA6纳米复合材料的制备及力学性能

采用RAFT活性聚合反应在碳纳米管表面接枝聚甲基丙烯酸甲酯(二硫代酯化合物作RAFT试剂),并制备了碳纳米管/PA6纳米复合材料。利用FT-IR、TEM、SEM、TGA等测试方法表征接枝聚合物后的碳纳米管,考察了碳纳米管的用量对碳纳米管/PA6纳米复合材料力学性能的影响,并观察了碳纳米管/PA6纳米复合材料冲击断面形貌。结果表明,聚合物接枝到了碳纳米管表面,碳纳米管/PA6纳米复合材料的力学性能明显提高。     

Surface-initiated atom transfer radical polymerization of methyl methacrylate from magnetite nanoparticles at ambient temperature

The synthesis of methyl methacrylate (MMA) brush from the surface of magnetite nanoparticles (core-shell structure), from initiator moieties anchored covalently to the nanoparticles, via room temperature atom transfer radical polymerization (ATRP) is described. The surface-initiated polymerization was carried out from a surface-confined initiator containing a 2-bromoisobutyrate moiety with Cu(I)Br/PMDETA catalytic system. The initiator moiety was covalently anchored to the nanoparticles via a two step modification reaction scheme. Controlled polymerization was observed if ethyl-2-bromoisobutyrate (2-EiBrB) was added as a free/sacrificial initiator. A linear increase of molecular weight and a narrow molecular weight distribution of the PMMA formed in solution, provide evidence for a controlled surface-initiated polymerization, leading to surface-attached polymer brushes under mild conditions. The grafted PMMA provides good stability and dispersibility for the nanoparticles in organic solvents.     

原子转移自由基聚合制备PMMA/POSS杂化材料

以八(γ-氯丙基)倍半硅氧烷(OCP-POSS)为引发剂,通过原子转移自由基聚合(ATRP)制备了PMMA/OCP-POSS有机/无机杂化材料.采用GPC、DSC和TGA对杂化材料的结构与性能进行了表征.结果表明,在DMF、异丙醇、甲苯等3种不同溶剂中均可合成分子量分布较窄的PMMA杂化材料.以DMF为溶剂,所得PMMA/OCP-POSS杂化材料的分子量分布系数可达到1.18.与分子量相当的线形PMMA相比,含OCP-POSS的PMMA杂化材料具有更高的玻璃化转变温度和热稳定性.     

Oxygen Barrier of Multiwalled Carbon Nanotube/Polymethyl Methacrylate Nanocomposites Prepared by in situ Method

Multiwalled carbon nanotubes (MWCNTs)/poly(methyl methacrylate) (PMMA) nanocomposites were prepared by ultrasonic assisted emulsifier free emulsion polymerization technique with variable concentration of functionalized carbon nanotubes. MWCNTs were functionalized with H 2 SO 4 and HNO 3 with continuing sonication and polished by H 2 O 2 . The appearance of Fourier transform infrared absorption bands in the PMMA/MWCNT nanocomposites showed that the functionalized MWCNT interacted chemically with PMMA macromolecules. The surface morphology of functionalized MWCNT and PMMA/MWCNT nanocomposites were studied by scanning electron microscopy. The dispersion of MWCNT in PMMA matrix was evidenced by high resolution transmission electron microscopy. The oxygen permeability of PMMA/MWCNT nanocomposites gradually decreased with increasing MWCNT concentrations.     

Influence of multiwall carbon nanotube functionality and loading on mechanical properties of PMMA/MWCNT bone cements

Poly (methyl methacrylate) (PMMA) bone cement—multi walled carbon nanotube (MWCNT) nanocomposites with weight loadings ranging from 0.1 to 1.0 wt% were prepared. The MWCNTs investigated were unfunctionalised, carboxyl and amine functionalised MWCNTs. Mechanical properties of the resultant nanocomposite cements were characterised as per international standards for acrylic resin cements. These mechanical properties were influenced by the type and wt% loading of MWCNT used. The morphology and degree of dispersion of the MWCNTs in the PMMA matrix at different length scales were examined using field emission scanning electron microscopy. Improvements in mechanical properties were attributed to the MWCNTs arresting/retarding crack propagation through the cement by providing a bridging effect and hindering crack propagation. MWCNTs agglomerations were evident within the cement microstructure, the degree of these agglomerations was dependent on the weight fraction and functionality of MWCNTs incorporated into the cement.     

Facile one-pot synthesis of brush polymers through tandem catalysis using Grubbs' catalyst for both ring-opening metathesis and atom transfer radical polymerizations

Using Grubbs' catalyst Cl2(PCy3)2Ru=CHPh for tandem catalysis, poly(methyl methacrylate)-based brush polymers were prepared by one-pot sequential ring-opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP) via an inimer having both an alpha-bromoisobutyrate ATRP initiator functionality and an exo-norbornenyl ROMP monomer functionality. The surface morphologies and aggregation behaviors of these nanoscopic single molecules were studied by tapping-mode atomic force microscopy measurements on mica.     

Facile synthesis of thick films of poly(methyl methacrylate), poly(styrene), and poly(vinyl pyridine) from Au surfaces

Atom transfer radical polymerization (ATRP) is commonly used to grow polymer brushes from Au surfaces, but the resulting film thicknesses are usually significantly less than with ATRP from SiO(2) substrates. On Au, growth of poly(methyl methacrylate) (PMMA) blocks from poly(tert-butyl acrylate) brushes occurs more rapidly than growth of PMMA from initiator monolayers, suggesting that the disparity between growth rates from Au and SiO(2) stems from the Au surface. Radical quenching by electron transfer from Au is probably not the termination mechanism because polymerization from thin, cross-linked initiators gives film thicknesses that are essentially the same as the thicknesses of films grown from SiO(2) under the same polymerization conditions. However, this result is consistent with termination through desorption of thiols from noncross-linked films, and reaction of these thiols with growing polymer chains. The enhanced stability of cross-linked initiators allows ATRP at temperatures up to ～100 °C and enables the growth of thick films of PMMA (350 nm), polystyrene (120 nm) and poly(vinyl pyridine) (200 nm) from Au surfaces in 1 h. At temperatures >100 °C, the polymer brush layers delaminate as large area films.     

4-(氯甲基)苯基三甲氧基硅烷引发的甲基丙烯酸甲酯的原子转移自由基聚合

以含双官能团的4-(氯甲基)苯基三甲氧基硅烷(CM TM S)为引发剂,CuC l/ligand为催化剂体系,二甲苯为溶剂,进行甲基丙烯酸甲酯(MMA)的原子转移自由基聚合(ATRP),重点研究了配体对聚合反应的影响。通过1H-NM R表征,证明PMMA是由CM TM S引发MMA聚合而得。聚合转化率和聚合物分子量及其分布测定结果表明,分别采用具有长链烷基的4,4'-二壬基-2,2'-联吡啶(dN bpy)和N,N,N',N',N″-五甲基二乙基三胺(PM DETA)为配体,所得聚合物的数均分子量与转化率之间的线性关系比较好,分子量分布较窄(M-w/M-n分别为1.27和1.30);而采用2,2'-联吡啶(bpy)为配体,所得聚合物数均分子量随转化率变化关系远远偏离理论分子量随转化率变化关系,且分子量分布相对较宽(M-w/M-n为1.41)。     

Microspherical poly(methyl methacrylate)/multiwalled carbon nanotube composites prepared via in situ dispersion polymerization

In this study, microspherical poly(methyl methacrylate)/multi-walled carbon nanotube (PMMA/ MWCNT) composites were directly prepared by in situ dispersion polymerization using poly (N-vinylpyrrolidone) in methanol media. PMMA/MWCNT microspheres having a diameter of 2.6 approximately 3.9 microm and a molecular weight of 58,000 approximately 65,000 g/mol with a 15.7 approximately 19.5% coefficient of variation (Cv) were synthesized. The morphology of the synthesized composite was investigated using scanning electron microscopy and transmission electron microscopy. The experimental results demonstrated that MWCNTs are well dispersed and embedded in the final PMMA/MWCNT microspheres. The prepared PMMA/MWCNT microspheres were investigated in terms of their capacity to serve as an electrorheological (ER) materials.     

多壁碳纳米管/聚醚砜环氧树脂复合材料的制备及力学性能

环氧树脂具有优异的热性能及力学性能,但本身脆性较大。为制备低成本、高性能的环氧树脂体系,使用聚醚砜（PES）和多壁碳纳米管（MWCNT）对环氧树脂进行增韧,制备了不同PES含量的PES-环氧树脂共混物,讨论了PES含量对环氧树脂力学性能的影响;采用熔融法,并配合使用机械搅拌、高剪切分散和超声分散制备了MWCNT/PES-环氧树脂复合材料,测试了其拉伸性能及断裂韧性,用SEM观察了MWCNT在树脂中的分散状态以及拉伸试样的断口形貌。结果表明：MWCNT的加入能够提高PES-环氧树脂体系的综合力学性能,且当MWCNT含量为0.7wt%时,树脂体系的综合力学性能最好;低PES含量下,小于1.0wt%的MWCNT的加入使材料力学性能超过用20.0wt%PES改性的环氧树脂;PES与MWCNT对环氧树脂具有协同增韧作用。     

含有POSS的嵌段聚合物的制备及热性能

以单官能团笼状结构倍半硅氧烷(POSS)为引发剂,氯化亚铜/2,2-联吡啶为催化体系,甲苯为溶剂,采用原子转移自由基聚合法(ATRP)制备了大分子引发剂POSS/PMMA和POSS/PMMA-PS嵌段聚合物。通过核磁共振(1H-NMR)、X射线光电子能谱(XPS)和凝胶渗透色谱(GPC)表征了大分子引发剂和嵌段聚合物的结构,实现了POSS在聚合物中的单分散。此外,热重分析(TGA)结果表明,POSS/PMMA和POSS/PMMA-PS嵌段聚合物的分解温度与纯聚甲基丙烯酸甲酯(PMMA)相比分别提高了60℃和151℃。