偏氯乙烯共聚物/层状双金属氢氧化物纳米复合材料的制备与表征

通过硝酸根插层层状双金属氢氧化物(LDH)与可逆加成-断裂链转移(RAFT)试剂S,S’-对(α,α’-二甲基-α″-乙酸)三硫代碳酸酯(CTA)阴离子的离子交换制备CTA阴离子插层LDH,再通过原位RAFT活性自由基聚合制备偏氯乙烯-丙烯酸甲酯(VDC-MA)共聚物/LDH纳米复合材料.采用傅里叶变换红外光谱、元素分析和X-射线衍射、透射电子显微镜、凝胶渗透色谱仪和热失重仪表征了CTA阴离子插层LDH和纳米复合材料的结构和性能.结果表明,CTA阴离子可以置换硝酸根阴离子插入到LDH层间,LDH层间距由0.89 nm增大到1.50 nm;在原位RAFT聚合过程中,LDH逐渐剥离,LDH以纳米层板形式分散在VDC-MA共聚物基体中;VDC-MA共聚物数均分子量随加入的插层CTA阴离子含量增加而减小,聚合具有活性特征.此外,含量LDH的引入可明显提高VDC-MA共聚物的热稳定性.     

结构型载体负载纳米银合成及催化性能

通过两步聚合法合成具有温度敏感性能的核-壳型聚(苯乙烯-N-异丙基丙烯酰胺)/N-异丙基丙烯酰胺共聚3-(甲基丙烯酰氧)丙基三甲氧基硅烷(P(St-NIPAM)/P(NIPAM-co-MPTMS))复合微凝胶材料.以经3-巯丙基-三甲氧基硅烷(MPS)表面修饰的复合微凝胶为载体,乙醇为还原剂,在温和条件下控制性还原制备纳米银微粒.通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外(FT-IR)光谱仪、X-射线光电子能谱(XPS)、X射线衍射(XRD)仪、热分析(TGA)和紫外-可见(UV-Vis)分光光度计等手段对P(St-NIPAM)/P(NIPAM-co-MPTMS)-(SH)Ag复合微凝胶的结构、组成和性质进行表征.同时,以硼氢化钠还原对硝基苯酚为模型反应,对该复合材料催化还原性能进行了评价.结果表明,载体含有巯基的有机-无机杂化网络结构的限域作用使原位合成的纳米银微粒的分散性较好.载体微凝胶壳层链节中无机组分MPTMS的引入在一定程度上降低了复合凝胶温敏性,但复合凝胶仍表现出催化还原反应的温敏性调控和良好的催化活性.以上实验结果与温敏性PNIPAM链节被无机网络分隔而有利于反应传质及壳层巯基对原位纳米银形成尺寸和空间分布的有效控制有关.本研究对功能性金属纳米催化复合材料的研究具有积极借鉴意义.     

乳液聚合法制备剥离型PS/MMT纳米复合材料

以阳离子表面活性剂十八烷基三甲基氯化铵(OTAC)和烯丙基十八烷基二甲基氯化铵(ATAC)为插层处理剂改性蒙脱土(MMT),原位乳液聚合分别制备了PS/C18MMT和PS/AC18MMT两种纳米复合材料.XRD和TEM分析表明,MMT均被剥离成单个或几个片层无规的分散在PS基体中,TGA分析表明,MMT的加入提高了材料的耐热性能,当PS基体与有机化处理的MMT片层发生一定的化学连接后,PS/AC18MMT纳米复合材料表现出更好的耐热性能.动态力学分析表明,MMT的加入提高了PS的玻璃态储能模量,降低了材料的动态损耗;PS/AC18MMT纳米复合材料的玻璃化温度较PS有所提高,而PS/C18MMT的玻璃化温度与PS相比略有降低.     

粘土/聚烯烃纳米复合材料研究进展

原位聚合;插层复合;粘土/聚烯烃纳米复合材料研究进展     

丙烯酸树脂／蒙脱土纳米复合材料的制备研究

采用离子交换法,用十六烷基三甲基溴化铵对钠基蒙脱土(Na-MMT)进行改性制备了有机蒙脱土(OMMT).用丙烯酸(AA)、硫酸化蓖麻油、乳化剂OP-10、过硫酸钾为原料进行水溶液聚合制得丙烯酸树脂.将丙烯酸树脂与改性蒙脱土通过聚合插层制备了丙烯酸树脂/ 蒙脱土纳米复合材料.通过傅立叶变换红外(FTIR)和X-射线衍射 (XRD)等手段对复合材料的结构进行了表征,结果表明:丙烯酸树脂插层进入有机蒙脱土内可形成插层型或剥离型的纳米复合材料.蒙脱土含量及蒙脱土与丙烯酸树脂的反应温度、反应时间均对复合材料的剥离行为产生影响,在蒙脱土含量为树脂固含量的7%、温度为70℃、反应4h的条件下可得到完全剥离的纳米复合材料.     

原位聚合法制备聚乳酸/黄腐植酸季铵盐插层皂石纳米复合材料及其结构表征

以新疆地产风化煤(weathered coal)为原料通过硝酸氧解工艺制备黄腐植酸(fulvic acid,FA),并对黄腐植酸进行季铵化改性,合成黄腐植酸季铵盐(quaternary fulvic acid,QFA).以皂石为原料通过超声波辐照法制备黄腐植酸季铵盐插层皂石(QFA-saponite).以丙交酯和QFA-saponite为原料,在辛酸亚锡催化作用下,制备了聚乳酸/黄腐植酸季铵盐插层皂石(PLA/QFA-saponite)纳米复合材料.通过正交实验探讨了聚合时间、聚合温度、催化剂和QFA-saponite加量对PLA分子量的影响,其最优反应条件为反应12 h、辛酸亚锡加量3%、温度150℃、QFA-saponite加量为2%,该正交优化条件下合成的PLA/QFA-saponite纳米复合材料的重均分子量可达95300.红外光谱分析表明黄腐植酸中引入了季铵根离子.X-射线衍射(XRD)对QFA-saponite的分析表明,QFA-saponite呈现部分剥离与插层共存的状态,其层间距达到1.57 nm,比皂石层间距增大0.17nm.用XRD、示差扫描量热仪(DSC)、偏光显微镜(POM)、热重分析(TGA)等方法对复合材料进行结构表征.结果表明,PLA/QFA-saponite纳米复合材料具有剥离型结构,QFA-saponite有效改善复合材料的结晶性能和热稳定性.抗菌实验表明,黄腐植酸季铵盐插层皂石对大肠杆菌(Escherichia coli),枯草杆菌(Bacillus subtilis),黑曲霉菌(Aspergillus)及青霉(Penicillium)有较强的抑菌效果,同时聚乳酸/黄腐植酸季铵盐插层皂石纳米复合材料也有良好的抗菌性能.     

层离型PMMA/镁铁双氢氧化物纳米复合材料的热降解研究

通过原位聚合方法制备了以非水溶性聚合物(聚甲基丙烯酸甲酯,PMMA)为基体,与MgFe双氢氧化物(LDH)具有良好相容性的层离型纳米复合材料.采用小角、广角X射线衍射(XRD)及透射电镜(TEM)对纳米复合材料的微观结构进行了分析,通过热重分析(TG)和玻璃化转变研究了纳米复合材料在空气和氮气氛围下的热降解过程.实验结果表明,MgFe-LDH的引入显著提高了聚合物基体的热降解温度和玻璃化转变温度,纳米复合材料的热稳定性显著提高.其中含量1.6 wt%的层离型纳米复合材料在失重50%时的热降解温度比纯样提高约69℃.并且整个纳米复合体系的相容性良好,含量8.0 wt%的样品,其可见光透过率仍可达90%以上.     

聚乳酸/壳聚糖季铵盐皂石纳米复合材料的原位插层聚合及性能表征

通过两步法将2,3-环氧丙基三甲基氯化铵接枝壳聚糖合成了水溶性壳聚糖季铵盐(HTCC),以其为插层剂对稀有的新疆皂石(Saponite)黏土矿物进行有机改性,制备了壳聚糖季铵盐皂石(HTCC-saponite),并以其为助剂,以丙交酯为单体,通过原位插层聚合法制备了聚乳酸(PLA)/HTCC-saponite纳米复合材料.最优化合成条件:聚合反应温度150℃,辛酸亚锡加量2%(质量分数),HTCC-saponite加量1%(质量分数)、聚合反应时间16 h.微观结构分析表明HTCC-saponite具有插层与剥离共存的结构.采用X射线衍射(XRD)、透射电子显微镜(TEM)、热重分析(TG-DTG)和差示扫描量热仪(DSC)等对PLA/HTCC-saponite纳米复合材料的微观结构、形貌及热稳定性进行了表征和分析.结果表明,HTCC-saponite有效改善了PLA的结晶性能,提高PLA的热稳定性.抗菌测试结果表明,HTCC-saponite具有良好的抗菌性,并赋予PLA/HTCC-saponite复合材料较强的抑菌能力.     

蒙脱土负载型引发剂的制备及在苯乙烯乳液聚合中的应用

通过正离子交换将引发剂AIBA负载在蒙脱土上制得负载型引发剂V50-MMT.进而采用原位乳液聚合方法引发苯乙烯聚合制备PS/MMT纳米复合材料.采用XRD、TGA、DSC、TEM和抽提等方法对负载型引发剂和纳米复合材料进行了表征.结果表明,负载过程中引发剂AIBA进入了MMT的片层之间;聚合过程中介于片层间的引发剂因发生分解一方面产生自由基引发St聚合,另一方面MMT发生了剥离分散;由此法制备的PS/MMT纳米复合材料,MMT片层无规、均匀地分散于PS基体中,片层厚度在几个纳米至十几个纳米之间,长度为几十至几百个纳米不等;大量的PS链段以化学键接枝在MMT的片层上,接枝在MMT片层上的PS的分子量及其分布与游离的PS不同.     

HPMA/OMMT和HPMA/CPMI/OMMT纳米复合材料的制备与表征

通过甲基丙烯酸羟丙酯(HPMA)单体与N-(4-羧基苯基)马来酰亚胺(CPMI)单体在有机蒙脱土(OMMT)中经原位插层自由基聚合反应制备了聚合物-无机纳米复合材料.OMMT由钠基蒙脱土通过十六烷基溴化铵插层处理制备.通过XRD和TEM对复合材料结构进行了表征,证实HPMA单体和HPMA/CPMI共单体在OMMT中原位插层共聚得到的复合材料均为剥离型纳米复合材料.OMMT含量为3 wt%的PolyHPMA/OMMT纳米复合材料起始分解温度为250℃,比相应的纯聚合物的热分解温度提高30℃.随着OMMT含量的增加,热分解温度进一步提高.但在测试温度范围内,PolyHPMA/OMMT纳米复合材料均没有出现明显的玻璃化转变温度.     

Synthesis and characterization of exfoliated polystyrene/ZnAl layered double hydroxide nanocomposite via emulsion polymerization

Exfoliated polystyrene (PS)/ZnAl layered double hydroxide (LDH) nanocomposites have been synthesized via emulsion polymerization in the presence of N-lauroyl-glutamate surfactants and long-chain n-hexadecane. The samples were characterized using elemental analysis, Fourier transform infrared (FTIR) spectrum, X-ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The XRD and TEM results demonstrate that the exfoliated ZnAl-LDH layers of 50-70 nm width and about 1 nm thickness were well dispersed at molecular level in the PS matrix. And the completely exfoliated PS/LDH nanocomposites can be obtained even at the 10 wt% LDH loading. When the 50% weight loss was selected as a comparison point, the decomposition temperature of exfoliated PS/LDH sample with 5 wt% LDH was ca. 28 degrees C higher than that of pure PS.     

熔融插层法制备LLDPE/MgAl-LDH 剥离型纳米复合材料及其热性能研究

The interlayer surface of MgAl layered double hydroxide （MgAl-LDH） was modified by exchanging about half of the interlayer nitrate anions by dodecyl sulfate anions （DS） to get MgAl（H-DS） LDH, and then the MgAl（H-DS） was melt intercalated by LLDPE to get the LLDPE/MgAl-LDH exfoliation nanocomposites. The samples were characterized by Fourier transform infrared （PTIR） spectroscopy, X-ray diffraction （XRD）, ion chromatography, transmission electron microscopy （TEM）, and thermogravimetry analysis （TGA）. The nanoscale dispersion of MgAl-LDH layers in the LLDPE matrix was verified by the disappearance of （001） XRD reflection of the modified MgAl-LDH and by the TEM observation. The TGA profiles of LLDPE/MgAl-LDH nanocomposites show a faster charring process between 210 and 370 ℃ and a higher thermal stability above 370 ℃than LLDPE. The decomposition temperature of the nanocomposites with 10 wt% MgAl（H-DS） can be 42 ℃ higher than that of LLDPE at 40% weight loss.     

Influence of four different types of organophilic clay on the morphology and thermal properties of polystyrene/clay nanocomposites prepared by using the γ-ray irradiation technique

Polystyrene (PS)/clay nanocomposites were successfully prepared by the γ-ray irradiation technique. Four different types of organophilic clays were used: three of the four contained a reactive group, while the other did not. Exfoliated PS/clay nanocomposites can be obtained by using reactive organophilic clay and intercalated PS/nanocomposites can be formed by using non-reactive ones, which was confirmed by X-ray diffraction (XRD) and by transmission electron microscopy (TEM). In the formation of exfoliated PS/nanocomposites, the effect of the double bond of the clay-intercalated agents is much more important than the alkyl chain length. The enhanced thermal properties of PS/nanocomposites were characterized by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). In particular, the enhancement of the thermal properties of PS/nanocomposites made using the reactive organophilic clay was much higher than that of the thermal properties of PS/nanocomposites incorporating non-reactive clay.     

Investigation of Structural,Rheological and Thermal Properties of PMMA/ONi-Al LDH Nanocomposites Synthesized via Solvent Blending Method: Effect of LDH Loading

This article addresses the synthesis of organically tailored Ni-Al layered double hydroxide(ONi-Al LDH) and its use in the fabrication of exfoliated poly(methyl methacrylate)(PMMA) nanocomposites. The pristine Ni-Al LDH was initially synthesized by co-precipitation method and subsequently modified using sodium dodecyl sulfate to obtain ONi-Al LDH. Nanocomposites of PMMA containing various amounts of modified Ni-Al LDH(3 wt%?7 wt%) were synthesized via solvent blending method to investigate the influence of LDH content on the properties of PMMA matrix. Several characterization methods such as X-ray diffraction(XRD), transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FTIR), rheological analysis, differential scanning calorimetry(DSC) and thermo gravimetric analysis(TGA), were employed to examine the structural, viscoelastic and thermal properties of PMMA/OLDH nanocomposites. The results of XRD and TEM examination confirm the formation of partially exfoliated PMMA/OLDH nanocomposites. The FTIR results elucidate that the characteristic bands for both pure PMMA and modified LDH are present in the spectra of PMMA/OLDH nanocomposites. Rheological analyses were carried out to examine the adhesion between polymer matrix and fillers present in the nanocomposite sample. The TGA data indicate that the PMMA nanocomposites exhibit higher thermal stability when compared to pure PMMA. The thermal decomposition temperature of PMMA/OLDH nanocomposites increases by 28 K compared to that of pure PMMA at 15% weight loss as a point of reference. In comparison with pure PMMA, the PMMA nanocomposite containing 7 wt% LDH demonstrates improved glass transition temperature(Tg) of around 3 K. The activation energy(Ea), reaction orders(n) and reaction mechanism of thermal degradation of PMMA/OLDH nanocomposites were evaluated using different kinetic models. Water uptake capacity of the PMMA/OLDH nanocomposites is less than that of the pure PMMA.     

The disorderly exfoliated LDHs/PMMA nanocomposites synthesized by in situ bulk polymerization: The effects of LDH-U on thermal and mechanical properties

The disorderly exfoliated layered double hydroxides/poly(methyl methacrylate) (LDHs/PMMA) nanocomposites were obtained in a two-stage process by the in situ bulk polymerization of methyl methacrylate (MMA) in the presence of 10-undecenoate intercalated LDH (LDH-U). The dispersed behavior of the LDH-U in the PMMA matrix was identified by using X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV/visible transmission spectroscopy. All these nanocomposites showed significantly enhancement of glass transition temperature (T_g) and the decomposition temperatures compared to pristine PMMA, as identified in differential scanning calorimetry (DSC) and thermogravimetric (TGA) analysis. The tensile modulus of these nanocomposites was also enhanced by incorporating the LDH-U into the PMMA matrix and increased as the amount of LDH-U increased. According to the analytical method of Ozawa-Flynn, the degradation activation energies of these nanocomposites are higher than that of pristine PMMA.     

乳液聚合法制备聚苯乙烯/Mg-Al层状双氢氧化物纳米复合材料

采用乳液聚合法制备阻燃性聚苯乙烯MgAl层状双氢氧化物(LDHs)纳米复合材料.通过对不同合成条件下复合材料的XRD谱,讨论了纳米复合材料的形成过程;经SEM图证实了LDHs是以剥离的纳米级层片分散在基体中的;TG和DSC谱图揭示了LDHs纳米层板可有效提高PS的热稳定性,并可使PS的玻璃化转化温度明显提高;当层状双氢氧化物在插层复合材料中含量为14.92%时,纳米复合材料的氧指数可达23.5%,其用量比在PS中直接添加纳米LDHs时要少约一倍.文中还分析了纳米复合材料的形成过程.     

Preparation and Characteration of UV-cured EA/MMT Nanocomposites Via In-Situ Polymerization

A long-chain surfactant, enzoylbenzyl-N,N-dimethyl-N-octadecylammonium bromide (BDOB) with a benzophenone group, was synthesized to modify the montmorillonites (MMT) for the preparation of nanocomposites via photo-induced polymerization. The BDOB-modified MMT was characterized by the fourier transform infrared spectrometer (FTIR), thermal gravimetric analyzer (TGA) and X-ray diffraction (XRD), and the results of XRD indicated that the intercalated structures of BDOB-modified MMT was obtained. The conversion of the bisphenol A epoxy diacrylate (EA) was quantified by the FTIR, and the results indicated that conversion increased with an increase in the amount of BDOB-modified MMT. The morphologies of the UV-cured EA/MMT nanocomposites prepared from this organically modified MMT were studied by means of XRD and TEM, and the results showed that all the samples contained an intercalated structure with partial exfoliated structure. The results of TGA and mechanical properties also indicated that the thermal and mechanical properties of UV-cured nanocomposites were significantly enhanced due to the presence of the long chain surfactant organically modified MMT.     

Synergistic effects of layered double hydroxide with phosphorus-nitrogen intumescent flame retardant in PP/EPDM/IFR/LDH nanocomposites

<正>Synergistic effects of layered double hydroxide(LDH) with intumescent flame retardanct(IFR) of phosphorus-nitrogen (NP) compound in the polypropylene/ethylene-propylene-diene/IFR/LDH(PP/EPDM/IFR/LDH) nanocomposites and related properties were studied by X-ray diffraction(XRD),transmission electron microscopy(TEM),scanning electron microscopy(SEM),limiting oxygen index(LOI),UL-94 test,cone calorimeter test(CCT) and thermo-gravimetric analysis (TGA).The XRD and TEM results show that the intercalated and/or exfoliated nanocomposites can be obtained by direct melt-intercalation of PP/EPDM into modified LDH and that LDH can promote the IFR additive NP to disperse more homogeneously in the polymer matrix.The SEM results provide positive evidence that more compact charred layers can be obtained from the PP/EPDM/NP/LDH sample than those from the PP/EPDM/LDH and PP/EPDM/NP samples during burning.The LOI and UL-94 rating tests show that the synergetic effects of LDH with NP can effectively increase the flame retardant properties of the PP/EPDM/NP/LDH samples.The data from the CCT and TGA tests indicate that the PP/EPDM/NP/LDH samples apparently decrease the HRR and MLR values and thus enhance the flame retardant properties and have better thermal stability than the PP/EPDM/LDH and PP/EPDM/NP samples.     

Investigation of structural,rheological and thermal properties of PMMA/ONi-Al LDH nanocomposites synthesized <Emphasis Type="Italic">via</Emphasis> solvent blending method: Effect of LDH loading

This article addresses the synthesis of organically tailored Ni-Al layered double hydroxide (ONi-Al LDH) and its use in the fabrication of exfoliated poly(methyl methacrylate) (PMMA) nanocomposites. The pristine Ni-Al LDH was initially synthesized by co-precipitation method and subsequently modified using sodium dodecyl sulfate to obtain ONi-Al LDH. Nanocomposites of PMMA containing various amounts of modified Ni-Al LDH (3 wt%-7 wt%) were synthesized via solvent blending method to investigate the influence of LDH content on the properties of PMMA matrix. Several characterization methods such as X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), rheological analysis, differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA), were employed to examine the structural, viscoelastic and thermal properties of PMMA/OLDH nanocomposites. The results of XRD and TEM examination confirm the formation of partially exfoliated PMMA/OLDH nanocomposites. The FTIR results elucidate that the characteristic bands for both pure PMMA and modified LDH are present in the spectra of PMMA/OLDH nanocomposites. Rheological analyses were carried out to examine the adhesion between polymer matrix and fillers present in the nanocomposite sample. The TGA data indicate that the PMMA nanocomposites exhibit higher thermal stability when compared to pure PMMA. The thermal decomposition temperature of PMMA/OLDH nanocomposites increases by 28 K compared to that of pure PMMA at 15% weight loss as a point of reference. In comparison with pure PMMA, the PMMA nanocomposite containing 7 wt% LDH demonstrates improved glass transition temperature (T _g) of around 3 K. The activation energy (E _a), reaction orders (n) and reaction mechanism of thermal degradation of PMMA/OLDH nanocomposites were evaluated using different kinetic models. Water uptake capacity of the PMMA/OLDH nanocomposites is less than that of the pure PMMA.