The preparation and physical properties of UP/montmorillonite nanocomposite by UV radiation curing

This article describes the preparation and properties of unsaturated polyester (UP)/montmorillonite (MMT) nanocomposite by UV radiation. Benzildimethylketal and 1‐hydroxy cyclohexyl phenyl ketone (HCPK) as a photoinitiator in UP were photolyzed under nitrogen condition. Analysis of X‐ray diffraction patterns of the composites shows that the interlayer spacing of MMT is substantially increased. The type and amount of photoinitiator affects the level of improvement in mechanical properties, and our results suggest that HCPK is a more efficient photoinitiator of UP curing reaction. The interaction between photoinitiators and MMT should be considered to acquire the reinforcement effect of the dispersed MMT nanolayers. The properties of nanocomposite are dependent upon the amount of MMT. The effect of MMT concentration on thermal and dielectric properties is also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3609–3615, 2006     

Effect of clay modification on the morphological,mechanical, and thermal properties of polyamide 6/polypropylene/montmorillonite nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic montmorillonite (OMMT) were prepared by melt compounding. The sodium montmorillonite (Na‐MMT) was modified using three different types of alkyl ammonium salts, namely dodecylamine, 12‐aminolauric acid, and stearylamine. The effect of clay modification on the morphological and mechanical properties of PA6/PP nanocomposites was investigated using x‐ray diffraction (XRD), transmission electron microscopy (TEM), tensile, flexural, and impact tests. The thermal properties of PA6/PP nanocomposites were characterized using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and heat distortion temperature (HDT). XRD and TEM results indicated the formation of exfoliated structure for the PA6/PP nanocomposites prepared using stearylamine modified montmorillonite. On the other hand, a mixture of intercalated and exfoliated structures was found for the PA6/PP nanocomposites prepared using 12‐aminolauric acid and dodecylamine modified montmorillonite. Incorporation of OMMT increased the stiffness but decreased the ductility and toughness of PA6/PP blend. The PA6/PP nanocomposite containing stearylamine modified montmorillonite showed the highest tensile, flexural, and thermal properties among all nanocomposites. This could be attributed to better exfoliated structure in the PA6/PP nanocomposite containing stearylamine modified montmorillonite. The storage modulus and HDT of PA6/PP blend were increased significantly with the incorporation of both Na‐MMT and OMMT. The highest value in both storage modulus and HDT was found in the PA6/PP nanocomposite containing stearylamine modified montmorillonite due to its better exfoliated structure. POLYM. COMPOS., 31:1156–1167, 2010. © 2009 Society of Plastics Engineers     

Unsaturated polyester/montmorillonite nanocomposites with improved mechanical and thermal properties fabricated by in situ polymerization

Although organically modified montmorillonite (OMMT) has been incorporated into unsaturated polyester (UP) resin to enhance properties, the aggregation often leads to defects which directly affect the properties of nanocomposites. In this work, OMMT slurry modified by a new allyl surfactant with carbon–carbon double bond, hexadecyl allyl dimethyl ammonium chloride (C₁₆‐DMAAC), was employed to prepare nanocomposites by in situ polymerization. The results illustrated that the existence of OMMT slurry helped monomers enter the OMMT galleries, leading to well‐dispersed OMMT in the UP matrix. The mechanical properties and thermal properties of OMMT nanocomposites were improved. With OMMT loading of 5 wt %, the tensile strength and flexural strength can be improved by 22% and 38%, respectively. Meanwhile, the onset thermal decomposition temperature (T_–10) value was ameliorated from 310.6 °C to 330.6 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45251.     

剥离型酚醛树脂/蒙脱土纳米复合材料研究

用十六烷基三甲基溴化铵(CTAB)对蒙脱土进行了有机化处理,使蒙脱土由亲水性变成亲油性。采用XRD、FTIR及TEM研究了有机蒙脱土及其在酚醛树脂中的剥离行为,制备了酚醛树脂/蒙脱土纳米复合材料并测试了其层间剪切性能和烧蚀性能。实验结果表明,经CTAB处理的蒙脱土与酚醛树脂具有良好的相容性,且CTAB的含量较多时所制得的有机蒙脱土的结构较好,根据Bragg方程计算,CTAB用量超过蒙脱土量50%时,蒙脱土的片层间距由原来的1.48 nm增加到2.33 nm;有机蒙脱土用量小于5%时生成完全剥离型酚醛树脂/蒙脱土纳米复合材料;与碳布增强酚醛树脂复合材料相比,碳布增强酚醛树脂/蒙脱土纳米复合材料的力学性能和烧蚀性能均有一定的提高和改善,层间剪切强度随蒙脱土含量的增多而增大,蒙脱土用量为15%时,层间剪切强度提高了27.1%,线烧蚀率在用量为3%时降低了48.5%,质量烧蚀率变化不明显。     

Thermo mechanical behaviour of unsaturated polyester toughened epoxy–clay hybrid nanocomposites

The intercrosslinked networks of unsaturated polyester (UP) toughened epoxy–clay hybrid nanocomposites have been developed. Epoxy resin (DGEBA) was toughened with 5, 10 and 15% (by wt) of unsaturated polyester using benzoyl peroxide as radical initiator and 4,4′-diaminodiphenylmethane as a curing agent at appropriate conditions. The chemical reaction of unsaturated polyester with the epoxy resin was carried out thermally in presence of benzoyl peroxide-radical initiator and the resulting product was analyzed by FT-IR spectra. Epoxy and unsaturated polyester toughened epoxy systems were further modified with 1, 3 and 5% (by wt) of organophilic montmorillonite (MMT) clay. Clay filled hybrid UP-epoxy matrices, developed in the form of castings were characterized for their thermal and mechanical properties. Thermal behaviour of the matrices was characterized by differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA) and dynamic mechanical analysis (DMA). Mechanical properties were studied as per ASTM standards. Data resulted from mechanical and thermal studies indicated that the introduction of unsaturated polyester into epoxy resin improved the thermal stability and impact strength to an appreciable extent. The impact strength of 3% clay filled epoxy system was increased by 19.2% compared to that of unmodified epoxy resin system. However, the introduction of both UP and organophilic MMT clay into epoxy resin enhanced the values of mechanical properties and thermal stability according to their percentage content. The impact strength of 3% clay filled 10% UP toughened epoxy system was increased by 26.3% compared to that of unmodified epoxy system. The intercalated nanocomposites exhibited higher dynamic modulus (from 3,072 to 3,820 MPa) than unmodified epoxy resin. From the X-ray diffraction (XRD) analysis, it was observed that the presence of d ₀₀₁ reflections of the organophilic MMT clay in the cured product indicated the development of intercalated clay structure which in turn confirmed the formation of intercalated nanocomposites. The homogeneous morphologies of the UP toughened epoxy and UP toughened epoxy–clay hybrid systems were ascertained from scanning electron microscope (SEM).     

Influence of the type of quaternary ammonium salt used in the organic treatment of montmorillonite on the properties of poly(styrene‐co‐butyl acrylate)/layered silicate nanocomposites prepared by in situ miniemulsion polymerization

Hybrid latices of poly(styrene‐co‐butyl acrylate) were synthesized via in situ miniemulsion polymerization in the presence of 3 and 6 wt % organically modified montmorillonite (OMMT). Three different ammonium salts: cetyl trimethyl ammonium chloride (CTAC), alkyl dimethyl benzyl ammonium chloride (Dodigen), and distearyl dimethyl ammonium chloride (Praepagen), were investigated as organic modifiers. Increased affinity for organic liquids was observed after organic modification of the MMT. Stable hybrid latices were obtained even though miniemulsion stability was disturbed to some extent by the presence of the OMMTs during the synthesis. Highly intercalated and exfoliated polymer‐MMT nanocomposites films were produced with good MMT dispersion throughout the polymeric matrix. Materials containing MMT modified with the 16 carbons alkyl chain salt (CTAC) resulted in the largest increments of storage modulus, indicating that single chain quaternary salts provide higher increments on mechanical properties. Films presenting exfoliated structure resulted in the largest increments in the onset temperature of decomposition. For the range of OMMT loading studied, the nanocomposite structure influenced more significantly the thermal stability properties of the hybrid material than did the OMMT loading. The film containing 3 wt % MMT modified with the two 18 carbons alkyl chains salt (Praepagen) provided the highest increment of onset temperature of decomposition. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

蒙脱土改性酚醛树脂复合材料的制备与性能研究

为提高酚醛树脂(PF)的热稳定性,利用原位插层法制备了PF/蒙脱土(MMT)、PF/有机化蒙脱土(OMMT)纳米复合材料,并比较了PF、PF/OMMT或PF/MMT经高温热处理后的力学性能和导电性能.研究表明,与PF复合后,OMMT和MMT都形成了剥离型的片层结构.与PF/OMMT复合材料相比,PF/MMT的质量保持率...     

Structure and Property of PU/MMT Nanocomposites by In-Situ Polymerization

A montmorillonite modified by octadecylammonium salt (OMMT) was prepared. A polyurethane (PU)/montmorillonite nanocomposite was synthesized by in-situ polymerization using the OMMT, poly(propylene glycol), 4,4-diphenylmethylate diisocyanate, and 1,4-butanediol. The MMT platelets were dispersed in PU matrix on a 10 ～ 50 nm scale. Compared to that of pure PU, the tensile strength and tear strength of the PU/OMMT nanocomposites increased, respectively, and the MMT platelets dispersed on a nanometer scale enhanced the PU. The temperature of initial weight loss of the PU/OMMT nanocomposites was lower than that of pure PU because of the acid catalytic action of protonated MMT platelets in the first thermodegradation step. But its temperature of initial weight loss was higher than that of pure PU because of the barrier effect of the MMT platelets in the second thermodegradation step.     

Chlorinated butyl rubber/two-step modified montmorillonite nanocomposites: Mechanical and damping properties

Montmorillonite (MMT) was modified by ultrasound and castor oil quaternary ammonium salt intercalation method to prepare a new type of organic montmorillonite (OMMT). The surface structure, particle morphology, interlayer distance, and thermal behavior of the samples obtained were characterized. The modified OMMT was then added to chlorinated butyl rubber (CIIR) by mechanical blending, and a composite material with excellent damping properties was obtained. The mechanical experiment results of CIIR nanocomposites showed that the addition of OMMT improved their tensile strength, hardness, and stress relaxation rate. Compared with pure CIIR, when the content of OMMT was 5 phr (part per hundred of rubber), the tensile strength of the nanocomposite was increased by 677% and the elongation at break was also increased by 105.4%. The enhancement of this performance was mainly due to the dispersion of the nanosheets in CIIR rubber and the chemical interaction between the organoclay and the polymer matrix, which was confirmed by morphology and spectral analysis. OMMT also endowed a positive effect on the damping properties of CIIR nanocomposites. After adding 5 phr of OMMT, the nanocomposite owned the best damping performance, and the damping factor, tanδ_max, was 37.9% higher than that of pure CIIR. Therefore, the good damping and mechanical properties of these CIIR nanocomposites provided some novel and promising methods for preparing high-damping rubber in a wide temperature range.     

Preparation of a long-alkyl-chain silane grafted organic montmorillonite and its nanocomposite with SEBS

In this study, a modified montmorillonite (W-H-OMMT) was prepared by intercalating pristine montmorillonite using a phosphorus salt and a subsequent grafting using a long-alkyl-chain silane, and the nanocomposites with poly[styrene–(ethylene-co-butylene)–styrene] (SEBS) were prepared by melt blending. The pristine and the modified MMT were characterized by XRD, FT-IR, XPS and SEM. The morphology of the SEBS nanocomposites was studied using XRD, SEM and TEM, and the results can be correlated well with transparency, color, surface contact angle, rheological behavior, thermal and mechanical properties of the nanocomposites. As compared with pristine and the modified clay, more uniform dispersion and improved compatibility are observed for the W-H-OMMT in the SEBS matrix, resulting in better transparency and more hydrophobic surface for the SEBS/W-H-OMMT nanocomposite. Better thermal stability, a synergetic effect in tensile strength and elongation at break were observed, which can be attributed to well dispersion of the W-H-OMMT, as well as perfect adhesion between the W-H-OMMT and the SEBS matrix from the enhanced molecular interaction between the long-alkyl chain and the SEBS molecules. Compared to pure SEBS, the strength and elongation of SEBS/W-H-OMMT nanocomposite increased by 8.5 and 7.6 %; meanwhile, the water contact angel and the 50 % weight loss temperature increased by 5.3 and 13.1 %, respectively. Appropriate silane grafted organic montmorillonite provided an efficient way for the overall performance improvement of SEBS.     

尼龙12/OMMT纳米复合粉末的制备及性能

利用十八烷基三甲基溴化铵(OTAB)对蒙脱土(MMT)进行有机改性,并通过溶液插层法制备尼龙12/有机蒙脱土(PA12/OMMT)纳米复合粉末。利用X射线衍射、傅立叶变换红外光谱、扫描电子显微镜等手段对改性后的MMT及PA12/OMMT纳米复合粉末的结构和微观形貌进行表征,并将复合粉末热压成型制成标准件,测试其力学性能和热性能。结果表明,经过有机改性,MMT的层间距由1.24 nm增加到了2.13 nm,且改性后的MMT能均匀地分散在PA12基体中,PA12/OMMT纳米复合粉末的成型件在拉伸强度、弯曲强度、冲击强度和热性能方面都优于纯PA12粉末。PA12/OMMT纳米复合粉末为选择性激光烧结技术(SLS)提供了一种性能良好的粉末材料。     

阻隔性尼龙611／有机蒙脱土纳米复合材料的研究

以11-氨基十一酸对蒙脱土(MMT)进行有机化改性,采用原位聚合法制备了尼龙611/有机蒙脱土(OM-MT)纳米复合材料.通过傅立叶变换红外光谱仪研究了OMMT及尼龙611/OMMT纳米复合材料的化学结构,使用扫描电子显微镜观察了纳米复合材料的形貌.详细考察了OMMT含量对尼龙611/OMMT纳米复合材料阻隔性能和力学性能的影响,探讨了OMMT的阻隔机理.结果表明,MMT经有机化改性后,其片层在尼龙基体中分散均匀,并与尼龙基体发生键合作用,使尼龙611分子的内聚力增强,分子链堆积程度提高,极大地提高了阻隔性能;OMMT质量分数为3%时,材料的拉伸强度达到最大值,但在常温、低温下冲击强度略有下降.     

聚酰胺6/环氧树脂改性蒙脱土纳米复合材料的制备与性能

采用环氧树脂改性蒙脱土（MMT）得到有机化蒙脱土（OMMT）,再用熔融插层法制备了聚酰胺6 （PA6）/ OMMT纳米复合材料。采用X射线衍射仪、透射电子显微镜、万能材料试验机、热重分析仪等研究了PA6/OMMT复合材料的形态结构、力学性能和热稳定性。结果表明,经环氧树脂改性得到的OMMT的层间距明显增加,从未改性的1.22 nm增加到5.13 nm,并以纳米尺度分散于PA6基体中;随着OMMT含量的增加,PA6/ OMMT复合材料的强度和模量增加,热变形温度提高,其拉伸强度可达76 MPa,弯曲模量达到3.462 GPa,热变形温度为134 ℃;PA6/ OMMT复合材料失重10 %时的温度为422 ℃,比纯PA6的406 ℃提高了16 ℃,改善了PA6的热稳定性。     

Effect of reactive diluents on properties of unsaturated polyester/montmorillonite nanocomposites

Unsaturated polyester (UP)/montmorillonite (MMT) nanocomposite was prepared by using hydroxypropylacrylate (HPA) as a reactive diluent instead of conventional styrene monomer and the effect of polarity of reactive diluent on properties of nanocomposite was investigated. X‐ray and mechanical test data indicated that mixing for an extended period of time is essential to enhance the physical properties of nanocomposites in the UP/Cloisite 6A system. This was attributed to the high polarity of HPA that may disturb the preintercalation of UP resin into the galleries of MMT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 238–242, 2004     

Effect of polymer matrix/montmorillonite compatibility on morphology and melt rheology of polypropylene nanocomposites

In this study, Ca²⁺‐montmorillonite (Ca²⁺‐MMT) and organo‐montmorillonite (OMMT) were modified by three compatibilizers with different degrees of polarity [poly(ethylene glycol) (PEG), alkyl‐PEG, and polypropylene (PP)‐g‐PEG]. PP/MMT nanocomposites were prepared by melt blending and characterized using X‐ray diffraction and transmission electron microscopy. The results showed the degree of dispersion of OMMT in the PP/PP‐g‐PEG/OMMT (PMOM) nanocomposite was considerably higher than those in the PP/PEG/OMMT and PP/alkyl‐PEG/OMMT nanocomposites, which indicated that the dispersion was relative to the compatibility between modified OMMT and PP matrix. Linear viscoelasticity of PP/MMT nanocomposites in melt states was investigated by small amplitude dynamic rheology measurements. With the addition of the modified MMT, the shear viscosities and storage modulus of all the PP/MMT nanocomposites decreased. It can be attributed to the plasticization effect of PEG segments in the three modifiers. This rheological behavior was different from most surfactant modified MMT nanocomposites which typically showed an increase in dynamic modulus and viscosity relative to the polymer matrix. The unusual rheological observations were explained in terms of the compatibility between the polymer matrix and MMT. In addition, the mechanical properties of PP/MMT nanocomposites were improved. A simultaneous increase in the tensile strength and toughness was observed in PP/PMOM nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

An in situ intercalative polymerization method for preparing UV curable clay–polymer nanocomposites

A novel in situ intercalative polymerization technique was used to disperse clay mineral in a precursor resin for use in UV curing by performing an in situ ion exchange reaction during polyesterification. Unmodified montmorillonite (MMT) was added to a reaction mixture composed of monomers and methyl, tallow, bis‐2‐hydroxyethyl ammonium (MTEtOH) during the synthesis of unsaturated polyesters to create resins containing highly dispersed, organically modified MMT. UV‐curable clay–polymer nanocomposite (CPN) films were then prepared utilizing donor–acceptor chemistry through reactions of the unsaturated polyester resin with triethylene glycol divinyl ether. Functional group conversion improved up to 15% by the incorporation of clay mineral into the polymer matrix through the in situ polymerization method. The CPNs also had improved barrier, mechanical, and thermal properties over a control film containing no clay mineral. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42601.     

Polypropylene nanocomposites prepared with natural and ODTABr‐modified montmorillonite

In this study, the main goal is to obtain montmorillonite nanocomposites of polypropylene (PP). To achieve this goal, a two‐phase study was performed. In the first part of the work, organomodified clay (OMMT) was synthesized and characterized. Octadecyltrimethylammonium bromide (ODTABr) cationic surfactant was added to the clay (Na‐activated montmorillonite, MMT) dispersions in different concentrations in the range of 5 × 10^?5–1 × 10^?2 mol/L. Rheologic, electrokinetic, and spectral analyses indicated that ODTABr has interacted with MMT at optimum conditions when the concentration was 1 × 10^?2 mol/L. In the second part, modified (OMMT) and unmodified (MMT) montmorillonite were used to obtain PP nanocomposites (OMMT/PP and MMT/PP, respectively). The nanocomposites were prepared by melt intercalation where the montmorillonite contents were 1 or 5% (w/w) for each case. The thermal analyses showed that the thermal properties of OMMT/PP nanocomposites were better than MMT/PP, and both of them were also better than pure polymer. Increase in the concentration of MMT (or OMMT) decreased the thermal resistance. Based on the IR absorption intensity changes of regularity and conformational bands, it is found that the content of the helical structure of macromolecular chains has increased with increasing concentrations of both MMT and OMMT in the nanocomposites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

环氧树脂/环氧液晶/蒙脱土纳米复合材料研究

采用液晶环氧预聚物(PHQEP)与有机蒙脱土(OMMT)共混改性环氧树脂制备三元共混体系的环氧基复合材料。用X射线衍射法(XRD)测试了有机化蒙脱土在被插层前后片层间距的变化,通过DSC、TGA及SEM等对PHQEP/OMMT增韧改性环氧树脂固化体系的力学性能,热性能及微观相态结构进行了研究。结果表明:当PHQEP质量分数为5%,添加1.5%的有机蒙脱土可以使环氧树脂的冲击强度达到最大值23.43 kJ/m2,比纯环氧树脂提高2倍左右,玻璃化转变温度及5%热分解温度比纯环氧树脂分别高出15℃和27℃。PHQEP与OMMT的加入使纳米复合材料的力学性能和热性能得到明显提高。     

Thermal and mechanical behavior of unsaturated polyester [derived from poly(ethylene terephthalate) waste] and montmorillonite‐filled nanocomposites synthesized by in situ polymerization

Postconsumer poly(ethylene terephthalate) waste bottles were glycolyzed as precursors of unsaturated polyester resin (UPR) and their montmorillonite (MMT)‐filled nanocomposites. The glycolysis product (hydroxyl‐terminated oligomers) was converted into UPR with various acid contents. These resins were miscible with styrene and could be cured with peroxide initiators to produce thermosetting unsaturated polyester (UP). Nanocomposites composed of UP matrix and organically modified clay were prepared by in situ polymerization. These were characterized for thermal and dynamic mechanical properties. Transmission electron microscopy was also used to study the morphology at different length scales and showed the nanocomposites to be compromised of a random dispersion of intercalated/exfoliated aggregates throughout the matrix. With an increase in unsaturated acid content (for a fixed content of clay), the value of storage modulus varied from 2737 to 4423 MPa. The glass‐transition temperatures of these nanocomposites ranged from 54 to 78°C, and the crosslink density varied from 3.70 × 10⁵ to 5.72 × 10⁵ mol/m³. The X‐ray diffraction (XRD) of modified MMT exhibited a peak that vanished completely in the polymer nanocomposites. Thus, the XRD results apparently indicated a distortion of the platy layers of nanofiller in the UP nanocomposites. The nanocomposites showed higher modulus values (2737–4423 MPa) compared to the pristine polymer (2693 MPa). From thermogravimetric analysis, all of the nanocomposites were stable up to 200°C and showed a two‐stage degradation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of hyperbranched polymer modified montmorillonite/chlorinated butyl rubber damping composites

In this work, Na⁺‐montmorillonite (MMT) was modified by hyperbranched polymer (HBP) and grafted with hindered phenol to improve the damping and other properties of the chlorinated butyl rubber (CIIR) composites. The hyperbranched polymer‐modified montmorillonite (HBP‐OMMT) was prepared by organic montmorillonite (OMMT) that was obtained from the cation exchange reaction between MMT and silane quaternary ammonium salt. The main characterization methods were Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance, X‐ray diffraction, scanning electron microscopy, energy dispersive spectrometer, and thermogravimetric (TG) analysis. The basal spacings of MMT, OMMT, and HBP‐OMMT were 1.47, 2.94, and 4.09 nm, respectively. The onset and center temperatures of decomposition (T_?5% and T_max) of HBP‐OMMT were improved from 301 and 369 °C to 332 and 398 °C, respectively. The CIIR damping composites were prepared by mechanical blending of HBP‐OMMT with pure CIIR. The tensile strength and elongation at break of the composites were improved from 5.4 MPa and 890% to 7.6 MPa and 1066%. From TG curves, T_?5% and T_max were increased from 297.4 and 406.0 °C to 323.3 and 410.5 °C, respectively. The dynamic mechanical analysis results showed that tan δ rose from the original 1.20 to 1.44 with the addition of HBP‐OMMT. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43645.