Application of Trialkylimidazolium Liquids and Salts to the Preparation

Chapter 12

Application of Trialkylimidazolium Liquids and Salts to the Preparation of Polymer-Layered Silicate Nanocomposites and Polymer-Carbon Nanotube Nanocomposites Downloaded by UNIV OF ARIZONA on April 19, 2013 | http://pubs.acs.org Publication Date: July 21, 2005 | doi: 10.1021/bk-2005-0913.ch012

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Douglas M. Fox , Severine Bellayer , Marius Murariu , Jeffrey W. Gilman , Paul H. Maupin , Hugh C. De Long , and Paul C. Trulove 2

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Chemistry Department, U.S. Naval Academy, Annapolis, M D 21402 Fire Research Division, Building and Fire Research Laboratory, National Institute of Standards and Technology, Gaithersburg, M D 20899 Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy, Washington, DC 20585 Directorate of Chemistry and Life Sciences, Air Force Office of Scientific Research, Arlington, V A 22203 Corresponding author: telephone: 410-293-6622; fax: 410-293-2218; email: [email protected] 3

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Polymer - layered silicate and polystyrene - carbon nanotube nanocomposites have been prepared via melt-blending. The thermal stability was analyzed using thermal gravimetric analysis and the extent o f nanoparticle dispersion has been examined using powder x-ray diffraction ( X R D ) and transmission electron microscopy (TEM). Phase behavior o f polystyrene nanocomposites were characterized using differential scanning calorimetry (DSC). The imidazolium salts used in this study were found to greatly expand the gallery d-spacing o f montmorillonite to produce nanocomposites with a predominantly intercalated structure and to greatly improve the dispersion o f M W N T in polystyrene to produce polymers with superior thermal properties.

© 2005 American Chemical Society In Ionic Liquids in Polymer Systems; Brazel, C., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2005.

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Introduction There is growing interest in improving the properties of polymers and resins through the incorporation o f nanoscale materials. These polymer nanocomposites often possess enhanced thermal stability and reduced flammability while also improving mechanical and barrier properties. In this work, we are investigating the preparation and properties of polymer - layered silicate nanocomposites (PLSNs) and polymer carbon nanotube nanocomposites (PCNNs). To prepare PLSNs, the clay needs to be compatiblized with the polymer using an organic modifier; currently this is achieved industrially by treating the clay with dimethyl-di(hydrogenated tallow) ammonium (DMDHtAmm) salts. One of the chief difficulties in the industrial production of PLSNs is the low thermal stability o f D M D H t A m m salts, which limits the operating temperature of the process. The use o f imidazolium compounds, specifically dimethylalkylimidazolium (DMA!) liquids and salts, in place of D M D H t A m m salts offers a significant improvement in die thermal stability o f the organo-clay and allows for a higher processing temperature of the PLSNs. ' Recently, we have used l-hexadecyl-2,3-dimethylimidazolium ( D M H d l ) salts to produce PLSNs with the polymers poly(ethylene terephthalate) (PET) and polyamide-6 (PA-6), which require process temperatures above the onset decomposition temperatures of D M D H t A m m compounds. ' In this work, we have prepared a new D M A I surfactant, 1,2-dimethyl-3-(benzyl ethyl iso-butyl polyhedral oligomeric silsesquioxane)imidazolium chloride (DMIPOSS-C1) and used it to prepare organically modified layered silicates (OMS) for use in PLSNs. In addition, we have employed these D M A I surfactants to produce PCNNs. Preliminary results of the P C N N s have suggested a similar improvement in thermal stability and greater reduction in flammability over the neat polymers. We present thermal stability and dispersion results for PLSNs and PCNNs with a variety of polymers, including PS, poly(ethylene-co-vinyl acetate) ( E V A ) and PA-6. A summary o f the abbreviations u§ed in this paper are given in Table 1.

Downloaded by UNIV OF ARIZONA on April 19, 2013 | http://pubs.acs.org Publication Date: July 21, 2005 | doi: 10.1021/bk-2005-0913.ch012

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Experimental

R T I L Preparation Chlorobenzyl ethyl iso-butyl-POSS (10 g, Hybrid Plastics) and a 30% excess of 1,2-dimethylimidazole (Sigma-Aldrich) were added to T H F (25 ml). After dissolution, the solution was heated to a gentle reflux for 3 days. The

In Ionic Liquids in Polymer Systems; Brazel, C., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2005.

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solution was cooled, dissolved in hot ethyl acetate and precipitated with addition o f acetonitrile. The solid product was washed with acetonitrile and dried under vacuum overnight. Duplicate elemental analysis performed by Galbraith Laboratories indicated the prepared DMIPOSS consisted of46.55 % C , 7.86 % H , and 2.45 % N (theoretical = 47.3 % C , 7.7 % H , and 2.6%N), H N M R (CDC1 , 300 M H z ) was characterized by the disappearance of the chloromethylene resonance from the starting material, 0 = 4.5 ppm (2H,s) and the appearence of new resonances at a = 2.7 ppm (3H,s), 3.9 pmm (3H,s), 5.4 ppm (2H, s), 7.5 ppm (1H, d) and 7.7 ppm (1H, d) corresponding to the imidazolium 2-methyl, the imidazolium 1-methyl, the imidazolium 3-benzylic methylene, and the 4 and 5 position imidazolium hydrogens, respectively. The 3.9 ppm peak was phase inverted. Assignments were made from comparision with Aldrich spectra of some simple imidazole and imidazolium compounds. D M H d I B F was prepared in acetonitrile, as previously described. Elemental analysis by Galbraith Laboratories resulted in mass errors o f 0.2% C, 1.0% H , and 1.2% N . The water content was determined to be 24 ppm using a Brinkmann Model 756/2 Karl Fischer Coulometric Titrator. J


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Table 1: Abbreviations for chemicals used in this study Abbreviation POSS DMIPOSS DMHdl DMDOdAmm MMT MWNT PS EVA PA-6 PLSN PCNN OMS

Definition Polyhedral oligomeric silsesquioxanes 1,2-dimethyl-3-(benzyl ethyl iso-butyl polyhedral oligomeric silsesquioxane)imidazolium cation 1 -hexadecyl-2,3-dimethylimidazolium cation N,N-dimethyl-N,N-dioctadecylammonium cation montmorillonite Carbon multi-walled nanotubes Polystyrene Poly(ethylene co-vinyl acetate) Polyamide-6 Polymer - layered silicate nanocomposites Polymer - carbon nanotube naocomposites Organically modified layered silicate

O M S preparation D M H d I - M M T and D M D O d A m m - M M T were prepared using standard exchange procedures as described previously. N a - M M T was exchanged with 2,3


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DMIPOSS using a slight modification to this procedure. DMIPOSS-C1 (3 g) was dissolved in THF (50 ml), then Na-MMT (3 g, Southern Clay Products) was added to form a slurry. The slurry was heated to boiling, deionized water (25 ml) was slowly added, and the mixture was removed from the heat. After stirring for 2 days, the slurry wasfilteredand washed with aliquots of hot THF (50 ml). The exchanged clay was leached with hot 75:25 ethanohwater, filtered, and dried at 100°C for 1 hr.

MWNT/DMHdl mixtures MWNT/DMHdIBF mixtures were prepared with massfractionratios of 1:1, 1:4, and 1:19 (MWNT to DMHdIBF ). DMHdIBF and M W N T were melt blended at 185°C in a conical co-rotation twin screw mini-extruder (DACA) at 5.2 rad/s for 2 min. The mixtures solidified upon cooling, and were ground into afinepowder for use in preparing PCNNs. 4

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Nanocomposite Preparation Polystyrene (PS) - carbon nanotube nanocomposites were prepared using the extruder described previously. Enough MWNT/DMHdIBF mixture was melt blended with PS at 195°C and 26 rad/s for 5 min to prepare nanocomposites with 0.5 wt-% MWNT. Additionally, composites were prepared using 0.5 wt-% pure MWNT and 0.5 wt-% pure DMHdIBF as PS + MWNT and PS + DMHdIBF references. All of the nanocomposites prepared (except PS + DMHdIBF ) had 0.5 wt-% MWNT, regardless of the imidazolium content Thus, PS + (1:1) MWNT:DMHdIBF contains 0.5 wt-% MWNT and 0.5 wt-% DMHdIBF ; PS + (1:4) MWNT:DMHdIBF contains 0.5 wt-% MWNT and 2.0 wt-% DMHdIBF ; and (1:19) MWNT:DMHdIBF contains 0.5 wt-% MWNT and 9.5 wt-% DMHdIBF . 4

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Instrumentation Thermal stabilities were determined using a TA Instruments, Hi-Res TGA2960 Thermogravimetric Analyzer. For the comparative TGA study, 4.0 mg to 6.0 mg samples were placed in open ceramic pans and heated at a scan rate of i0°C/min while purged with 100 ml/min N . For all TGA anlyses, the mean of three replicate measurements was typically reported. The temperature 2


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of both the onset (5% mass fraction loss) and peak mass loss rate have an uncertainty of cr = ± 4°C. The mass loss rate has a relative uncertainty ofcr/x = ± 10%. Melting and freezing properties were characterized using a T A Instruments DSC2910 Differential Scanning Calorimeter connected to a Refrigerated Cooling System. 3.0 mg to 5.0 mg samples were hermetically sealed in aluminum pans and were heated and cooled at a scan rate of 5°C/min while purged with 100 ml/min N . Data were collected during the second consecutive scans. Powder x-ray diffraction experiments were performed on a Bruker A X S D8 Powder diffractometer. The d-spacing was calculated from peak positions using Cu Koc radiation (A. = 0.15418 nm) and Bragg's Law. Clay samples were ground to a fine powder prior to loading. PLSNs samples were prepared by pressing (6 atm) 0.5 g in a 2 cm x 1.6 m mold at temperatures above the melting point. Standard x-ray measurements were performed over a scanning 28 range of 2.5° 12° using a step size of 0.05° for 20 sec. A l l T E M samples were ultra-microtomed using a diamond knife on a Leica Ultracut U C T microtome at room temperature. The cut samples (100 nm nominal thickness) were transferred to 400 mesh Cu/Rh grids. A Philips 400T electron microscope was used to obtain bright-field T E M images at 120 k V under low-dose conditions. To ensure the collection of representative images, several images of various magnifications with 2-3 sections per grid were obtained.


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Results and Discussion

Polymer - Layered Silicate Nanocomposites The thermal stability of the organically modified clays (OMS) were determined using thermal gravimetric analysis (TGA) in nitrogen. As shown in Figure 1, D M I P O S S - M M T exhibits a thermal stability in nitrogen which is 50°C higher than l-hexadecyl-2,3-dimethylimidazolium exchanged clay ( D M H d l M M T ) and 200°C higher than the conventional N,N-dimethyl-N,Ndioctadecylammonium exchanged clay ( D M D O d A m m - M M T ) . To help facilitate exfoliation o f the clay layers during the preparation of the PLSNs, it is desirable to exchange the N a with a surfactant that will also swell the silicate layers. We used powder x-ray diffraction ( X R D ) to measure the expansion o f the montmorillonite layers after cation exchange. The use o f DMIPOSS as the organic surfactant greatly increases the d-spacing between the clay layers. A s shown in Figure 2, this expansion is far greater than any previously used imidazolium treatment or the commonly used quaternary +


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Temperature (C) Figure J. TGA of organically modified clays (OMC) in N at 10°C/min 2


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2-Theta (degrees) Figure 2. XRD of OMCs. Plots have been shifted upward for clarity. ammonium treatment. It is important to note that D M I P O S S - M M T exhibits peaks at 8.3° and 10.6° (not shown) 29, which are characteristic POSS crystalline peaks. The large d-spacing and POSS cystallinity peaks suggests that the DMIPOSS cations on adjacent clay layers may be arranged as a bilayer in the gallery with significant POSS-POSS interactions. 6,7,8

The thermal stabilities of the processed polymer - layered silicate nanocomposites (PLSNs) in nitrogen were measured using T G A . The thermal stabilities of polystyrene nanocomposites are shown in Figure 3. Similar to other P L S N studies, the melt blending of D M I P O S S - M M T and PS results in a significant improvement in thermal stability and an increase in char yield. Although the use of D M I P O S S - M M T does improve the thermal characteristics of the polymers, it is not as effective as other O M S , as indicated in Table 2. The larger d-spacing of D M I P O S S - M M T , smaller expansion o f the clay galleries upon blending with the polymers (A5), and loss o f X R D peaks associated with the POSS crystallinity (not shown) all indicate that the polymers form a predominantly intercalated structure with D M I P O S S - M M T . The higher thermal stability of PLSNs using D M H d I - M M T is due to exfoliation of the clay layers (i.e. complete separation of the clay layers which is indicated by a loss of the X R D peak associated with the clay gallery spacing), which increases the amount of clay-polymer interactions. 9,10



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Temperature (C) Figure 3. TGA of PS + 5%DMIPOSS-MMT

in N at 10°C/min 2

Table 2: T G A Onset and Peak Temperatures and Shifts in XRD peak associated with the gallery d-spacing of the OMCs. AS (nm) v. OMMT

Tpeak co*

PS (180°C, 200rpm, 5m)

Tonset (°C)» 346

404

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+5% D M H d I M M T

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428

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+5% D M I P O S S M M T

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352/457

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+5% D M H d I M M T

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353/470

exfoliated


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PA-6 (250°C, 200rpm, 5m)

383

443

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+5% D M H d I M M T

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438

exfoliated


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Composite

E V A (170°C, 200rpm, 5m)


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Transmission electron microscopy ( T E M ) images o f the PS + 5 % D M I P O S S - M M T nanocomposite shown in Figure 4 reveal the presence of a significant number of multi-layer tactoids throughout the polymer. Similarly to the X R D data, the T E M images suggest significant intercalation with an average of 6-10 layers per tactoid, indicating about 15% of the layers exfoliated from the adjacent layer. The large d-spacing of the O M S and rigid structure of the POSS cages lowers the entropic gain o f both the surfactant and the intercalated polymer. The lack of favorable polymer-surfactant or polymer-clay interactions plus the presence of strong POSS-POSS interactions results in a lack of favorable enthalpic conditions for exfoliation. Hence, the free energy gain for exfoliation is low, resulting in predominantly intercalated structures. Downloaded by UNIV OF ARIZONA on April 19, 2013 | http://pubs.acs.org Publication Date: July 21, 2005 | doi: 10.1021/bk-2005-0913.ch012

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Polymer - Carbon Nanotube Nanocomposites The X R D of D M H d I B F (see Figure 5) exhibits three peaks in the low angle region (28 = 3.2°, 6.4°, and 12.8°), characteristic of the crystalline solid phase and representing the (001) reflections from interdigitated bilayer structure with an interlayer distance o f 2.75 n m . ' In the (1:1) M W N T : D M H d I B F mixture, these peaks disappear and new peaks form at higher angles, representative of alkyl chain ordering in the lamellar structure. The X R D o f the (1:4) M W N T : D M H d I B F and (1:19) M W N T : D M H d I B F (not shown) mixtures exhibit peaks consistant with both structures, suggesting the mixtures consist of 2 separate phases. 4

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2-Theta (degrees) Figure S. XRD of DMHdIBF4 MWNT, and MWNT-DMHdIBF have been shifted upwardfor clarity. t

mixtures. Plots

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The polymer nanocomposites prepared from PS and the M W N T / D M H d I B F mixtures were characterized using D S C , T E M , and T G A . The melting characteristics were investigated using D S C and are shown in Figure 6. D M H d I B F exhibits liquid crystalline behavior, with a melting point at 70°C and a clearing point at 175°C. Pure PS exhibits a glass transition around 100°C. The P C N N prepared from (1:1) M W N T : D M H d I B F does not exhibit any peaks characteristic of pure D M H d I B F and has the same glass transition temperature as the pure PS. This suggests that the D M H d I B F is completely 4

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associated with the M W N T s . It also indicates that, similarly to the poly(methyl methacralate)/MWNT results obtained by Tatro, et. al., low loadings of M W N T s do not retard PS chain motion. P C N N s prepared using D M H d I B F rich mixtures do have endotherms associated with D M H d I B F melting and liquid crystal clearing points, indicating that the excess imidazolium salt has phase separated from the PS matrix. 14

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PS + (1:10) MWNTDM-HIBF*

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DMHdlBF

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Temperature (C) Figure 6. DSC of PS and PS-Carbon Nanotube Composites. Plots have been shifted upwardfor clarity. The dispersion o f M W N T and phase separation of excess D M H d I B F can be visualized using T E M . T E M images o f PS + M W N T and PS + (1:1) M W N T : D M H d I B F are shown in Figure 7. The background was removed in a portion of the images to conduct image analyses, which indicated that the images were indeed representative of the entire samples. When untreated M W N T are directly incorporated in the PS matrix, poor dispersion is obtained, with a median nearest neighbor distance of 38 ± 13 nm. The use o f (1:1) M W N T : D M H d I B F greatly improves dispersion, with the M W N T median nearest neighbor distance of 109 nm ± 6 nm. The theoretical nearest neighbor distance for a perfectly mixed sample should be 120 nm ± 15 nm for PS + untreated M W N T and 132 nm ± 20 nm for PS + (1:1) M W N T : D M H d I B F . These results illustrate the natural tendency for M W N T to agglomerate and show that D M H d I B F interacts with both M W N T and PS to reduce this agglomeration and improve dispersion. The nanocomposites prepared using (1:4) and (1:19) 4

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M W N T : D M H d I B F produces M W N T dispersion similar to that o f the (1:1) sample, but also reveal holes in the T E M images (not shown). This illustrates the phase separation behavior revealed in the D S C and suggests a 7t-stacking type interaction between the imidazolium cation and M W N T . 4


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Figure 7. TEM images of (a) PS + MWNT and (b) PS + (1:1) MWNT:DMHdIBF 4

The thermal stability of PS + (1:1) M W N T : D M H d I B F in N was measured using T G A . PS, PS + M W N T , and PS + DMHdIBF4 thermal stabilities were also measured to evaluate the effectiveness of the M W N T / D M H d D 3 F mixture. The thermogram is shown in Figure 8. Both the onset and maximum decomposition temperatures o f PS were not affected by the addition o f either M W N T or D M H d I B F . However, the addition of the (1:1) M W N T : D M H d I B F mixture improved the thermal stability o f PS by 20° ± 3°C. This stabilization may be explained by the enhanced dispersion of M W N T in this nanocomposite, which increases the contact surface between M W N T and the polymer matrix. 4

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Conclusions Polymer-Layered Silicate Nanocomposites A new imidazolium compound (DMIPOSS-C1), consisting of a POSS cage tethered to one o f the nitrogen groups, was prepared and successfully used as a


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surfactant for the preparation o f an organically modified clay. DMIPOSS-C1 expands the galleries of the clay, montmorillonite, to a greater extent than quaternary ammonium or other imidazolium surfactants. The large d-spacing o f the DMIPOSS treated clay, the strong POSS-POSS interactions within the clay galleries, and the incompressibility of the POSS cages prevent complete delamination of the clay layers in PS, E V A , and PA-6 nanocomposites, leading to predominantly intercalated structures. Thus, the thermal stability o f the PS P L S N is improved, but not as much as using clays modified by other imidazolium surfactants. Polvmer-Carbon Nanotube Nanocomposites Trialkylimidazolium salt compatibilized M W N T s have been used to prepare high quality PS nanocomposites using a melt-blending process. DSC, X R D , and T E M reveal that (1:1) M W N T : D M H d D B F mixtures can be blended with PS to produce single phase nanocomposites with good M W N T dispersion. M W N T / D M H d I B F mixtures with higher ratios of D M H d I B F result in phase separation of the excess D M H d I B F . The PS + (1:1) M W N T : D M H d I B F nanocomposite exhibits a thermal stability that is 20°C higher than the pure PS. Thus, well-dipersed, single phase PS nanocomposites can be prepared using a very low loading of M W N T to improve die thermal properties of the polymer. 4

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References


* - The policy of the National Institute of Standards and Technology (NIST) is to use metric units of measurement in all its publications, and to provide statements of uncertainty for all original measurements. In this document however, data from organizations outside NIST are shown, which may include measurements in non-metric units or measurements without uncertainty statements. The identification of any commercial product or trade name does not imply endorsement or recommendation by NIST or the United States A i r Force (USAF). Opinions, interpretations, conclusions, and recommendations are those of the authors and are not necessarily endorsed by the U S A F or NIST. †- Financial support was provided by the U S A F and NIST. 1. 2.

3.

4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14.

M . Alexandre and P. Dubois, Mater. Sci. Eng. R: Rep., 2000, 28, 1. W . H . Awad, J. W . Gilman, M . Nyden, R. H . Harris Jr., T. E . Sutto, J. Callahan, P. C. Trulove, H . C . De Long, and D . M . Fox, Thermochim. Acta, 2004, 409, 3. J. W . Gilman, W . H . Awad, R. D . Davis, J. Shields, R. H . Harris Jr., C. Davis, A . B . Morgan, T. E . Sutto, J. Callahan, P. C . Trulove, and H . C. De Long, Chem. Mater., 2002, 14, 2776. C . H . Davis, L.J. Mathias, J.W. Oilman, D . A . Schiraldi, P.C. Trulove, T.E. Sutto, H.C. De Long, J. Polym. Sci., Poly. Phys., 2002, 40, 2661. D . M . Fox, W . H . Awad, J. W. Gilman, P. H . Maupin, H . C . De Long, and P. C. Trulove, Green Chem., 2003, 5, 724. J. B . Carroll, A . J. Waddon, H . Nakade, and V . M . Rotello, Macromolecules, 2003, 36, 6289. L . Zheng, A . J. Waddon, R. J. Farris, and E . B . Coughlin, Macromolecules, 2002, 35, 2375. A . J. Waddon and E . B . Coughlin, Chem. Mater., 2003, 15, 4555. Z . M . Wang, T. C . Chung, J. W . Gilman, and E . Manias, J. Polym. Sci. B: Polym. Phys., 2003, 41, 3173. S. Bourgibot, J. W . Gilman, and C. A . Wilkie, Polym. Degrad. Stab., 2004, 84, 483. R. A . Vaia and E . P. Giannelis, Macromolecules, 1997, 30, 8000. S. Bellayer, J. W . Gilman, N . Eidelman, S. Bourbigot, X . Flambard, D . M . Fox, H . C . De Long, and P. C . Trulove, Adv. Mater., submitted. F. Neve, O. Francescangeli, and A . Crispini, Inorg. Chim. Acta, 2002, 338, 51. S. R. Tatro, L . M . Clayton, P. A . O. Muisener, A . M . Rao, and J. P. Harmon, Polymer, 2004, 24, 1971.


Application of Trialkylimidazolium Liquids and Salts to the Preparation

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