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2-D Hybrid Organic-Inorganic Materials based on Organic Polymers Intercalated in Layered Inorganic Solids A new strategy to prepare materials

with synergetic or complementary behavior between the polymer and the inorganic solids interacting at the molecular scale the constrained environment is expected to lead to higher degree of polymer ordering promising applications : optics, electronics, ionics, mechanics and biology 3 main synthesis strategies : direct intercalation of a preformed polymer into the host lattice simultaneous intercalation and polymerization of monomer molecules which can be induced by redox properties of the layered host : redox intercalative polymerization (RIP) intercalation of monomer molecules with subsequent chemical, thermal or photo-induced in situ polymerization

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1

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1 - Intercalation of a preformed polymer into the host lattice a) direct intercalation of PEO into phyllosilicates poly(ethylene oxide) (CH2-CH2-O)n- : the simplest water-soluble polymer. As an infinite crown-ether, its salt complexes are promising solid electrolytes for applications in solid-state batteries and electrochromic devices phyllosilicates : layers built up by two tetrahedral silica sheets and a central octahedral sheet of magnesia or alumina. Isomorphous substitutions, mainly in the octahedral sheets, give a negative charge located in the layers which is compensated by exchangeable cations in the interlayer space Na-montmorillonite : Nax(Al2-xMgx)(Si4O10)(OH)2.mH2O Na-hectorite : Nax(Mg3-xLix)(Si4O10)(OH)2.mH2O

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1

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driving force of the polymer insertion process : the solvation of the alkali guest ions by the oxygen atoms of the polyether :
POE/H2O Tamb Na+-montmorillonite 6 < d < 8

the longer the macromolecules, the slower the reaction helical conformation as in crystalline PEO intercalated PEO amount is proportional to PEO concentration in aqueous solution d depends only on the cation size ionic conductivity close to that determined for conventional PEO-salt complexes, but better thermal stability b) intercalation of water-soluble polymers in V2O5 after previous swelling in water
OMe MeO MeO O OMe MeO O MeO O n O

polyvinylpyrrolidone n (PVP)
N O
HO O H n

mthylcellulose (MeCel)

poly(propylene glycol) (PPG)

V2O5.nH2O (xero)gels : prepared by polycondensation of decavanadic acid. Orientated films present a layered structure with an interlayer spacing of 11.5 and n 1.6. It is proposed that V2O5 layers are composed of corrugated ribbons with a step of 2.8 with the intraribbon structure close to the layers of orthorhombic V2O5 : layers of vanadium-oxygen square pyramids are connected by d-p covalent V=OV=O bonds :
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 6-3

V2O5.1.6H2O gel structure

orthorhombic V2O5 structure

driving force of the polymer insertion process : it would be the entropy stabilization by adsorption into the solid experimental conditions : aqueous polymer solutions are mixed with V2O5 solution and stirred at room temperature for several hours, prior to film casting. After slow water evaporation, a red film is formed the crystallinity decreases as the polymer loading increases in (PVP)xV2O5.nH2O : as x increases, the interlayer distance increases continuously and linearly up to x = 3 with an increment of 7 per PVP mole. The deviation at x > 3 values is attributed to the saturation of V2O5 galleries and the polymer deposition outside the host

polymer/V2O5 films become flexible with MeCel, but brittle with PPG and PVP
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 6-4

c) intercalation through complete exfoliation/ reflocculation of the MoS2 host Non-topotactic method where the inorganic layered host is completely exfoliated (colloidal dispersion) : then, the separated layers interact with organic macromolecules and precipitate from the solution, by re-stacking the single-layers and trapping the macromolecules in the interlayer galleries General method (except for smectic clays as Na+montmorillonite, which exfoliate by simple dissolution in water) : the reduction of layered compounds the destroying re-oxidation by hydrolysis metal dichalcogenide lattices consist of two hexagonally close-packed chalcogen layers between which reside the metal ions, which are found in sites of either octahedral or trigonal prismatic symmetry

direct intercalation in MoS2 is possible only with highly reducing agent such as alcali metals :
MoS2 + BuLi LiMoS2 + x H2O LiMoS2 + Bu-Bu (MoS2)single-layer + x LiOH + x/2 H2 (polymer)xMoS2 reduction exfoliation flocculation

(MoS2)single-layer + x polymer

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1

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so the MoS2 layers sandwich the polymer chains in a remarkably well-ordered way to produce a single-phase product (here : intercalation of polyamide-6)

among the intercalated polymers through this route : MeCel, PEO, PPG, PVP and :
O

nylon-6

n N n n H H polyaniline (PANI) poly(ethylene imine) (PEI)

NH

the electrical conductivity of (PEO)xMoS2 and (PPG)xMoS2 with respective room temperature of 0.1 and 0.2 S.cm-1 are among the highest reported for polymer/host nanocomposites potential cathodes in solid state high energy lithium batteries, because the encapsulated polymers when complexed with Li would provide the desired solid electrolyte and because the high conductivity of the layers should not necessitate the addition of conductive additives (e.g. graphite, carbon black)

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1

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d) nucleation and growth of a lamellar mineral in presence of macromolecules General method : nucleation and growth of inorganic crystals from homogeneous solutions containing the polymer chains as co-solutes ex : organoceramics synthesized by growing calcium aluminate crystals (double hydroxides) Ca2Al(OH)6[X].nH2O where X-= OH- or CO32- from a supersaturated calcium aluminate solution and a saturated calcium hydroxide solution in the presence of poly(vinyl alcohol) (PVA)

this route allows to overcome large entropic barriers and incorporate significant amounts of polymer, in some cases up to 38 wt.% the layered structure of the organoceramic was found to be stable up to a temperature of 400C, whereas the pure layered double hydroxide lacking organic material decomposed at 125C ; this phenomenon may be due to an extensive and strongly bonded interface between organic and inorganic components compacted into a cylinder the organoceramic has more than twice the compressive strength than the pure calcium aluminate
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 6-7

e) polymer "melt" intercalation General method : annealing a mixture of polymer and layered silicate powders above Tg or Tf in order to further the diffusion of the macromolecules from the bulk polymer melt into the van der Waals galleries between the silicate layers Li-fluorohectorite : Lix(Mg3-xLix)(Si4O10)F2.mH2O polystyrene -(CH2-CH)n- : Tg 100C
Li+-fluorohectorite + H2N-(CH2)17-CH3 cationic exchange (octadecylammonium)+-fluorohectorite + polystyrene mixing formed into a pellet at 70 MPa annealing at 150C

Figure : high-resolution bright-field TEM image of an intercalated primary particle near the polystyrene matrix (ultra-thin section)
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 6-8

+ polymer intercalated material

delaminated material

original properties of such materials when compared to their pure polymer constituent or their "microcomposites" counterparts : compatibility with current polymer processing techniques (injection, extrusion) higher modulus lower thermal expansion coefficient reduced gas permeability increased solvent resistance enhanced ionic conductivity

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1

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2 - Monomer intercalation and in situ polymerization a) redox intercalative polymerization (RIP) General principle : oxidative intercalation/polymerization of organic monomers with concomitant reduction of the inorganic lattice oxidatively polymerizable monomers :
NH2
NH NH2

aniline

4-anilinoaniline
Me

thiophene

2,2-bithiophene

3-methylthiophene
Me
Me Me

NH

N Me

NH

NH

pyrrole

N-methylpyrrole
O

3-methylpyrrole

3,4-dimethylpyrrole

terfurane

The oxidative polycondensation leads to electrically conductive polymers, whose structure is 3-dimensional and remains poorly understood :
n oxidant S thiophene S polythiophene
n

+ 2n e-

+ 2n H+

electron-acceptor inorganic hosts : they contain transition metals, which may be reduced : V2O5.nH2O, FeOCl, VOPO4 or some montmorillonites with preintercalated Fe3+ or Cu2+ cations
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 6 - 10

experimental conditions : a mixture of inorganic host and a solution of monomer in acetonitrile (neat monomer may also be used) is stirred at 50C for several days under N2. A black solid is obtained and collected by filtration. It consists in oriented electroactive polymer chains between the layers of the inorganic host (2-dimensional organization) the necessary and sufficient condition for RIP : the anodic potential of the Epa monomer must be less positive 2,06 V S than the redox potential of the 1,86 V inorganic host. Here the RIP of S thiophene and 3-methylthiophene in FeOCl failed contrarily to 2,2'FeOCl bithiophene. So upper and lower bounds can be placed on the redox S 1,32 V potential of FeOCl at 1.32 < E < S 1.86 V FeOCl structure is orthorhombic, characterized by double sheets of distorted octahedra which share edges : each iron atom is coordinated to four oxide anions and two chloride anions electronic conductivity : (C4H2S)0.28FeOCl : 5 S.cm-1

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b) intercalation/polymerization of MMA in Na-montmorillonite experimental conditions : the clay is saturated with MMA guest molecules, followed by desorption of the excess monomer by means of repeated washings. No spontaneous polymerization is observed. The polymerization is initiated with -ray irradiation or by cointercalated benzoyl peroxide observed results : d = 7.6 polymer yield is below 50 % the PMMA/montmorillonite nanocomposite has a greater thermal stability than conventional PMMA because of steric factors hindering the thermal motion of the polymer segments sandwiched between the inorganic sheet NMR spectroscopy shows short stereo-sequences with a predominant isotactic component, due to strong dipole-ion interactions between MMA and Na+

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c) intercalation/polymerization of -caprolactone in CrIII-fluorohectorite -caprolactone : cyclic monomer leading to biodegradable poly(-caprolactone) : -[(CH2)5-CO-O]n-

experimental conditions : mixing at 25C for 12 h followed by heating at 100C for an additional 48 h

observed results : the polymerization reaction appears to proceed through cleavage of the acyl-oxygen bond catalyzed by the interlayer Cr3+ ions intercalated polymer is strongly adsorbed onto the silicate layers and shows no melting transition
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 6 - 13

d) intercalation/polymerization of aniline in hydrogen uranyl phosphate HUO2PO4.4H2O : the layers consist of dumbbell-shaped UO2+ ions with the uranium further coordinated by four equatorial oxygen atoms of four PO43- tetrahedra forming two-dimensional sheets ; the galleries contain two water layers and H+ ions with can be exchanged with cations or neutralized with bases :

HUO2 PO4.nH2O + C6 H5NH2 excess

(C6 H5NH3)UO2 PO4.0.5H2O pale-yellow solid

130C/air (PANI)0.94 UO2 PO4.0.4H2O 3 weeks black solid

observed results : IR analysis of extracted polymer shows a small degree of cross-linking with 2-dimensional structure air oxygen is uniquely responsible for polymerization of intercalated anilinium ions on the contrary, solvated oxidants such (NH4)2S2O8, FeCl3, lead to the release of anilinium ions (by ionexchange with NH4+, H3O+) which are polymerized in solution outside of the host
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n bibliography w Poly(ethylene oxide)-silicate intercalation materials by P. Aranda and E. Ruiz-Hitzky, Chem. Mater., 4, 1395-403 (1992) w Intercalation of water-soluble polymers in V2O5 xerogel by Y.J. Liu et al., Adv. Mater., 5, 369-72 (1993) w Encapsulation of polymers into MoS2 and metal to insulator transition in metastable MoS2 by M.G. Kanatzidis and coll., J. Chem. Soc., Commun., 1582-5 (1993) w Synthesis of nanocomposites : organoceramics by P.B. Messersmith and S.I. Stupp, J. Mater. Res., 7, 2599-611 (1992) w Microstructural evolution of melt intercalated polymerorganically modified layered silicate nanocomposites by E.P. Giannelis and coll., Chem. Mater., 8, 2628-35 (1996) w In situ intercalative polymerization chemistry of FeOCl. Generation and properties of novel, highly conductive inorganic/organic polymer microlaminates by M.G. Kanatzidis et al., Solid State Ionics, 32/33, 594-608 (1989) w Polymerization of monolayers. V - Tacticity of the insertion poly(methyl methacrylate) by A. Blumstein and coll., J. Polym. Sci. : part A2, 8, 1599-1615 (1970) w Polymer-layered silicate nanocomposites : in situ intercalative polymerization of -caprolactone in layered silicate by E.P. Giannelis and coll., Chem. Mater., 5, 1064-66 (1993) w Topotactic polymerization of aniline in layered uranyl phosphate by M.G. Kanatzidis et al., Inorg. Chem., 32, 2989-91 (1993) w Acrylate intercalation and in situ polymerization in iron substituted nickel hydroxides by E. Duguet and coll., Polym. Int., 48, 277-282 (1999).
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