WO2002031002A1 - Nanostructures formees par polymerisation de cyclohexadiene - Google Patents

Nanostructures formees par polymerisation de cyclohexadiene Download PDF

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WO2002031002A1
WO2002031002A1 PCT/US2001/032007 US0132007W WO0231002A1 WO 2002031002 A1 WO2002031002 A1 WO 2002031002A1 US 0132007 W US0132007 W US 0132007W WO 0231002 A1 WO0231002 A1 WO 0231002A1
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pchd
polymerization
chd
sec
buli
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PCT/US2001/032007
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WO2002031002A9 (fr
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Jimmy Wayne Mays
Kunlun Hong
Samuel Patrick Gido
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Uab Research Foundation
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F232/06—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to the formation of nanostructures through polymerization reactions and, more particularly, to the formation of nanotubes through the controlled polymerization of cyclohexane.
  • Reference to Related Art Synthesis of PCHD Synthetic polymers are an indispensable and remarkably versatile class of materials. The suitability of a polymer for a particular application is controlled by its specific structural and molecular properties such as molecular weight (MW), molecular weight distribution (MWD), local and global architecture, and functionality.
  • MW molecular weight
  • MWD molecular weight distribution
  • local and global architecture and functionality
  • PCHD and its derivatives should have higher mechanical strength and better thermal and chemical stability compared to common, i.e., vinyl, polymers due to the alicyclic structures (six-membered rings) in the main chain.
  • PCHD can be modified by various dehydrogenation procedures, such as bromination followed by dehydrobromination. aromatization by p-chloranil, or catalytic dehydrogenation.
  • PCHD polymers have good heat, weather, impact, abrasion, and chemical resistances, low water absorption, and birefringence; they also serve as good optical materials due to their excellent transparency and rigidity.
  • the copolymer of 1,3-CHD with, cyclopentadiene has been used as an active element in photomicrolithographic devices, and the optical resolution is greatly enhanced by the addition of PCHD blocks. It has also been proposed that PCHD may be useful as a plastic material for undersea applications because of its high hydrolytic stability.
  • Block copolymers composed of thermodynamically incompatible blocks covalently bonded together, can self-assemble into well-ordered nano- domains because of the mutual repulsions between unlike chain segments and the constraints imposed by the connectivity of the blocks.
  • Even the simplest linear AB diblock copolymers consisting of two flexible chains can exhibit a rich variety of morphologies depending on their volume fractions.
  • Nonlinear architectures such as miktoarm stars and grafted block copolymers, have been demonstrated both theoretically and experimentally to allow control of morphology independent of the familiar composition windows found in linear AB diblock morphologies.
  • this morphology was demonstrated to be the equilibrium state of the system. This unusual morphology is presumably due to the graft architecture of the molecule and the relationship between the particular volume fraction and the concavity of the PS/PI interface on which the two PI chains per molecule must reside. At the same volume fraction and molecular weight, a linear PS-PI diblock would have PI spheres distributed in PS matrix. Also, for a regularly spaced, tetrafunctional multigrafted block copolymer (PI backbone with double PS grafts) with ⁇ 9 vol % PS, instead of producing PS sphere/PS cylindrical structure as predicted by Milner's theory, an unusual new morphology was formed.
  • the morphology can be described as a microphase-separated mesh of PS struts or wormlike domains in a PI matrix.
  • AB diblock copolymers consisting of a flexible coil and a rigid rod block (so-called rod-coil block copolymers) represent the extreme case of conformational asymmetry. These materials have stimulated much research interest over the past decade, and a variety of supramolecular architectures have been observed for rod-coil block copolymer systems.
  • the aggregation behavior of rod-coil systems reflects two different ordering phenomena: (i) the microphase separation of the coil and rod blocks into ordered periodic structures and (ii) the tendency of the rodlike block to form anisotropic, ordered structures.
  • PS-PCHD polystyrene-block-poly(l ,3- cyclohexadiene)
  • PS-PCHD polystyrene-block-poly(l ,3- cyclohexadiene)
  • This asymmetry might be expected given the fact that PCHD has para-linked cyclohexene rings inco ⁇ orated into the main chain of the polymer.
  • 1 ,3-CHD polymers are a very interesting class of materials because of their unique structures and expected advantageous properties.
  • star polymers are ideal for investigation into the structure-property relationships of branched polymers.
  • the first star polymers were synthesized in 1948 through condensation chemistry. Since then, virtually all polymerization methods have been used to make various star polymers; however, all of these methods are variations of two more general methodologies.
  • the first method involves the polymerization of a monomer "out of" a multifunctional initiator. This can be an experimentally expedient and clean approach, but common practical difficulties with this method involve synthesis of an appropriate initiator and adequately promoting its efficiency. (To obtain narrow molecular weight distribution materials, all initiating sites must react quickly.)
  • the second general method for making stars involves linking prepolymerized living polymer chains "rnto" a coupling reagent.
  • Divinylbenzene (DVB) and chlorosilanes are the most popular linking agents used. Chlorosilanes have become the classic linking agents for the synthesis of star polymers using anionic polymerization because of the clean and quantitative nature of the linking reaction (assuming steric effects are adequately considered).
  • DVB provides robust but relatively less well-defined branched materials, since precise control over the number of arms is not possible and stars produced by this method are always mixtures of materials having different numbers of arms.
  • the linking agent SiCl 4 was titrated with living (Pl-b-PS) Li solution until two arms were linked to SiCL, as determined by size exclusion chromatography (SEC). The difunctional macromolecular linking agent was then treated with a small excess of the living (PS-b-PI)Li solution to prepare the inverse star-block copolymer. The order of the addition was dictated by steric factors.
  • Tsiang synthesized several four-armed stars with three polybutadiene arms and one polystyrene-block-polybutadiene arm, (PS-b- PB)Si(PB) 3 . See Tsiang, R. C. C. Macromolecules 1994, 27, 4399.
  • the key step for this method is the successful synthesis of the pure (PB) 3 SiCl intermediate, which is obviously demanding.
  • Molenberg and co-workers 18 synthesized four-armed polybutadiene-b-poly(diethylsiloxane) (PB-b-PDES) star-block copolymers by the reaction of living PB-b-PDES chains with 1 ,4- dimethyl-l,l,4,4-tetrachloro-l,2-disily-ethane.
  • PB-b-PDES polybutadiene-b-poly(diethylsiloxane) star-block copolymers by the reaction of living PB-b-PDES chains with 1 ,4- dimethyl-l,l,4,4-tetrachloro-l,2-disily-ethane.
  • the star-block copolymers were cross- linked by hydrosilylation of the PB double bonds with chloro-dimethylsilane followed by condensation of the chloro-silane groups with water.
  • Nanotubes derived from carbon and "tubules" derived from phospholipids have also received a great deal of attention.
  • the former system is of fundamental interest as a true macromolecular system with a known architecture.
  • carbon nanotubes may be viewed as pure carbon fibers where the structure is entirely known to the atomic level, making them ideal materials for testing predictions of theoretical modeling.
  • Lipid tubules are hollow phospholipid bilayer cylinders that are mo ⁇ hologically similar to a soda straw. They have lengths of tens or hundreds of microns and diameters between 0.1 and 1 mm, making them very large relative to carbon nanotubes, which are several micrometers in length and 1-25 nm in diameter (larger sizes are for multi-walled species). To make lipid tubules useful in advanced materials applications, they may be metallized by coating with Ni or other metals; this imparts mechanical robustness and conductivity to the tubules. These tubules may be used as "nano-vials" for controlled release of marine antifouling agents (release over many years) and controlled release of drugs (release over days to months).
  • the metal clad structures also have interesting electromagnetic properties and are under investigation as miniaturized microwave circuits and as abso ⁇ tive filters.
  • carbon and phospholipid nanotubes there have been recent reports of nanotubes from metal oxides, amino acids, and organic precursors.
  • they have serious practical limitations. For example, they are extremely expensive: purified single-walled carbon nanotubes cost about $2,000 per gram and the cost of lipid tubules is comparable.
  • it is difficult to manufacture and purify the large amounts of these materials necessary for applications, although progress in scaling up single-walled carbon nanotubes is being made.
  • there are limitations to the sizes that can be created it is difficult to form ordered arrays, and the surface chemistries (important for functionalization and modifying surface interactions) are not readily manipulated.
  • Block copolymers through self-assembly in bulk or in solution can form various nanostructures such as spheres, cylinders, vesicles, etc. Even nanotube formation has been reported for block copolymer systems by Eisenberg, although these tubes were not crosslinked and thus their stability is dependent on their solvent environment. K. Yu and A. Eisenberg, "Bilayer Mo ⁇ hologies of Self-Assembled Crew cut Aggregates of Amphiphilic PS-b-PEO Diblock Copolymers in Solution" Macromolecules, 31, 3509 (1998). Liu recently reviewed work in the area of nanostructures from “functional block copolymers", where a block is crosslinkable thus allowing the nanostructure to be stabilized.
  • Liu and his co-workers have synthesized various stabilized nanostructures including star polymers, nanospheres, tadpole molecules, crosslinked polymer brushes, and nanofibers. See G. Liu, “Nanostructures of Functional Block Copolymers", Curr. Opinion Coll. Interface Sci,, 3, 200 (1998); J. Tao, S. Stewart, G. Liu, M. Yang, “Star and Cylinder Micelles of Polystyrene-block-poly(2-cinnamoylethyl methacrylate)", Macromolecules,
  • Nanotubes Angew. Chern. Int. Ed., J2, 340 (2000). They prepared cylindrical nanocylinders of a poly(/ert-butylacrylate-b-2-cinnamoylethyl methacrylate-b- isoprene) (PtBA-PCEMA-PI) triblock copolymer in methanol, followed by crosslinking of the PCEMA and removal of the inner PI block by ozonolysis.
  • PtBA-PCEMA-PI poly(/ert-butylacrylate-b-2-cinnamoylethyl methacrylate-b- isoprene) triblock copolymer in methanol, followed by crosslinking of the PCEMA and removal of the inner PI block by ozonolysis.
  • the present invention concerns the synthesis and characterization of a new type of nanotube based on self-assembled block copolymers of polystyrene (PS) and poly(cyclohexadiene) (PCHD).
  • PCHD is a structurally interesting polymer because it may be converted to poly(phenylene) (PP), a crystalline and chemically and thermally stable material, by aromatization. Furthermore, doping of PP will generate a conducting synthetic metal.
  • Poly(phenylene) nanostructures have recently been reviewed.
  • Monodentate additives do not yield controlled polymerization, while some polydentate additives, such as N,N,N',N'-tetramethylethylenediamine (TMEDA), 1 ,2-dimethoxyethane (DME), and l,4-diazabicyclo[2.2.2]-octane (DABCO), are effective in minimizing side reactions, if combined with the suitable butyllithium isomer.
  • TEDA N,N,N',N'-tetramethylethylenediamine
  • DME 1 ,2-dimethoxyethane
  • DABCO l,4-diazabicyclo[2.2.2]-octane
  • PCHD samples with narrow MWD and good MW control is possible using the /.-BuLi/DME/0°C or sec-BuLi/DABCO/20°C in benzene.
  • the "living" character of these polymerizations is disclosed. Additionally, the synthesis of block copolymers of
  • PCHD poly(l,3-cyclohexadiene)
  • PS-PCHD poly(styrene-l,3-cyclohexadiene)
  • PCHD-PS poly(l,3- cyclohexadiene-styrene)
  • 1,4- Diazabicyclo[2.2.2]octane was used to control the anionic polymerization of 1,3-CHD; it also acted as a promoter during the linking reaction.
  • the star polymers were fractionated to remove excess arm material and thoroughly characterized by size exclusion chromatography, matrix- assisted laser deso ⁇ tion ionization time-of-flight mass spectrometry, and light scattering.
  • PCHD poly(cyclohexadiene)
  • PS polystyrene
  • nanotubes of varying radius, wall thickness, and aspect ratio can be obtained.
  • composition of the block copolymer By varying the composition of the block copolymer, other shapes besides tubes (cylinders, plates) can also be made.
  • Reactive hydroxyl groups present on the surface of these molecular objects can be used to manipulate their processing characteristics and to provide strong bonding to matrix materials.
  • the PP nanotubes may be insulating or they may be made conducting by doping. Such materials could also be used as a component in a smart composite designed to transmit an electronic signal if, for example, impacted by a projectile. Opto-electronic and nanoprobe applications are also envisioned for these materials.
  • Figure B Block copolymers prepared by polymerization of 1,3-CHD with sec-BuLi in benzene followed by the addition of styrene (A); Styrene polymerized by sec-BuLi in benzene followed by addition of 1,3-CHD without use of any additive, the PSLi initiated the polymerization of 1,3-CHD (B).
  • Figure E Synthesis of diblock copolymer of PS and PCHD with ester bond.
  • Figure 1. SEC traces of PCHD from sec-BuLi in benzene at 0°C: (a) polymerization time 2 h; conversion ⁇ 43%; (b) polymerization time 6 h, conversion - 51%.
  • FIG 7. Compositions of PCHD in PS-PCHD copolymer (from the polymerization of 1,3-CHD and styrene simultaneously using sec-BuLi in benzene) vs polymerization time.
  • Figure 9. MALDI-TOF-MS spectra of PS-PCHD polymers: (A)
  • PCHD wt % 26.1 ;
  • PCHD wt % 11.1.
  • FIG. 13 SEC chromatograms from the synthesis of three-armed PCHD star: (A) PCHD arm, (B) first sampling (120 min), (C) unfractionated three-armed PCHD star, (D) fractionated three-armed PCHD star.
  • FIG. 14 SEC chromatograms from the synthesis of three-armed PCHD star with end-capping: (A) PCHD arm, (B) 1,3-butadiene end-capped PCHD arm, (C) first sampling (60 min), (D) unfractionated three-arm PCHD star, (E) fractionated three-armed PCHD star.
  • Figure 15. SEC chromatograms from the synthesis of three-armed polybutadiene star: (A) PBD arm, (B) first sampling (15 min), (C) second sampling (60 min), (D) unfractionated three-arm PBD star.
  • FIG. 16 SEC chromatograms from the synthesis of PS-PCHD three- arm star-block copolymer: (A) PS segment of the diblock arm, (B) PS-PCHD diblock arm, (C) first sampling (60 min), (D) unfractionated PS-PCHD three- arm star-block co-polymer, (E) fractionated PS-PCHD three-arm star-block copolymer (once).
  • FIG. 1 SEC chromatograms from the synthesis of PCHD-PS three- arm star-block copolymer: (A) PCHD segment of the diblock arm, (B) PCHD- PS diblock arm, (C) first sampling (60 min), (D) unfractionated PCHD-PS three-arm star-block co-polymer, (E) fractionated PCHD-PS three-arm star- block copolymer four times.
  • Figure 18 TEM Micrographs of PS/PCHD Diblocks. The light regions are PS and the dark regions are PCHD stained with osmium tetraoxide. These specimens were prepared by solvent casting and annealing; shearing may be used to enhance long range order, (a) End on view of core-shell cylinders in band across the center of this image, (b) Side-on view of core-shell cylinders.
  • 1,3-CHD was polymerized using several anionic initiators under different conditions, and the results are summarized in Table 1.
  • This table shows that the "traditional" anionic initiators, isomers of BuLi, do not work very well in controlling the polymerization of 1,3-CHD if used without additives. «-BuLi only produced trace amounts of polymer (not shown in
  • the side reactions during initiation are isomerization of the monomer to produce its 1,4-isomer and further to benzene; in some cases cyclohexene was detected.
  • the main side reactions during chain propagation are chain transfer through proton elimination and chain termination via hydride abstraction, as shown in Figure A. Under anionic polymerization conditions (strong base), chain transfer through hydride elimination (reaction a) and/or allylic proton abstraction (reaction b) always compete with chain propagation
  • 1,4-CHD a very reactive chain-transfer agent for alkyllithium-initiated polymerizations
  • 1,3-CHD The ability of 1,4-CHD to decrease strongly the observed molecular weight in the lithium-naphthalenide-initiated polymerization of 1,3-CHD has been demonstrated.
  • Lower polymerization temperatures also gave better results (runs 3 and 4 in Table 1), but poor solubility of the polymerization products under these conditions prevented further pursuit of this approach. Polymerization carried out in THF at low temperature also did not give the desired result (run 5 in Table 1).
  • BuLi/t-BuOK system regarded as "second generation" super base, yielded polymers with reasonably narrow MWD (Table 2 run 3), but the molecular weights were much lower than anticipated.
  • One possible reason is that the polymerization has to be carried out in THF at low temperature (-78°C), and chains could not grow very long due to solubility problems (high MW PCHD has limited solubility in THF; the solubility also depends on the microstructure).
  • Zhang and Rubenstein selectively polymerized the styrene group in 4-(vinylphenyl)-l- butene to generate a polymer with a polystyrene backbone and functional butenyl side chains. See Zhang, H.; Ruckenstein, E. Macromolecules 1999, 32, 5495. However, their targeted molecular weight was only about 4000 g/mol.
  • DME a weak-chelating agent
  • PCHD obtained from BuLi isomers with DPPE are listed in Table 2 (runs 7-9). Better results could be achieved if the reactions were carried out under optimal conditions with regards to solvents, temperatures, and the amount of the additive (ratios of BuLi/DPPE).
  • the 1,4 to 1,2 ratio of the PCHD from this polymerization system is about 57/43.
  • DABCO, a bulky chelating agent, combined with sec-BuLi or /er/-BuLi gives the best control over MW and polydispersity in the polymerizations of 1,3-CHD, as indicated in Table 2 (runs 13-15) and Table 3 (runs 1-7) (also Figure 2b).
  • the resulting PCHD has a 1,4 to 1 ,2 additions ratio of 93/7.
  • 1,4-CHD which is always present at some level in 1,3-CHD under strong base conditions, is a very effective chain terminator. While the possible reinitiation to create PCHD homopolymer quantitatively on the basis of the data at hand cannot be ruled out, the spectrum in Figure 5 strongly suggests that this process does not play a major role in our studies. These results show that it is very difficult to prepare PS-PCHD samples with high 1 ,3-CHD content by sequential polymerization of styrene, and then 1,3-CHD, using sec- BuLi alone as initiator.
  • Table 4 also gives the characteristics of block copolymers prepared by polymerization of 1,3-CHD with sec-BuLi in benzene followed by the addition of styrene ( Figure B (A)).
  • PCHDLi chains can initiate the polymerization of styrene very rapidly under these conditions, as demonstrated by the yellow color turning to red-orange instantly upon addition of styrene.
  • SEC traces for products of this reaction are shown in Figure 6.
  • the polymerization of 1,3-CHD initiated by sec-BuLi in the absence of additives does not proceed in a controlled manner.
  • the PCHD blocks are moderately polydisperse (Mw/Mn>1.2), as are the final PCHD-PS diblocks.
  • PCHD-PS block copolymer With a short PCHD block, the resulting PCHD-PS block copolymer is monomodal (Figure 3a). However, bimodal PCHD-PS is formed when the PCHD block is longer (higher molecular weight) (Figure 3d). It is difficult to remove the low molecular weight shoulder from this material by conventional toluene/methanol fractionation. This is probably because part of the PCHDLi was deactivated before all the monomer (1,3-CHD) was consumed, and toluene is not a very good solvent for the PCHD block. More importantly, these results show that PCH-DLi can rapidly initiate the polymerization of styrene in hydrocarbon solvents even without the use of polar additives. This is in stark contrast to the copolymerization behavior of styrene and acyclic dienes.
  • PSLi with 1,3-CHD in benzene at room temperature is comparable to that of PCHDLi with styrene.
  • Natori reported the copolymerization behavior of 1,3- CHD with styrene in cyclohexane using the «-BuLi/TMEDA (4/5) initiating system at 40°C. See Natori, I.; Inoue, S. Macromolecules 1998, 31, 982. He found that styrene was preferentially polymerized in the initial stage, and the polymerization of 1,3-CHD started only when most of the styrene was consumed.
  • the MALDI-TOF-MS spectrum of the polymerization product from the first sampling of the "random copolymerization" is shown in Figure 9a along with a spectrum of a PS-PCFID diblock with similar composition ( Figure 9b).
  • Figure 9a The single peak around 6000 g/mol and the monomodal SEC traces ( Figure 9) suggest that the copolymerization was of a statistical nature. The drastic intensity differences in the two spectra are noteworthy. It was consistently observed that the MALDI-TOF-MS signals for PS-PCHD block copolymers are very weak. A possible reason for the low response of PS-PCHD block copolymers in MALDI-TOF-MS spectra is that effective MALDI requires that individual polymer chain be dispersed in matrix crystals.
  • PCHD segments are rather rigid and tend to aggregate during the preparation of MALDI samples. Consequently, only a small portion of the PS-PCHD chains can be ionized. However, the intensity for the "random copolymerization" product is much higher than that for PS-PCHD diblock copolymers. This also implies that the styrene and 1 ,3-CHD units are statistically distributed in the former copolymer (i.e., not blocky), making aggregation of PCHD more difficult. Furthermore, the rates of crossover reactions from PCHDLi to styrene and vice versa were comparable for the sec-BuLi/benzene system based on visual observations (as noted above).
  • the ,?-BuLi/DME or sec-BuLi/DABCO initiating systems can polymerize 1,3-CHD in a controlled manner with regard to molecular weight and Mw/Mn.
  • Typical results are listed in Table 4 (runs 9-12), and characterization data are given in Tables 5 and 6.
  • PCHDLi efficiently initiates the polymerization of styrene and vice versa, as shown in Figure 11.
  • the targeted composition for PCHD was lower than 30 wt %, the resulting PS- PCHD block copolymers were unimodal, and the polydispersities were low
  • compositions can be calculated from the intensities of styrene (6.2- 1.2 ppm, 5H) and 1 ,3-CHD (5.4-5.8 ppm, 2H) repeating units. This is because 1,3-CHD terminated some PSLi and/or PS-PCHDLi chains.
  • the low molecular weight shoulder was very difficult to remove by toluene/methanol fractionation if 1,3-CHD was polymerized first. The shoulder was probably formed by the self-termination of the PCHDLi chains, since the possibility of PCHDLi chains being terminated by styrene is low.
  • PCHD-PS 3 SiCH 3
  • the PCHD block shows a symmetric peak, but the PCHD-PS arm has a small peak at the low molecular weight end, which corresponds to the PCHD blo ⁇ k as shown in Figure 17.
  • the molecular weight of the PCHD block is low ( ⁇ 10 000 g/mol). This indicates that the crossover reaction from PCHDLi to styrene is not 100% complete when the PCHD block is very long. In this case, the 1,3-CHD polymerization takes longer to attain high molecular weight PCHD, and during this time some PCHDLi can be terminated or undergo chain transfer.
  • Nanostructures Applicants previously synthesized poly(styrene-block-cyclohexadiene) and collaborated on a study of the mo ⁇ hology of self-assembled, microphase- separated diblock copolymer of PS and PCHD.
  • An unusual core-shell cylinder-in-cylinder mo ⁇ hology not previously found in neat diblock copolymers was observed in three different specimens of different molecular weights but all having similar composition (about 37% by volume PCHD).
  • This structure consists of hexagonally packed cylinders of PCHD dispersed in a PS matrix; in the center of each PCHD cylinder there is a PS cylinder ( Figure 18).
  • This structure is the precursor to the novel nanotubes that are the subject of this proposal; by removing the PS inside and outside the PCHD cylinder, PCHD nanotubes may be produced.
  • the present invention is directed to the core-shell cylinder-in-cylinder mo ⁇ hology that was observed for PS/PCHD diblocks as a means to synthesize functional polymer nanotubes.
  • PS/PCHD diblocks To be able to remove the PS blocks it is necessary to have cleavable linkages connecting the two chain segments in the block copolymers.
  • Such diblock copolymers can be synthesize by esterification of hydroxyl groups placed at one end of the PCHD chains with carboxylic acid groups placed at one end of the PS chains (see Figure E).
  • the chemistries to be used for chain end functionalization (carboxylation of PS chain ends with CO 2 and reaction of
  • PCHD chain ends with ethylene oxide are based on well-established literature procedures. For example, reaction of PCHD anions with ethylene oxide followed by protonation creates the desired end functionalized PCHD, while reaction of PS anions with CO 2 under appropriate conditions yields the complementary end reactive PS.
  • the compositions of the materials is controlled at about 37 vol % PCHD, since this is the composition that yielded cylinder-in-cylinder mo ⁇ hologies for three PS-PCHD diblocks, having different molecular weights.
  • the diameter of the nanotubes is controlled by the molecular weight of the PCHD block.
  • Nanotubes are formed by casting films of the diblocks annealing and or using shearing to orient the dispersed cylinders, photocrosslinking of the PCILD phase, hydrolysis of the ester linkages under acidic conditions, and washing out of the PS material with solvents.
  • the processing conditions controls the extent of long range order present in the microphase separated structure and can be used to control the aspect ratio — and thus properties - of the nanotubes.
  • THF or dioxane containing aqueous acid may be used for hydrolysis. This solvent system will swell the polymer phases permitting cleavage of ester linkages to occur.
  • the removal of the PS phase, especially the PS inside the PCHD nanocylinders requires careful solvent selection to preferentially swell the crosslinked PCHD domains.
  • PCHD can be aromatized using p-chloranil or the more efficient reagent 2,3-dichloro-5,6 ⁇ dicyano-l,4-benzoquinone.
  • These nanotubes have hydroxyl groups on their surface due to cleavage of the ester linkages. These groups are then used to attach things to the nanotubes or to promote interactions between the nanotubes and some matrix in which they are dispersed. These surfaces are above be chemically modified to create a wide range of tunable surface chemistries.
  • Nanotubes based on this block copolymer precursor approach are intermediate in diameter to single-walled carbon nanotubes and lipid tubules, with diameters ranging from about 10-100 nm and controlled through block copolymer molecular weight (MW), composition, and optional addition of homopolymer. Their lengths can be controlled over the range of tens to many thousands of nm, giving them controllable and potentially very long aspect ratios. Compared to other nanotubes, these materials are inexpensive to manufacture, amenable to scale up, and ordered arrays on a surface may be readily created through self-assembly. In addition, the synthesis route will yield products with controlled surface functionality. Both conducting and nonconducting materials can be generated. In addition to the synthesis of nanotubes, the general synthetic approach described herein could also be used to synthesize PP nanocylinders (nanowires after doping), nanospheres (a new type of quantum dot), or sheets of nanoscale thickness.
  • MW block copolymer molecular weight
  • Staining with OsO allows TEM imaging of the nanoscopic PCHD hollow tubes, which have self assembled onto a hexagonal lattice (34).
  • Small angle scattering experiments are performed in order to accurately determine the lattice symmetries and dimensions of the mo ⁇ hologies.
  • Control of nanotube size via control of molecule weight and composition will be confirmed by microscopy and scattering; it is important to employ a combination of both TEM and scattering techniques in the determination of mo ⁇ hological structure since the two techniques compensate for each others weaknesses.
  • SAXS X-ray
  • SAX-ray can be done using a rotating anode sources and a two-dimensional area detector at the University of Massachusetts.
  • the dispersed nanotubes are deposited on amo ⁇ hous carbon substrates for imaging via TEM and electron diffraction characterization of crystallinity in cases where the structures are converted to PP.
  • the nanotubes are then imaged via FEGSEM which is capable of resolving structures of 4 nm without need of metal coatings.
  • characteristic X-ray detectors on both the TEM and FEGSEM instruments will allow spatially resolved mapping of elemental composition variations. Atomic force microscopy will also be used to observe the nanotubes.
  • AFM provides a convenient means of accurately measuring tube dimensions, and mechanical properties of individual tubes can be probed by applying pressure with the AFM tip.
  • the proposed structures have a number of exciting optical device applications as well as uses as nanoprobes and in field emission.
  • Ordered two- dimensional arrays of the nanotubes may be made by solvent etching of a surface having the cylinders oriented pe ⁇ endicular to the surface.
  • Nanolithographic patterning may be performed by selective masking during the UN irradiation step.
  • the ordered tubes can be selectively filled with desired materials, e.g. metals.
  • Other architectures besides tubes can also be made based on cylindrical or lamellar mo ⁇ hologies. These molecular objects can be useful for miniaturization of optical and electrical devices and micromechanical systems (MEMS).
  • SIP Surface initiated polymerization
  • TMEDA (Aldrich, >99%), N,N,N',N',N'- pentamethyldiethylenetriamine (PMETE-DA, Aldrich, 99%), DME (Acros, >99%), and 1,2-dipiperidino-ethane (DPPE, Sigma, >99%o) were stirred over freshly crushed CaH 2 powder for at least 24 h and distilled from potassium (K) mirror twice and finally from potassium/sodium alloy under high vacuum.
  • PMETE-DA N,N,N',N',N'- pentamethyldiethylenetriamine
  • DME Acros, >99%
  • DPPE 1,2-dipiperidino-ethane
  • Naphthalene (Aldrich, >99%) and l,4-diazabicyclo[2.2.2]octane (DABCO, Aldrich, 98%) were sub-limed under high vacuum three times and then diluted in cyclohexane and benzene, respectively.
  • Potassium tert-butoxide (t-BuOK, Aldrich, 95%) was diluted in THF, and phenyllithium (PhLi, Aldrich, 1.8 M in ether and cyclohexane) and tert-butyllithium (t-BuLi, Aldrich, 1.5 M in pentane) were used as received.
  • 1,3-CHD (Aldrich, 97%) was cleaned by treating over CaH 2 followed by exposure to sodium mirrors at room temperature 2-3 times for 24 h each. This "roughly" purified 1,3-CHD was finally treated with n-BuLi or dibutylmagnesium (MgBu2 Aldrich, 1.0 M in heptane) at 0°C for 30 min just before the polymerization. Butyllithiums (sec-
  • BuLi and n-BuLi were prepared by reactions of the corresponding butyl chloride with lithium powder in hexane under vacuum. Cumyl potassium
  • the stabilized polymer was isolated by filtration and dried under high vacuum.
  • Number-average molecular weights (Mn) and polydispersity indices (Mw/Mn, where Mw is weight-average molecular weight) were obtained from size exclusion chromatography (SEC) relative to calibration with polystyrene (PS) standards in either THF or chloroform (CHCL).
  • SEC in THF flow rate: 1 mL/min; Waters Styragel 100, 500, 10 3 ,10 4 , and 10 5 A columns
  • SEC in CHCI 3 flow rate: 0.3 mL/min; columns: Polymer Lab.
  • Tetrahydrofuran (THF, Aldrich, 99.9%) was refluxed over sodium for at least 6 h and collected into a flask containing sodium dispersion under argon. This flask was then connected to the vacuum line; the solvent was degassed and distilled into a flask with sodium/potassium alloy. After stirring for some time, the bright blue color that developed showed that the THF was free from impurities deleterious to anionic polymerizations.
  • TMEDA Aldrich, >99%
  • DME AdME
  • K potassium
  • Styrene Aldrich, 99%>
  • Diazabicyclo[2.2.2]-octane (DABCO, Aldrich, 98%) was purified by sublimation three times under vacuum and then diluted in benzene or cyclohexane. Naphthalene was also purified by sublimation three times but diluted in THF. 1,3-CHD (Aldrich, 97%) was cleaned by treating over CaH 2 , sodium mirror (3 times), and finally H-BuLi or MgBu 2 .
  • Butyllithium (sec-BuLi or //-BuLi) was prepared from the reaction of 2-chlorobutane (Aldrich, g 99%) or 1 -chlorobutane (Aldrich, > 99%) with lithium powder (Aldrich, high sodium, 99%o) in hexane.
  • Potassium naphthalenide was made by reacting naphthalene with a K mirror in THF at -78°C for 2 h just before polymerization. Polymerization. All polymerizations were carried out under high vacuum using custom-made glass reactors, and detailed procedures are outlined in the literature.
  • PS-PCHD diblocks by either polymerizing 1,3-CHD first, followed by addition of styrene ( Figure B, (A)), or by polymerizing styrene first, followed by addition of 1,3-CHD ( Figure B,
  • the final product was found to have a weight-average molecular weight (Mw) of 18.6 kg/mol (from multiangle laser light scattering (MALLS)), a number-average molecular weight (Mn) of 15.4 kg/mol (from MALDI-TOF-MS), a polydispersity (Mw/Mn) of 1.03, and a composition of PCHD with 66.0 wt % (from ⁇ NMR).
  • Mw weight-average molecular weight
  • Mn number-average molecular weight
  • MALDI-TOF-MS MALDI-TOF-MS
  • Mw/Mn polydispersity
  • the polymerization was stopped by adding degassed methanol.
  • the final diblock copolymer had Mw of 41.8 kg/mol (MALLS), Mn of 44.2 kg/mol (SEC), Mw/Mn of 1.07 (SEC), and a composition of PCHD of 39.4 wt % (from ⁇ NMR).
  • the polymer solutions were precipitated in a large excess of methanol with 2,6-di-tert-butyl-4- methylphenol (butylated hydroxytoluene, BHT) added as antioxidant.
  • BHT butylated hydroxytoluene
  • the final polymer was isolated by filtering and drying under high vacuum. For some samples, solvent/nonsolvent fractionation (toluene/methanol) was used to remove homopolymer contaminants.
  • This system was also connected to a Wyatt DAWN DSP MALLS detectors equipped with 5 mW linearly polarized He-Ne laser (wavelength) 632.8 nm).
  • the MALLS unit has 18 detectors with fixed detector angles from 22° to 147°.
  • dn/dc values of the samples are required.
  • the refractive index increments (dn/dc) for PCFLD and PS in CHC13 were measured with a Brice-Phoenix differential refractometer, operating at 632.8 nm and calibrated with aqueous potassium chloride solutions.
  • H NMR experiment was carried out in CDC13 at 30°C using a Bruker ARX 300 instrument.
  • MALDI-TOF-MS spectra were obtained with a PerSeptive Biosystems Voyager Elite DE instrument using linear mode. A 20 kV acceleration was used with delayed extraction. The spectra were collected by summing 250 shots by using a nitrogen laser (337 nm, 3 ns pulse width) operated at 5 Hz. Samples were prepared by mixing matrix (dithranol, - 10 mg/ mL) and ionizing salt (silver trifluoroacetate, ⁇ 1 mg/mL) with polymer species ( ⁇ 1 mg/mL) in a ratio of 20/20/1 (v/v). CHC1 3 was the solvent. Approximately 0.5 ⁇ L of the sample solution was applied to the sample plate. All spectra were baseline corrected and smoothed. Peptide standards were used to calibrate the instrument externally.
  • Tetrahydrofuran (THF, Aldrich, 99.9%>) was refluxed over sodium for at least 6 h and collected into a round flask containing sodium dispersions under argon. This flask was then connected to the vacuum line; the solvent was degassed and distilled into a flask with sodium/potassium alloy. After stirring for some time, the bright blue color showed that the THF was free from impurities deleterious to anionic polymerizations.
  • 1,3-Butadiene (1 ,3-BD, Aldrich, >
  • l,4-Diazabicyclo[2.2.2]octane (DABCO, Aldrich, 98%) was purified by sublimation three times under vacuum and then diluted in benzene or cyclohexane. 1,3-CHD (Aldrich, 97%) was cleaned by treating over CaH 2 , sodium mirror (three times), and finally /.-BuLi or MgBu2, and the details was described elsewhere. 28 sec-Butyllithium (sec-BuLi), prepared from the reaction of sec-butyl chloride (Aldrich, > 99%) with lithium powder in hexane, was used as the initiator.
  • sec-BuLi sec-Butyllithium
  • Methyltrichloro-silane (CH 3 SiCl 3 , United Chemical Technologies, Inc., > 99.9%) was stirred over CaH 2 overnight, followed by fractional distillation on the vacuum line (collecting the middle 1/3 fraction) and then subdivided into ampules. It was diluted to the desired concentration with purified hexane.
  • the linking reaction started by adding 2.9 mL of CH 3 SiCl 3 (4.6 x 10. 5 mol/mL in hexanes). The linking process was monitored by taking aliquots on a scheduled basis and checking with SEC. After the linking reaction was completed, degassed methanol was added to terminate the excess arm. The polymer solutions were precipitated in a large excess of methanol with 2,6-di-tert-butyl-4-methylphenol (butylated hydroxytoluene, BHT) added. The final polymer was filtered and dried under high vacuum. After fractionation, the Mw of the three-arm PCHD star from the polymerization described above is 41.2 kg/mol with a MWD of 1.06 as determined by SEC equipped with a multiangle laser light scattering (MALLS) detector.
  • MALLS multiangle laser light scattering
  • Solvent/nonsolvent (toluene/methanol) fractionation was used at room temperature to remove the excess unreacted arm material. Methanol was added slowly to the polymer solution in toluene (concentration ⁇ 0.5% w/v) until turbidity appeared. The solution was heated gently to eliminate turbidity while stirring. It was then transferred to a warm separator/ funnel. This system was left undisturbed overnight to allow phase separation. This procedure was repeated as necessary.
  • This system was also connected to a Wyatt DAWN DSP MALLS detectors equipped with 5 mW linearly polarized He-Ne laser (wavelength) 632.8 nm).
  • the MALLS unit has 18 detectors with fixed detector angles from 22° to 147°.
  • dn/dc values of the samples are required.
  • the refractive index increments (dn/dc) for PCHD and PS in CHCI 3 were measured with a Brice- Phoenix differential refractometer, operating at 632.8 nm and calibrated with aqueous potassium chloride solutions (dn/dcPS ) 0.172 mL/g and dn/dcPCHD) 0.125 mL/g).
  • the dn/dc for the star-block polymers were calculated from the weighted average dn dcstar) xPS(dn/dc)PS + (1 - xPS)(dn/dc)PCHD, where xPS is the PS weight fractions determined by ⁇ NMR.
  • the ⁇ NMR experiment was carried out in CDCI 3 at 30°C using a Bruker ARX 300 instrument. Matrix-assisted laser deso ⁇ tion/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) spectra were obtained with a PerSeptive Biosystems Voyager Elite DE instrument using linear mode. 20 kV acceleration was used with delayed extraction.
  • the spectra were collected by summing 250 shots by using a nitrogen laser (337 nm, 3 ns pulse width) operated at 5 Hz.
  • Samples were prepared by mixing matrix (dithranol, - 10 mg/mL) and ionizing salt (silver trifluoroacetate, _ 1 mg/mL) with polymer species (-1 g/mL) in a ratio of 20/20/1 (v/v).
  • CHC13 was the solvent.
  • a From MALDI-TOF-MS; b : via SEC; c : From SEC-MALLS; d : via ⁇ -NMR; e: in ml/g and calculated from the weight composition and the dn/dc data for PS and PCHD in CHC1 3 (0.172 and 0.125 ml/g, respectively).

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Abstract

L'invention concerne un procédé de formation de nanostructures, qui comprend l'étape consistant à polymériser un diène dans des conditions permettant d'obtenir une structure qui présente au moins une dimension comprise entre 1 et 100 nanomètres. Plus spécifiquement, l'auto-assemblage de copolymères séquencés de styrène et de 1,3-cyclohexadiène est utilisé afin de former une morphologie du type « cylindre dans cylindre » ; une réticulation est ensuite mise en oeuvre sur le poly(cyclohexadiène) (PCHD), ainsi qu'une élimination des segments de polystyrène (PS) afin de produire de nouveaux nanotubes PCHD fonctionnalisés. PCHD peut servir à former un dérivé aromatique, le poly(phénylène) (PP), un polymère industriel résistant, cristallin et stable thermiquement. Ces matières sont caractérisées par leurs dimensions, formes, propriétés de chimie de surface et mécaniques. Les composites incorporant ces nanotubes peuvent être utilisés dans une nouvelle classe de matériaux robustes, légers et à haute résistance.
PCT/US2001/032007 2000-10-11 2001-10-11 Nanostructures formees par polymerisation de cyclohexadiene WO2002031002A1 (fr)

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