WO2007044587A2 - Systemes polymeres a directions vectorielles et procedes d'auto-assemblage de nano-structures - Google Patents

Systemes polymeres a directions vectorielles et procedes d'auto-assemblage de nano-structures Download PDF

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WO2007044587A2
WO2007044587A2 PCT/US2006/039262 US2006039262W WO2007044587A2 WO 2007044587 A2 WO2007044587 A2 WO 2007044587A2 US 2006039262 W US2006039262 W US 2006039262W WO 2007044587 A2 WO2007044587 A2 WO 2007044587A2
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polymer
conformational
atoms
aromatic moieties
structures
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WO2007044587A3 (fr
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Steven W. Fowkes
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Fowkes Steven W
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule

Definitions

  • This invention relates generally to polymers (classes of polymers) polymer systems and methods for making polymers. More specifically, this invention relates to polymers and polymer systems with ordered and extended structures and methods for making the same.
  • Standard-art polymers have multiple backbone bonds with no significant restraints on bond rotational freedom.
  • the aliphatic backbone bonds in polyolefins are all free to rotate.
  • the carbon-carbon backbone bonds and half of the carbon-nitrogen backbone bonds are free to rotate.
  • Even in aromatic polymers with rigid rings aramids like Kevlar and Nomex, bisoxazoles like Zylon, and imidazoles like M5
  • polymers that exhibit extended or backbone vector directionality in two or three dimensions.
  • Such polymers can be used to make nano-structural materials for a variety of different applications, including electronic fabrication technologies, aerospace technologies, biological technologies, medical technologies, battery storage technologies and energy technologies name a few.
  • the present invention is directed to polymers and polymer systems that can form extended two and three-dimensional structures and hence are referred to as vector-directional polymers.
  • the backbones of the polymers, or portions thereof, are energetically and/or sterically stabilized to have conformational rigidity or semi- rigidity as a result of a combination of chemical groups and bonding features, such as are described below. These chemical groups and bonding features constrain bond movement and bond rotation along the polymer backbone and between nearest neighbor aromatic moieties.
  • the polymers include a backbone consisting of aromatic moieties bonded together with what are refereed to herein as "conformational linkage units.”
  • the aromatic moieties are benzenoid structures and/or heterocyclic structures.
  • the heterocyclic aromatic moieties can include, for example, one or more nitrogen atoms and still have a substantial degree of aromatic character (delocalized pi- bonding).
  • the conformational linkage units can include one or more "conformational ring structures" that can include hetero-atoms. Where a conformational ring structure includes one or more hetero-atoms, the structure is also referred to herein as a "conformational heterocyclic structure.”
  • the conformational ring structures typically include hydrogen atoms that engage in hydrogen bonding to form or close the conformational ring structures.
  • the conformational ring structures can include other Lewis acid features (election acceptors) that interact with adjacent Lewis base features (electron donors) in the conformational ring structures and provide ionic interactions that form or close the conformational ring structures.
  • the conformational ring structures can include hetero atoms, such as nitrogen atoms that act as Lewis bases, and/or metal atoms that act as Lewis acids.
  • the metal atoms are preferably cationic metal atoms from the s-block of the periodic table.
  • metals atoms used in the present invention include, but are not limited to, lithium, beryllium, sodium, magnesium, potassium and calcium. It will be clear to one skilled in the art a number of other transition metal ions can also be employed with the present invention. Because the ring structures described above are not closed or bonded through purely covalent bonds, the term conformational ring structure has been used herein. Alternatively, the ring structures described above can be referred to as virtual ring structures.
  • the conformational ring structures include direct bond linkages or covalent segments that bond neighboring aromatic moieties through covalent bonds. These direct bond linkages can include 2 to 6 atoms, but preferably have three or fewer atoms.
  • the direct bond linkages can include hetero atoms, such as nitrogen atoms and can also include atoms that are structurally shared between or common with more than one and adjacent conformational ring structures.
  • each polymer of this invention assembles into a specific conformation determined by the monomers from which is it assembled. And because of structural and isomeric variability of monomers within each polymer class, each polymer system of this invention can be used to assemble a multiplicity of extended three-dimensional structures or arrays.
  • These extended structures may be straight rods (e.g., see Figures lla-b); sinusoids; circles, coils or tubes (e.g., see Figures 12a-b, and schematic of Figure 13b); polygons and polygonal cross-section tubes ( Figures 12a, but with straight-rod diamine oligomer); planar films; weaves (see schematic Figure 13a); meshes and tangles (with mixed-vector monomer blending); matrices and latices (e.g., Figure 13a, but with reversed positions of primary and secondary functionalities); and combinations of the above.
  • straight rods e.g., see Figures lla-b
  • sinusoids circles, coils or tubes
  • circles, coils or tubes e.g., see Figures 12a-b, and schematic of Figure 13b
  • polygons and polygonal cross-section tubes Figures 12a, but with straight-rod diamine oligomer
  • planar films weaves (see schematic Figure 13a); meshes
  • the polymer backbone is an amide polymer that can include aromatic structures and/or heterocyclic structures that are linked together through amide linkages or moieties.
  • Amide polymers and amide linkages that form them are described in detail in the U.S. Patent Application Serial No. 10/788,509, titled "AROMATIC AMIDE POLYMER SYSTEMS AND METHODS FOR MAKING THE SAME", the contents of which are incorporated by reference.
  • conformational rigidity of the conformational linkage units can bond nearest neighbor aromatic moieties throughout the polymer backbone or the conformational rigidity or the conformational linkage units can be interspersed throughout the backbone of the polymer in an ordered, random or blocked fashion.
  • the present invention can be used to make rigid polymer structures, semi-rigid polymer structures or polymer structures with rigid sections linked through flexible sections.
  • Fig. Ia shows a schematic representation of a portion of a polymer backbone, in accordance with the embodiments of the invention.
  • Figs. Ib illustrates nearest neighbor aromatic moieties bonded through amide direct bond linkages and stabilized through conformational ring structures, in accordance with the embodiments of the invention.
  • Figs. 2a-d illustrate how aromatic moieties are stabilized through a conformational ring structure, in accordance with the embodiments of the invention.
  • Figs. 3a-b illustrate how aromatic moieties are stabilized through a two-atom direct bond linkage and a conformational ring structure that exhibits hydrogen bonding, in accordance with the embodiments of the invention.
  • Figs. 4a-b illustrate how nearest neighbor aromatic moieties are stabilized by a covalently bonded 5-membered ring structure, in accordance alternative embodiments of the invention.
  • Figs. 5a-b illustrate how nearest neighbor aromatic moieties are stabilized by a covalently bonded 6-membered ring structure, in accordance alternative embodiments of the invention.
  • Figs. 6a-d show examples of nearest neighbor aromatic moieties bonded through two-atom direct bond linkages and stabilized through conformational ring structures, in accordance with the embodiments of the invention.
  • Figs. 7a-f show further examples of nearest neighbor aromatic moieties bonded through two- atom direct bond linkages and stabilized through conformational ring structures, in accordance with the embodiments of the invention.
  • Figs. 8a-e show examples of nearest neighbor aromatic moieties bonded through three-atom direct bond linkages and stabilized through conformational ring structures, in accordance with the embodiments of the invention.
  • Figs. 9a-b show examples of nearest neighbor aromatic moieties bonded through direct bond linkages with more than three atoms and stabilized through conformational ring structures, in accordance with further embodiments of the invention.
  • Fig. 10 illustrates an example of nearest neighbor aromatic moieties bonded through a two- atom direct bond linkage and stabilized through parallel conformational ring structures, in accordance with still further embodiments of the invention.
  • Figs. 1 la-d show extended portions of polymer backbones with nearest neighbor aromatic moieties bonded through amide direct bond linkages and stabilized through conformational ring structures, in accordance with further embodiments of the invention.
  • Figs. 12a-b show extended and coiled portions of polymer backbones with nearest neighbor aromatic moieties bonded through amide direct bond linkages and stabilized through conformational ring structures, in accordance with further embodiments of the invention.
  • Figs. 13a-b show schematic representations of a layered three-dimensional structure and a coiled structure formed by polymer and polymer systems with conformational linkage units bonding nearest neighbor aromatic moieties, in accordance with the embodiments of the invention.
  • the present invention utilizes selectively chemically modified aromatic (pi-bonded) molecular sub-assemblies (i.e., aromatic mono- and/or polycyclic monomers), the modified features (chemical groups or atomic constituents) of which form secondary bonds (bonds in addition to the initial, essential and/or primary polymer linkage bonds) with one or more chemical features of their adjacent polymer linkages and/or with one or more chemical features of adjacent (nearest or second-nearest neighbor) monomers to form additional bonds that form new covalent, metallo-ionic and/or hydrogen-bonded rings which restrict bond rotation and movement of bonds within the polymer linkage and newly formed rings or conformational linkage units to a single, preferred conformation. Additionally, chemical features may also restrict bond rotation through steric hindrance which blocks or obstructs conformations that might otherwise be possible or likely.
  • Aromatic molecular systems or moieties are bonded together by pi-bonds, which constrain all involved atoms to lie in a single plane.
  • pi bonds may flip, invert or rotate, converting from a cis to trans (or right to left, or up to down) conformation.
  • the circular connections between pi-bonded atoms does not allow any bond rotation within the rings. This has structural utility to chemists in creating stereospecific molecules (e.g., ortho, meta and para orientations).
  • single bonds connecting the rings to other, external atoms are capable of rotation. This invention specifies methods for involving these "external" atoms in additional ring systems that form during or following polymerization.
  • These ring systems may be entirely covalent (including aromatic and aliphatic components), or they may contain ionic, metal-coordination and/or hydrogen bonding features. However, despite these variations, these rings have one thing in common: they serve to extend the structural stability, rigidity and stereospecificity of the core monomer aromatic ring system outward into the polymer linkages, which can "overlap" with the adjacent monomers' extended systems to create conformationally deterministic (one-way-only) polymer linkages.
  • the present invention constrains the rotational freedom of polymer linkages to a single sterically and energetically preferred orientation or conformation. In turn, this allows the stereospecific features of the monomer subunits to be preserved and conserved down the polymer strand, instead of being randomized by rotation, hinging and pivoting of standard-art polymer backbones. It is believed that this approach represents a significant advancement in polymer art and the ability to selectively allow bond rotational freedom can advance the synthesis of molecular assemblies that can move in constrained ways and function as mechanical devices at the nano scale.
  • polymers and polymer systems of the present invention can be used to make straight rods, sinusoids, circles, coils, tubes, polygons, polygonal tubes, weaves, meshes, tangles, lattices, matrices, and combinations thereof.
  • Figure Ia shows a schematic representation of a polymer backbone structure 1, in accordance with the embodiments of the invention.
  • the polymer backbone structure 1 includes nearest neighbor aromatic moieties 2 and 3.
  • the nearest neighbor aromatic moieties 2 and 3 are bonded together through a conformational linkage unit 4.
  • the conformational linkage unit 4 includes a directed bond linkage 5 that covalently bonds the nearest neighbor aromatic moieties 2 and 3.
  • the directed bond linkage 5 can include two to six atoms, but preferably includes three or fewer atoms.
  • the atoms within the directed bond linkage 5 can exhibit double bond character and can be hetero atoms.
  • the conformational linkage unit 4 also includes one or more conformational ring structure 6 and 7, which can also include hetero atoms.
  • the conformational ring structures 6 and 7 prevent or restrict rotation or movement between nearest neighbor aromatic moieties 2 and 3 through or around the direct bond linkage 5.
  • the conformational ring structures 6 and 7 typically include hydrogen atoms that engage in hydrogen bonding to form or close the conformational ring structures 6 and 7.
  • the conformational ring structures can include other Lewis acids (election acceptors) that interact with a Lewis bases (electron donors) that provide ionic interactions that form or close the conformational ring structures.
  • the conformational ring structures 6 and 7 can include hetero atoms, such as nitrogen atoms that act as Lewis bases, and/or metal atoms that act as Lewis acids.
  • the conformational ring structures include metal atoms
  • the metal atoms are preferably cationic metal atoms from the s-block of the periodic table.
  • metals atoms used in the present invention include, but are not limited to, lithium, beryllium, sodium, magnesium, potassium and calcium. It will be clear to one skilled in the art that silver ions as well as a number of other transition metal ions can also be employed with the present invention. Because the ring structures described above are closed or bonded through purely covalent bonds, the term conformational ring structure has been used herein.
  • Figures Ib illustrates nearest neighbor aromatic moieties bonded through amide direct bond linkages and stabilized through conformational ring structures, in accordance with the embodiments of the invention.
  • Fig. Ib illustrates an iminol-configuration 70 of an direct bond amide linkage 78 with an aromatic structure 72 and a heterocyclic structure 74.
  • hetero-atom 71 such as a nitrogen atom, that is positioned beta relative to the nitrogen atom 76 that forms the amide leakage 78.
  • the enol-configuration 70 can promote hydrogen bonding 79 between the iminol-hydrogen atom 75 and the hetero-atom 71.
  • the enol-configuration 70 can have a hydroxyl group or alcohol functional group 73 that is positioned beta on the aromatic structure 72 relative to the carbon atom of the amide linkage 78. It is believed that hydroxyl groups, such as the hydroxyl group 73, can contribute to hydrogen bonding to the nitrogen atom that forms the amide linkage 78, as indicated by the dotted line 77, and thus form an additional conformational ring structure that stabilize the conformation of the iminol-configuration 70. The hydrogen bond 77 is believed to further stabilize the amide linkage 78 and add to the rigidity and/or stability of an extended polyamide structures having multiple amide linkages, as shown.
  • the structure described above with reference to Figure Ib, as well as those described below are all considered to be potentially useful in the synthesis of vector directional polymers.
  • Figures 2a-d are used to illustrate how aromatic moieties are stabilized through a conformational ring structure, in accordance with the embodiments of the invention.
  • a basic aromatic polymer structure (see Figure 2a) of directly connected benzene rings (102), allows each ring to rotate about the carbon-carbon bonds 101 between rings, and the introduction of an annular nitrogen atom (112, Figure 2b) alpha to the connecting bond (101) on one side of the connecting bond and a hydroxy group 113 on the same position on the opposite side of the connecting bond (also alpha positioned) allows a hydrogen bond 114 to form a new ring 115, which can only form when both the annular nitrogen atom 112 and hydroxy group 113 are on the same side of the carbon-carbon 101 bond (i.e., the nitrogen and hydroxy are cis oriented with respect to each other).
  • This extra bonding feature 117 not only provides a stabilizing influence for one conformation over the other, it also destabilizes the alternative conformation (see Figure 2c) by creating steric conflict (*) between the neutral, beta-located ring hydrogen atom 121 and the electronegative oxygen atom 123 of the hydroxy group.
  • this bonding feature converts an otherwise non-deterministic polymer linkage into a deterministic one. In other words, only one backbone conformation is favored.
  • annular (ring) nitrogen atoms and hydroxy groups the polymer backbone can be directed into any number of simple or convoluted conformations.
  • a similar bonding feature can also be created by use of a thiol instead of a hydroxy group, using a metal ion instead of a hydrogen ion to create oxygen-metal and metal-nitrogen coordination bonds.
  • a similar but oppositely charged bonding feature can be created by the use of annular boron atoms instead of annular nitrogen atoms (see Figure 2d), with requisite anionic instead of cationic functionality on the opposite ring.
  • anionic functionalities include but are not limited to nitro (shown), nitrate, nitrite, nitroso, carboxylate (shown), carbonate, borate, phosphate, perchlorate, sulfonyl (shown), sulfate, sulfite and sulfoxide groups, ethers and/or esters.
  • the annular nitrogen atom 112 serves as a Lewis-base feature which bonds with a proximal Lewis-acid feature (the proton located on the hydroxy (113), amino or thiol group, or a metal-atom analog of such groups), which is located on the adjacent ring (i.e., on the other side of the rotatable bond).
  • a proximal Lewis-acid feature the proton located on the hydroxy (113), amino or thiol group, or a metal-atom analog of such groups
  • the annular boron atoms in Figure Id serve as Lewis acids which bond to proximal Lewis-base features connected to the adjacent ring system.
  • Lewis acid-base pairings in these examples is not intended to exclude the use of two Lewis base groups and a Lewis-acid "bridging" group (e.g., two annular nitrogen atoms with coordination bonds to a transition metal) or two Lewis acids bridged by a Lewis base. These examples are also not meant to exclude covalent linkages, examples of which will be discussed below.
  • FIGS 3a-b will now used to illustrate how aromatic moieties are stabilized through a two-atom direct bond linkage and a conformational ring structure that exhibits hydrogen bonding, in accordance with the embodiments of the invention.
  • aramid polymers there are two atoms between adjacent aromatic rings, one of which is carbon and the other of which is nitrogen (see Figure 3a). Bond rotation can occur at all three bonds, but is significantly restricted about the center carbon-nitrogen bond 201 due to its substantial double-bond character.
  • Figures 4a-b illustrate how nearest neighbor aromatic moieties are stabilized by a covalently bonded 5-membered ring structure, in accordance with alternative embodiments of the invention.
  • a hydroxy group (304, Figure 4a) can be located at the same beta position as above (i.e., ortho to the ring-linkage attachment).
  • this creates dramatic steric conflict (*) in this configuration, it also enables a dehydration reaction with the adjacent amide group 305 to produce a 5-membered oxazole ring system (317, Figure 4b).
  • the oxazole ring system 317 restricts bond rotation of the ring-to-nitrogen (301, 311) and ring-to-carbon (302, 312) bonds of the amide polymer linkage, but like Examples shown in Figures 3a-b, does not restrict the carbon-to-ring bond (303, 313).
  • Analogs to those described above include replacement of the hydroxy group and can be a thiol group. If the hydroxy group is substituted with an amine group, an imidazole ring is formed. Although the imidazole ring successfully restricts bond rotation about the same two bonds, the two imidazole nitrogen atoms are essentially equivalent to hydrogen tautomerization, which has disadvantageous conformational consequences that will be discussed later.
  • Elements other than oxygen, sulfur and nitrogen suited to this feature are boron, phosphorus and silicon.
  • Figures 5a-b illustrate how nearest neighbor aromatic moieties are stabilized by a covalently bonded 6-membered ring structure, in accordance alternative embodiments of the invention.
  • a methylhydroxy group 404 can be used (see Figure 5a). This introduces two differences (see Figure 5b): 1) the resulting ring 419 is 6-membered instead of 5-membered, and 2) there is a saturated element (the methyl group, 418) in the newly-formed, rotation-restricting ring system 419.
  • the same analogs as discussed above with reference to Figures 4a-b also apply in the examples shown in Figures 5a-b.
  • Figures 6a-d show examples of nearest neighbor aromatic moieties bonded through two-atom direct bond linkages and stabilized through two conformational ring structures, in accordance with the embodiments of the invention. Note that in the examples above, only two of the three bonds capable of rotation are stabilized. In other words, one bond of the polymer linkage remains unstabilized against rotation. This may be remedied by adding a second bonding feature that forms a second, additional ring system that includes this third bond. In the case of the example shown in Figures 3a-b above, this second bonding feature can be a hydroxy (see Figure 6a) or thiol group, which can hydrogen bond 502 to the amide nitrogen lone electron pair. Metallic analogs of hydrogen bonds are additional types of this example (see Figure 6b).
  • Lithium 513 is illustrated as an example of a small-ion, pi-bonding metal (such as beryllium and boron, and the larger sodium, magnesium 537 and aluminum ions).
  • Copper 514 is illustrated as an example of a first-period transition metal, although more highly ionized second and third period transition metals and rare earth metals can be used.
  • the examples shown in Figures 6a and 6b involve 6-membered rings, boron derivatives (and other single-atom Lewis-acid analogs) can create 5-membered stabilizing rings (see 525 in Figure 6c, and 536 in Figure 6d). Oxygen analogs of aramids (esters) can be stabilized in a similar manner.
  • Figures 7a-f show further examples of nearest neighbor aromatic moieties bonded through two-atom direct bond linkages and stabilized through conformational ring structures, in accordance with the embodiments of the invention.
  • the same bonding features described with reference to Figures 6a-d above to stabilize the third linkage bond such as described in the example shown in Figures 3a-b can also be equally applied here (see Figures 7a and 7b, respectively).
  • the oxazole ring system 604 stabilizes amide-linkage bonds 601 and 602
  • the hydrogen-bonded thiol ring system 605 stabilizes amide-linkage bonds 602 and 603.
  • a covalent ring 616 stabilizes bonds 611 and 612 against rotation and hydrogen-bonded ring 617 stabilizes bonds 612 and 613 against rotation.
  • the choice of bonding feature can result in two 5-membered rings (see Figure 7c), a combination of one 5-membered ring and one 6-membered ring (see Figures 7d and 7e), or two 6-membered rings (see Figure 7f).
  • Figures 8a-e show examples of nearest neighbor aromatic moieties bonded through three-atom direct bond linkages and stabilized through conformational ring structures, in accordance with the embodiments of the invention. Two-ring stabilization is sufficient to stabilize a three-atom linkage provided that the two rings "overlap" (i.e. contain atoms in common, as in the previous two examples).
  • Figure 8a shows a 3-atom polymer linkage containing two carbon atoms and one nitrogen atom where one ring 701 includes two of the three linkage atoms and the other ring 702 includes all three linkage atoms.
  • Figures 8b and 8c show 3-atom polymer linkages of two nitrogen atoms and one carbon atom where one ring (713 and 725) contains two linkage atoms and the other ring (714 and 726) contains all three atoms.
  • Figures 8d and 8e both show 3-atom linkages where the two rings both contain only two linkage atoms each. However, in Figure 8d, the two rings contain a common non-linkage atom 732, which successfully constrains the linkage against rotation. This is not the case in Figure 8e where the two rings fail to overlap and there is conformational indeterminacy about the central carbon-carbon bond 748.
  • a third, additional bonding feature would be needed to constrain rotation about this carbon-carbon bond.
  • Figures 9a-b show examples of nearest neighbor aromatic moieties bonded through direct bond linkages with more than three atoms and stabilized through conformational ring structures, in accordance with further embodiments of the invention. Although bond linkages involving more than three atoms may be impractical, they can be never-the-less stabilized by this invention.
  • Figure 9a shows an example of a six-atom linkage which is constrained by only two rotation-restricting ring systems. The six-atom linkage is successfully constrained only because both of the rings contain four linkage atoms each, two of which are common to both rings, which results in the "overlap" that is required.
  • Figures 10 illustrates an example of nearest neighbor aromatic moieties bonded through a two-atom direct bond linkage and stabilized through parallel conformational ring structures, in accordance with still further embodiments of the invention.
  • the previous examples of ring-stabilized polymer linkages involve single overlapping rings. This is not meant to imply that parallel (redundant) stabilizing rings are not possible, or desirable.
  • the covalent borazole ring 901 stabilizes the ring-nitrogen and nitrogen-carbon linkage bonds, and two hydrogen-bond rings (902, 903) stabilize the nitrogen-carbon and carbon-ring linkage bonds.
  • the linkage nitrogen atom is a Lewis base
  • the linkage has only one conformation, which is enforced by dual (parallel) bonding features: 1) the pairing of the Lewis acid phenol proton with the linkage nitrogen atom (forming ring 902), and 2) the pairing of the Lewis base nitro oxygen atom with the boron atom (forming ring 903).
  • FIG. 11a shows a portion of a amide polymer backbone 1500 that can be formed by combining an aromatic dicarboxylic acid precursor and a heterocyclic diamine precursor.
  • the aromatic dicarboxylic acid precursor used to form the amide polymer backbone 1500 has reactive carboxylic acid groups that are positioned para with respect to each other on an aromatic ring and the heterocyclic diamine precursor used to form the amide polymer backbone 1500 has reactive amine groups that are positioned para with respect to each other on a heterocyclic ring.
  • each of the nearest neighbor aromatic moieties in this amide polymer backbone 1500 are bonded through amide direct bond linkages and stabilized through conformational ring structures.
  • Fig. lib shows a portion of an amide polymer backbone 1525 that can be derived from a heterocyclic amino-acid precursor by a self polymerization process.
  • the heterocyclic amino acid precursor used to form the amide polymer backbone 1525 has a reactive carboxylic acid group and a reactive amine group that are positioned para with respect to each other on a heterocyclic ring.
  • each of the nearest neighbor aromatic moieties in this amide polymer backbone 1525 is bonded through amide direct bond linkage and stabilized through conformational ring structures.
  • Figures 12a-b show extended and coiled portions of polymer backbones with nearest neighbor aromatic moieties bonded through amide direct bond linkages and stabilized through conformational ring structures, in accordance with further embodiments of the invention.
  • Figure 12a shows a portion of amide polymer 1600 that has substantial curvature resulting from a combination of alternating meta-orientated dicarboxylic monomer and para- orientated diamine heterocyclic monomers.
  • the amide polymer 1600 circles around to a point 1551 where the amide polymer 1600 can terminate or, alternatively, can continue to extend in a spiral or helical fashion.
  • Figure 12b shows a portion of an amide polymer 1650 that exhibits even greater curvature than the polymer 1600.
  • the polymer 1650 results from the self-polymerization of a heterocyclic amino-acid monomer. In this case, a carboxylic acid group is positioned meta relative to the reactive amine group.
  • the amide polymer 1650 formed by the reaction described above can circle around to a point 1563 where the amide polymer 1650 can terminate or, alternatively, can extend in a spiral or helical fashion.
  • Addition examples of extended polymers with backbone structures that have amide direct bond linkages between nearest neighbor aromatic moieties and that have conformational ring structures that stabilize the conformation of the polymer backbone are further described in the U.S. Patent Application Serial No. 10/788,509, titled "AROMATIC AMIDE POLYMER SYSTEMS AND METHODS FOR MAKING THE SAME," referenced previously.
  • Figures 13a-b show schematic representations of a layered three-dimensional structure and a coiled structure formed by polymer and polymer systems with conformational linkage units bonding nearest neighbor aromatic moieties, in accordance with the embodiments of the invention.
  • the aromatic nature of the polymer backbones and the conformational restrictions imposed by the boding between nearest neighbor aromatic moieties allow for the polymers of the present invention to assemble into or form extended three-dimensional structures.
  • polymers of the present invention can form a woven stacked sheet structure 1300, such as illustrated in Figure 13a and in Figures 12a-b, wherein the aromatic moieties are in the planes of the stacked sheet structure 1300.
  • the polymers of the present invention can form a stacked coil structure 1310, such as illustrated in Figure 13b, wherein aromatic moieties within the stacked coil structure eclipsing or partially eclipse each other.
  • This invention provides a systematic approach to creating rotation-restricted and movement-inhibited polymer linkages which allow preservation and conservation of stereospecific monomer features down the length of the polymer.
  • Each kind of stereospecific polymer linkage can be created by selected combinations of one, two or more members of a family or set of monomers which is defined by the presence of the requisite chemical groups attached to a monocyclic or polycyclic aromatic structure. This necessarily includes all isomers and analogs of the minimal (unsubstituted) monomers in the set.
  • Each set of monomers constitutes a "nanostructural toolset" for designing and assembling nanostructures and nanostructural sub-assemblies (dimers, trimers and oligomers).
  • stereo-determinism of the polymer linkages extends to stereo-determinism in oligomers and to "vector directionality" in derived polymers.
  • this invention includes “hybrid” monomers that may contain the requisite groups for forming two or more different stereospecific linkages on the same monomer. These "bridging” or “welding” monomers allow 1) the integration of different nanostructural toolsets in the design, synthesis and manufacture of nanostructural substances and materials, and 2) the use of different chemistries during different phases of molecular assembly.

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  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

La présente invention concerne des polymères et des systèmes polymères à directions vectorielles. Selon des modes de réalisation décrits dans cette invention, le polymère comprend des fragments aromatiques qui sont restreints ou fixés par des unités de liaison conformationnelle reliant les fragments aromatiques voisins les plus proches afin de former un squelette polymère. Ces unités de liaison conformationnelle comprennent, de préférence, des structures annulaires qui présentent des une liaison hydrogène ou d'autres types d'interactions tels que acide de Lewis-base de Lewis. Ces structures annulaires conformationnelles peuvent comprendre des hétéro-atomes et des atomes métalliques cationiques. Les groupes chimiques et les caractéristiques de liaison du squelette polymère freinent le mouvement de la liaison et la rotation de la liaison le long du squelette polymère. Ainsi, les polymères à directions vectorielles décrits dans cette invention peuvent s'assembler pour former des matrices ou des structures tridimensionnelles étendues.
PCT/US2006/039262 2005-10-07 2006-10-06 Systemes polymeres a directions vectorielles et procedes d'auto-assemblage de nano-structures WO2007044587A2 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6214923B1 (en) * 1998-07-17 2001-04-10 Jsr Corporation Polyimide-based composite, electronic parts using the composite, and polyimide-based aqueous dispersion
WO2003055859A1 (fr) * 2001-12-27 2003-07-10 Sony Corporation Complexes metalliques de composes aromatiques heterocycliques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6214923B1 (en) * 1998-07-17 2001-04-10 Jsr Corporation Polyimide-based composite, electronic parts using the composite, and polyimide-based aqueous dispersion
WO2003055859A1 (fr) * 2001-12-27 2003-07-10 Sony Corporation Complexes metalliques de composes aromatiques heterocycliques

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WO2007044587A3 (fr) 2007-07-12

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