ADAMANTANE POLYMERIC COMPOSITIONS

Abstract: Polymers are disclosed which comprise monomer units bonded through octahedrally disposed atoms of the monomers. Adamantane exemplifies the skeletal structure of such monomers.

Description: ADAMANTANE POLYMERIC COMPOSITIONS The present invention relates to adamantane polymeric compositions. Adamantane, trιcyclo-[3.3.1.1 3'7]decane, is a polycyclic al ane with the structure of three fused cyclohexane rings. The ten carbon atoms which define the framework structure of adamantane are arranged in an essentially strainless manner. Four of these carbon atoms, the bridgehead carbons, are tetrahedrally disposed about the center of the molecule. The other six (methylene carbons) are octahedrally disposed. The reactivity of the bridgehead and methylene carbons is known. However, the importance of bonding through the octahedrally disposed carbons to form polymers has not previously been recognized. See Adamantane. The Chemistry of Diamond Molecules. Raymond C. Fort, Marcel Dekker, New York, 1976. Adamantane has been found to be a useful building block in the synthesis of a broad range of organic compounds, as exemplified by the following references. U.S. Patent 3,457,318 to Capaldi et al. teaches the preparations of polymers of alkenyl adamantanes useful as coatings, electrical appliance housings, and transformer insulation. The process, yielding polymers bonded through the tetrahedral bridgehead carbons, comprises contacting an adamantyl halide in the presence of a suitable catalyst with a material selected from the group consisting of substituted allyl halides and olefins to produce adamantyl dihaloalkanes or adamantyl haloalkanes as an intermediate product. The intermediate product is then dehalogenated or dehydrogalogenated, respectively, to produce the alkenyl adamantane final product. U.S. Patent 3,560,578 to Schneider teaches the reaction of adamantane or alkyladamantanes with a C--C 4 alkyl chloride or bromide using Aid- or AlBr. as the catalyst. The reference describes polymerization through C.-C. linkages connecting bridgehead carbon atoms in the starting adamantane hydrocarbon. U.S. Patent 3,580,964 to Driscoll discloses polyesters containing hydrocarbyladamantane moieties as well as novel intermediate diesters and crosslinked polymers prepared therefrom. The hydrocarbyladamantane moieties are bonded through the tetrahedral bridgehead carbons U.S. Patent 3,639,362 to Dulling et al. discloses novel copolymers having low mold shrinkage properties which are prepared from adamantane acrylate and methacrylates. The adamantane molecule is bonded to the polymer chain through tetrahedral bridgehead carbon atoms. U.S. Patent 3,832,332 to Thompson teaches a polyamide polymer prepared from an alkyladamantane dia ine. The polymer comprises repeating units which include the backbone structure of adamantane, in which the adamantane structure is bonded to the polymer chain through its bridgehead carbons. In its broadest aspect, the present invention resides in a polymer comprising at least three monomer units bonded through octahedrally disposed non-metallic atoms of the monomers. Normally, said octahedrally disposed atoms will have a valance of 4 and typically will be members of Group IVB of the Periodic Table of the Elements, catalog number S-18806, published by Sargent-Welch Scientific Company of Skokie, Illinois, 60077. Preferably, said atoms are carbon. Preferably, said monomer units have the skeletal structure of adamantane. As used herein, the term "octahedrally disposed" refers to points in space which exhibit octahedral geometry with respect to a common center point. The methylene carbons in adamantane define such octahedrally disposed points in space. The phrases "skeletal structure of adamantane" and "adamantane skeletal structure" as used herein designate a structure comprising four constituents which are tetrahedrally disposed with respect to the center of the molecule and six constituents which are octahedrally disposed with respect to the center of the molecule. Organic compounds exhibiting octahedral geometry are rare. Inorganic compounds commonly exhibit octahedral geometry. There are a few known examples in which organometallic compounds exhibit this arrangement. An example of such an orgamometallic compound is taught by B.F. Hoskins and R. Robson, "Infinite Polymeric Frameworks Consisting of Three- Dimensionally Linked Rodlike Segments", 111 Journal of the American Chemical Society. 5962 (1989) . The polymers of the present invention may include pendant substituent groups replacing one or more hydrogens of the monomer units. These substituent groups may also be interposed between monomer units as connecting groups or may be bonded to a monomer unit at the end of a polymer chain, thus forming a terminal substituent group. As used herein, the term "connecting substituent" refers to a constituent which connects two or more monomers in a polymer. The term "terminal substituent" refers to a constituent other than the repeating monomer unit which ends the polymer chain. The term "pendant substituent" refers to a group attached to the polymer backbone. Terminal substituents are a subset of pendant substituents. Referring to the following structural formula: T.1-A-A-A-A-Ai-B-Aι-A-A-T2, P P where A is a repeating monomer unit, and B is a connecting substituent which connects two monomers; T. and T- are terminal substituents which differ from the repeating monomer and which end the polymer chain; and P. and P. are pendant substituents attached to the polymer backbone. Non-limiting examples of such substituent groups include 8 -C 2 - aromatics, --C 20 linear and branched alkyl groups, 2 -C 2 - linear and branched alkenyl groups, --C-- linear and branched alkynyl groups, C 3~ C 20 c clo lk y 1 groups, 5 -C 20 cycloakenyl groups, C 7 -C- 0 cycloalkynyl groups, halogens, amines, diazo compounds, azide compounds, hydrazines, mercaptans, sulfides, polysulfides, ethers, alcohols, esters, organometallic compounds, amides, anhydrides, carba ates, ureas, imides, sulfonic acids, sulfinic acids, sulfinates, carboxylic acids, nitriles, isonitriles, heterocycles, metals, phosphates, phosphites, borates, ketones, aldehydes, aryl compounds, acid halides, hydrogen, and the reaction products thereof. The monomer units comprising the polymers of the present invention may be bonded through one or more of six octahedrally disposed atoms as illustrated above with reference to adamantane. Thus by selecting the number and location of octahedrally disposed atoms through which the monomers are bonded, the resulting polymers may assume linear, zig-zag, laminar, helical, or framework configurations as well as the myriad structures which may be synthesized from combinations of one or more of these configurations. The skeletal structure of the monomer units themselves may be modified and expanded. The positions occupied by the bridgehead and methylene carbons as illustrated above with reference to adamantane may be occupied not only by atoms other than carbon but also by substituent groups which can be substituted into the skeletal structure. Further, the skeletal structure may be expanded by inserting linear groups of uniform size between each of the bridgehead and each of the adjacent methylene positions. In addition to the inherent functionality of the inserted groups, the inserted groups expand the monomer unit while preserving the octahedral geometry of its bonding atoms. The invention will now be more particularly described with reference to the ccompanying drawings in whic ; Figures l and 2 show the structural formula of adamantane. Figure 3 shows synthesis of the adamantane linear rod polymer via McMurry coupling of at least 2 adamantane monoketone units, 3a, and at least 1 adamantane 2,6-diketone, 3b, to evolve the adamantane linear rod polymer, 3c. Figure 4 shows two examples of structures for the linear adamantane rod polymer wherein n is at least 1 and X. through X g are substituent groups. Figure 5 illustrates additional structures for adamantane rod polymers containing one or more functional groups in the terminal positions, wherein Ad has the skeletal stucture of adamantane and n is at least 3, and preferably is from 5 to 1 , and wherein R. and 2 comprise hydrogen or non-polar (hydrophobic) constituent groups having from 1 to about 20 carbon atoms, and wherein R. and R. comprise constituent groups having from 1 to about 20 carbon atoms, with at least one of said R. and R. being polar. Figure 6 illustrates four adamantane rod polymers corresponding to the structure 5a of Figure 5 in which R 1 and R 2 comprise C g H, 7 , n is 3, and R 3 and R 4 comprise CC- H. Figure 7 schematically illustrates synthesis of the zig-zag adamantane homopolymer via McMurry coupling of the 2,4-diketone of adamantane. The 2,4-diketone of adamantane is designated 7a and a portion of the resulting zig-zag polymer is designated as 7b. The general structure of the zig-zag adamantane homopolymer is designated 7c. Figure 8 is a simplified structural illustration showing the synthesis of adamantane dimer diketones from a monochlorinated adamantane dimer. The monochlorinated adamantane dimer starting material is designated as 8a, the intermediate adamantane monoketone dimer is designated as 8b, and four examples of the resulting diketones are designated ad 8c, 8d, 8e and 8f, respectively. Figure 8 further illustrates the acid-catalyzed interconversions between structures 8c and 8f and structures 8d and 8e. Figure 9 shows conversion of the linear adamantane trimer, 9a, to the intermediate monochlorinated adamantane trimer, examples of which include 9b and 9c, and subsequently to a mixture of linear adamantane trimer monoketones, two examples of which are designated 9d and 9e. Figure 10 shows conversion of an adamantane dimer diketone, designated as 8d, above in Figure 8, to a cyclic adamantane tetramer and polymers. Figure 11 shows the conversion of the cyclic adamantane tetramer shown in Figure 10, to the corresponding tetraketone by a two-step synthesis technique. Figure 12 shows the three-dimensional framework structure formed by 8 adamantane units. Figure 13 shows a two-step synthesis of adamantane dimer diketones from a monochlorinated adamantane, 13a, which is converted to the corresponding adamantane dimer monoketone, 13b, and finally to a mixture of adamantane dimer diketones, examples of which are designated 13c, 13d, 13e and 13f. Structures 13c and 13f as well as structures 13d and 13e interconvert in the presence of acid, for example, H 2 S0 4 . Figure 14 illustrates one technique for converting adamantane dimer diketone, designated as 13d in Figure 13, to a cyclic tetramer via McMurry synthesis. Figure 15 shows the conversion of an adamantane cyclic tetramer, 15a, through the cycle tetraketone, 15b, to a mixture of polymers including the framework octa er structure designated as 15c. Figure 16 illustrates four examples of repeating units which can be assembled to form adamantane homopolymer framework structures. Figure 17 illustrates four repeating adamantane units which can be assembled to form framework structures. Figure 18 shows conversion of an adamantane trimer monoketone, shown above as structure 9d in Figure 9, to an intermediate adamantane trimer diketone, 18a, and subsequently to the adamantane pentamer star polymer, 18b, by reaction with adamantane monoketone (adamantanone) in the presence of McMurry reagent. Figure 19 shows the conversion of the adamantane pentamer star polymer, designated as 19a, first to the adamantane pentamer star polymer diketone, 19b, and subsequently to the adamantane heptamer star polymer, 19c, via reaction with adamantane monoketone in the presence of McMurry reagent. Figure 20 schematically illustrates the adamantane star heptamer as a three-dimensional Maltese cross in which each adamantane skeletal unit is represented as a cube. Figure 21 shows a polymer derived from the heptamers of Figure 20 by bonding through the octahedrally disposed atoms in the methylene positions of the adamantane skeletal structure. Figure 22 illustrates a polymer formed from the adamantane star heptamer monomer units of Figure 20 in which pore sizes are increased by synthesizing a framework structure having a two-unit spacing. Figure 23 shows synthesis of the meso- and dl-hexamers from the adamantane trimer monoketone designated ' in Figure 9 as structure 9a. Figure 24 is a schematic top view of the dl-hexamer. Figure 25 shows a top view and a side view, designated 25a and 25b, respectively, of packed dl-hexamers of the type shown in Figure 24. Figure 26 shows conversion of the monochlorinated adamantane dimer 26a to the corresponding monoketone 26b. Figure 27 shows conversion of one of the adamantane dimer onoketones resulting from the synthesis shown in Figure 26 to a mixture of adamantane dimer diketones, examples of which include the structures 27a, 27b, 27c and 27d. Figure 28 shows the conversion of diketone 27b, shown in Figure 27, to the cyclic adamantane tetramer via ketone coupling. Figure 29 illustrates an alternative synthesis of sheet structures through the adamantane trimer monoketone, 29a. The monoketone 29a is coupled to form the meso-hexamer 29b, which is then converted to the sheet structure 29c at elevated temperature in the presence of a catalyst such as Pd or Pt. Figure 30 shows a section of an adamantane-based sheet structure derived from either of the syntheses shown in Figures 28 or 29. Figure 31 shows polymerization of an adamantane dimer diketone via McMurry coupling to form the helical adamantane homepolymer. Figure 32 illustrates a helical adamantane polymer in which adamantane is copolymerized with a second monomer unit, specifically 2,4-diketoadamantane, 2,6-diketoadamantane and 1,3-diaminobenzene and 1,4-diaminobenzene are copolymerized to produce a mixed helical polymer, a section of which is shown. Figure 33 shows a substituted and/or expanded adamantane skeletal structure. Figure 34 shows nonli iting examples of suitable subsituents for the skeleton-expanding X positions shown in Figure 33. Figure 35 shows an expanded adamantane skeleton in which the Y positions are replaced with adamantane. Figure 36 illustrates an expanded admantane skeleton in which a benzene ring is interposed between each of the bridgehead and methylene positions. Figure 37 illustrates one example of X and Y replacement in which acetylene is in the X position and adamantane is in the Y position. Figure 37 further shows a suitable synthesis from a triethynladamantane starting material. The triethynladamantane can be synthesized from triacetyladamantane. Figure 38 shows one technique by which the monomer illustrated in Figure 37 can be polymerized. Figures 39, 40 and 41 show nonlimiting examples of methylene Z position substitutions in an adamantane skeleton. Figure 42 illustrates the inclusion of spacing units G comprising substantially linear groups bonded to one or more moieties in the methylene Z positions. Figure 43 shows nonlimiting examples of suitable G substituents for linking adamantane skeletal structures as illustrated in Figure 42. Figure 44 shows the conversion of adamantane dimer, 44a, to the monochlorinated adamantane dimer, one example of which is illustrated as structure 44b. Figure 45 shows examples of adamantane dimer dichlorides synthesized in Example XXII. Figure 46 shows examples of adamantane dimer diketones derived from the conversion of adamantane dimer dichlorides, examples of which are shown in Figure 45. Referring to Figure 1, adamantane has four bridgehead carbon atoms which are designated B 1 , B 2 , B, 3, and B4.. Each of these four carbon atoms is bonded to three other carbons atoms as well as to a single hydrogen. These four carbons atoms will hereinafter be referred to by their common name: the bridgehead carbons. The bridgehead carbons are tetrahedrally disposed with respect to the center of the molecule. This tetrahedral geometry is common in organic chemistry with such elementary examples as the four hydrogens in methane as well as the four methyl groups in 2,2-dimethylpropane. Referring to Figure 2, the remaining six carbon atoms in adamanatane are each bonded to two (bridegehead) other carbon atoms and to two hydrogen atoms. These non-bridgehead carbons are designated M., M 2 , M_, M., M 5 , and M- and will hereinafter be referred to as the methylene carbons. These methylene carbons are octahedrally disposed with respect to the center of the molecule as shown in Figure 2. The Linear Adamantane Homopolymer The linear adamantane homopolymer finds utility in numerous applications including high temperature lubricants, heat transfer fluids and films. The rod-shaped linear adamantane homopolymer is formed via bonding through opposing methylene carbons and is characterized by a substantially square cross-section. This synthesis is described below and in Example XIV and includes the McMurry coupling of 2,6-diketones of adamantane to form the intermediate chain together with McMurry coupling of one adamantane monoketone to each end of the intermediate chain to terminate the polymer. McMurry coupling of ketones to form symmetrical olefins is taught in U.S. Patent 4,225,734 to McMurry. See also McMurray, "Improved Procedures for the Reductive Coupling of Carbonyls to Olefins and for the Reduction of Diols to Olefins," 896 J. Orσ. Chem. 41 (1976); McMurry et al. , "Titanium-Induced Reductive Coupling of Carbonyls to Olefins," 43 J. Pro. Chem. 3255 (1978) ; and McMurry, "Titanium-Induced Dicarbonyl-Coupling Reactions", 16 Ace. Chem. Res. 405 (1983) . Synthesis of the adamantane linear rod polymer 3c via McMurry coupling is shown in Figure 3, where n is at least 1 and preferably from 3 to 5000. The adamantane 3a monoketone and diketones 3b may be synthesized from the corresponding chlorinated adamantane as shown below in Example I with reference to the adamantane dimer. The adamantane rod polymer may also be synthesized via olefin metathesis of 2-methylene adamantane and 2,6-dimethylene adamantane in the approximate molar ratio of 2 mols 2,6-dimethylene adamantane:1 mol 2-methylene adamantane. For a general discussion of olefin metathesis, see Chapters 11 and 14 of K.J. Ivin, Olefin Metathesis. Academic Press, New York, 1983, as well as Chapter 4 of V. Dragutan, A.T. Balahan and M. Dimonie, < Olefin Metathesis and Ring Opening Polymerization of Cvcloolefins. John Wiley, New York, 1983. An alternative synthesis technique for the adamantane linear rod polymer is described below in Example XVII. The coupling synthesis reacts adamantane monoketones and 2,6-diketones in the presence of TiCl_, Na, and 1,4-dioxane to derive the adamantane linear rod polymer. Structures exemplifying the linear adamantane polymer containing terminal substituent groups are shown in Figure . , where X. through X g are substituents selected from those listed above and n is at least 1, preferably from 3 to 5,000 repeating units. The linear adamantane homopolymer may further include pendant substituent groups as described above. The terminal monomer groups, i.e. X. through X g , above, may contain active terminal substituents such as polar groups. The adamantane homopolymer with an added terminal polar group such as carboxylic acid is useful as a barrier film, particularly as a barrier film between a polar liquid, e.g. water, and a nonpolar liquid, e.g. petroleum oil. Such polymers may be suitably synthesized via McMurry coupling of the corresponding ketones, as well as by olefin metathesis. Alternatively, the polymers may be synthesized from the corresponding ketones in the presence of TiCl_, Na, and 1,4-dioxane as described above. The structural formulae designated as 5a, 5b, 5c and 5d in Figure 5 exemplify such polymers, wherein Ad has the skeletal structure of adamantane and n is at least 3, and preferably is from 5 to 7, and wherein R. and R 2 comprise hydrogen or nonpolar (hydrophobic) constituent groups having from 1 to about 20 carbon atoms, and wherein R. and R. comprise constituent groups having from 1 to about 20 carbon atoms, with at least one of said R- and R. being polar. The four structures shown above indicate that the terminal substituent groups can be attached either to methylene or bridgehead positions. Nonlimiting examples of suitable nonpolar substituents R. and R 2 include normal and branched alkanes, alkene and alkynes, cycloakanes, cycloalkenes and cycloalkynes, as well as aromatics. Nonlimiting examples of suitable polar (hydrophilic) substituents R 3 and R 4 include ionizable species such as carboxylates, amines, quaternary ammonium salts, sulfonates and phosphates. One example of such a polymer is shown in Figure 6. The Zig-Zag Polymer The zig-zag adamantane homopolymer is formed via bonding through the 2,4-methylene carbons of the adamantane skeleton. Suitable syntheses include the McMurry coupling of 2,4-diketones of adamantane to form the intermediate chain together with McMurry coupling of one adamantane monoketone to each end of the intermediate chain to terminate the polymer. Synthesis of the intermediate chain via McMurry coupling is shown in Figure 7 with the 2,4-diketone designated as 7a and a portion of the resulting zig-zag structure designated as 7b. An alternate synthesis of the zig-zag polymer is set forth below in Example XXI. The zig-zag polymer may also be synthesized via olefin metathesis of 2,4-dimethyleneadamantane as described above. The general structure of the zig-zag adamantane homopolymer is shown in Figure 7 and is designated as 7c, wherein X. and X 2 have the skeletal structure of adamantane, and n is at least 1, preferably 3 to 5,000, more preferably 3 to 500. The zig-zag polymer may further comprise pendant, terminal and/or connecting substituent groups, illustrative examples of which are listed above. Potential uses for the zig-zag adamantane homopolymer include high temperature lubricants, heat transfer fluids, and films. The potential uses multiply with the addition of pendant, terminal and/or connecting substituent groups. Synthesis of Ketone Intermediate Units The sheet and framework adamantane homopolymers are most preferably synthesized via ketone dimer, trimer and tetramer intermediates. Example I Synthesis of the Ketone Dimer The mono-chlorinated adamantane dimer was first prepared by the known method of contacting the dimer with N-chlorosuccinimide; see 47 ____ Orσ. Cftem. 2005 (1982) . The adamantane dimer was purchased commercially, but may be synthesized as shown in 38 Journal of Organic Chemistry 3061 (1973). The synthesis then proceeds as schematically shown in Figure 8 by contacting the monochlorinated dimer 8a with base, for example KHCO. or NaHCO., in the presence of dimethylsulfoxide (DMSO) to produce the monoketone adamantane dimer intermediate 8b. Repetition of the process produces the four diketones designated as 8c, 8d, 8e and 8f. Further, certain of the resulting structures interconvert in the presence of acid, for example H 2 S0 4 . Specifically, structures 8c and 8d interconvert with structures 8f and 8e as indicated in Figure 8. Note further that the chlorination of the monochlorinated adamantane dimer designated as 8a yields a complex mixture of products, which mixture contains substantial amounts of compounds other than chloroketones. Example II Synthesis of the Ketone Trimer The linear adamantane trimer is prepared as described above via McMurry synthesis. The linear trimer is then converted to the linear monoketone trimer isomers as shown in Figure 9, by chlorinating the linear trimer 9a to monochlorinated linear adamantane trimers, examples of which include the structures 9b and 9c. The mixture of monochlorinated linear adamantane trimers is then reacted as shown at elevated temperature in the presence of DMSO and KHC0 3 to yield a mixture of linear adamantane trimer monoketones, two examples of which are designated 9d and 9e. Example III Synthesis of the Tetramer Diketone 8d of Example I, above, is converted to the cyclic adamantane tetramer in the presence of McMurry reagent as shown in Figure 10. Alternatively, this diketone dimer may be converted to the cyclic adamantane tetramer in the presence of TiCl 3 /Na/ 1,4-dioxane employing the synthesis set forth below in Example XV. The cyclic adamantane tetramer exhibits the sheet structure and is useful as an intermediate building block for framework structures. Example IV Synthesis of the Ketone Tetramer The cyclic adamantane tetramer of Example III is converted to the tetraketone by the two-step synthesis technique shown in Figure 11. The Framework Structure The framework structure formed by polymerizing monomer units through octahedrally disposed nonmetallic atoms of the monomers finds utility as a molecular sieve. The pore openings of the molecular sieve may be adjusted for particular applications by inserting substituent groups between the atoms occupying the bridgehead and methylene positions as described below. The framework structure formed by 8 adamantane units is shown in Figure 12. The framework structure is preferably synthesized by first assembling intermediate units such as tetramers and then linking these intermediate units to form the three-dimensional framework structure. Example V Synthesis of the Framework Structure Referring to Figure 13, the monochlorinated adamantane dimer 13a was prepared by reaction with N-chlorosuccinimide as illustrated in Example I. This monochlorinated adamantane dimer was then converted first to the corresponding monoketone 13b, which was then converted to the diketones by the conversion shown in Figure 13. Examples of the adamantane dimer diketones produced are designated 13c, 13d, 13e and 13f. Diketone 13d is isolated and converted to the cyclic tetramer as shown in Figure 14. The cyclic adamantane tetramer is then converted to the tetraketone via a two-step process. The tetraketone is then polymerized by McMurry or TiCl_/Na/l,4-dioxane synthesis as shown in Figure 15. Example VI Through assemblage of extended sheets, tetramers or octamers, a three-dimensionally extended crystalline network is made. It can be recognized by its characteristic X-ray pattern. The calculated X-ray diffraction pattern for this adamantane framework polymer is shown in Table I. Ul, These diffraction data are collected with a diffraction system, using copper K-alpha radiation. The diffraction data are recorded by step-scanning at 0.02 degrees of two-theta, where theta is the Bragg angle. The interplanar spacings, d's, are calculated in Angstrom units (A) , and the relative intensities of the lines, I/I 0 , where I is one-hundredth of the intensity of the strongest line, above background, are derived with the use of a profile fitting rountine (or second derivative algorithm) . The intensities are uncorrected for Lorentz and polarization effects. The relative intensities are given in terms of the symbols vs = very strong (75-100), s = strong (50-74), m ■ medium (25-49) and w = weak (0-24). It should be understood that diffraction data listed as single lines may consist of multiple overlapping lines which under certain conditions, such as differences in crystallite sizes or very high experimental resolution or crystallographic changes, may appear as resolved or partially resolved lines. Typically, crystallographic changes can include minor changes in unit cell parameters and/or a change in crystal symmetry, without a change in topology of the structure. The adamantane homopolymer framework structure comprises at least 4 repeating units selected from the group consisting of the four structures illustrated in Figure 16, and designated as 16a, 16b, 16c and 16d. Framework structures may also be synthesized which bond through the octahedrally disposed 2,4,6,8,9, and 10-methylene positions. Such framework structures comprise at least 4 repeating units having the structure of the four structures shown in Figure 17, and designated as 17a, 17b, 17c and 17d. Example VII Synthesis of Additional Framework Polymers-The Pentamer Additional framework structures may be synthesized via stepwise addition to the ketone trimer as illustrated below. To synthesize the adamantane pentamer, the trimer monoketone, structure 9d shown in Figure 9 and referred to in Example II, is first converted as shown in Figure 18 to the diketone, 18a. The diketone trimer is then reacted with adamantanone at a molar ratio of about 2 moles adamantanone per mole of diketone trimer in the presence of McMurry Reagent (TiCl 3 , Li, dimethoxyethane solvent) or TiCl., Na, 1,4-dioxane solvent to form a mixture of polymers including the pentamer star polymer, 18b. Example VIII Synthesis of Addition Framework Polymers-The Heptamer The pentamer of Example VII is converted to the heptamer through the pentamer diketone as shown in Figure 19. Referring now to Figure 19, the adamantane pentamer star polymer is designated as 19a. NCS represents N-chlorosuccinimide; RCO.H represents a peroxy acid, for example, perbenzoic, metachloroperbenzoic, or peracetic acid; PCC represents pyridium chlorochrornate and DMSO is dimethyl sulfoxide. The adamantane pentamer star polymer 19a is converted as shown to the adamantane pentamer star polymer diketone, 19b. The adamantane pentamer star polymer diketone is then polymerized in the presence of (TiCl 3 , Na, dimethoxyethylene) or (TiCl 3 , Na, 1,4-dioxane) and about 2 moles of adamantanone per mole of the pentamer diketone to form the adamantane heptamer star polymer shown as 19c. The adamantane heptamers may then be further polymerized to form framework structures. Suitable synthesis techniques include McMurry synthesis through the ketones as illustrated above. For ease of description, the adamantane heptamer described above in Example VIII can be envisioned as a three-dimensional Maltese cross in which each adamantane skeletal unit can be represented as a cube as shown in Figure 20. This pictorial description is not rigorously geometrically correct, as the methylene carbons would be located at the center of each of the faces of the cubes. However, this remains an excellent description of polymer assemblage from monomers having the skeletal structure of adamantane. Polymerizing these heptamers by bonding through the octahderally disposed atoms in the methylene position of the adamantane skeletal structure produces a framework structure with regularly spaced pores as shown in Figure 21. Pore sizes may be increased by synthesizing a framework structure having a unit spacing of 2 or more. A section of such a framework structure having 2 unit spacing is shown in Figure 22. Example IX Synthesis of the meso- and dl-Hexamers Monomer units having the skeletal structure of adamantane may also be assembled to form a dl-hexamer. In Example II, above, the monoketone trimer designated as structure 9a in Figure 9 may be further polymerized to the meso- or the dl-hexamer. Synthesis of the meso- and dl-hexamers is diagra atically illustrated in Figure 23, with the dl-isomer designated as 23a and the meso-isomer designated as 23b. The meso- and dl-Hexamers The meso-hexamer is a useful intermediate for making small sheet structures comprising one or two cyclic tetramer units. The dl-isomer, on the other hand, exhibits unique stacking characteristics. To visualize such stacking arrangements, the dl-hexamer may be schematically represented by the top view of Figure 24 in which each of the two rectangles represents an adamantane trimer unit. From the representation of Figure 24 the packing characteristics of the dl-hexamer may be shown as illustrated in Figure 25, with the top view designated as 25a and a side view designated as 25b. Uses for the dl-hexamer and its derivatives include films and lubricant additives. The Sheet Structure The sheet structure formed by polymerizing monomer units through octahedrally disposed nonmetallic atoms of the monomers finds utility, among other applications, as a film or coating material. Synthesis of the sheet structure preferably proceeds through intermediates, nonlimiting examples of which include dimers, tetramers, and meso-hexamers. The sheet structure synthesis through the adamantane dimer is initiated by converting the adamantane dimer to the monoketone of the adamantane dimer. The intermediate is then converted to the diketone and then polymerized via ketone coupling, for example, in the presence of (TiCl 3 , Na, dimethoxyethane) or (TiCl., Na, 1,4-dioxane) . Example X Synthesis of the Sheet Structure The monochlorinated adamantane dimer shown below was prepared as shown above in Example I. Figure 26 shows conversion of the monochlorinated adamantane dimer 26a to the monoketone 26b. The monoketone 26b is then converted to a mixture of diketone isomers as shown in Figure 27 and designated as 27a, 27b, 27c and 27d. Diketone 27b, shown in Figure 27, is then converted to the cyclic adamantane tetramer via ketone coupling as shown in Figure 28. To convert tetramer to larger sheet, sequential synthesis proceeds through the conversion to the di- or tetra-ketone followed by coupling, for example, in the presence of TiCl-, Li, dimethoxyethane (McMurry coupling) or TiCl 3 , Na, 1,4-dioxane as illustrated in Figure 28. Example XI Alternative Synthesis of the Sheet Structures The sheet structure is also synthesized through the mono-ketone, 29a, of the adamantane trimer as schematically illustrated in Figure 29. The mono-ketone 29a is coupled to form the meso-hexamer, designated as 29b. The meso-hexamer, 29b, is then converted to the sheet structure 29c at elevated temperature in the presence of Pd or Pt. A section of an adamantane-based sheet structure derived from this synthesis is schematically illustrated in Figure 30. The Helical Structure The helical structure, forming a rigid or semi-rigid coil spring shape, is useful as an elastomer. The helical polymer may be synthesized via McMurry coupling of the 2,4-diketone as well as through olefin metathesis of the 2,4-dimethyleneadamantane. However, the most preferred synthesis technique for the helical adamantane homopolymer is through diketone 8c, shown in Figure 8 and described above in Example I. Example XII Synthesis of the Helical Homopolymer The diketone dimer shown in Figure 31 is polymerized via McMurry coupling to form the helical adamantane homopolymer. The monomer unit having octahedrally disposed atoms may also be copolymerized with a second monomer unit, as is exemplified by the combination of 2,4- and 2,6-diketoadamantane with 1,3- and 1,4-diaminobenzene. A section of the resulting polymer is schematically illustrated in Figure 32. The helical polymer typically comprises from 5 to 5,000 repeating units bonded through octahedrally disposed nonmetallic atoms of the repeating units. The Expanded Adamantane Skeleton The skeletal structure of the monomer units themselves may be modified and expanded. The positions occupied by the bridgehead and methylene carbons as illustrated above with reference to adamantane may be occupied not only by atoms other than carbon but also by substituent groups which can be substituted into the skeletal structure through tetrahedrally located bonds of the substituent groups. Further, the skeletal structure may be expanded by inserting rigid semi-rigid linear groups of uniform size between each of the atoms or substituent groups occupying the bridgehead ethylene positions. In addition to the contributing properties inherent to the functionality of the rigid linear groups, these inserted groups expand the monomer unit while preserving its octahedral geometry. The expanded and/or substituted adamantane skeleton may then be used in its monomeric form as a thermally stable fluid or may be polymerized as described above through its octahedrally disposed nonmetallic atoms. The substituted and/or expanded adamantane skeleton is shown in Figure 33. Nonlimiting examples of suitable substituents for the skeleton-expanding X positions include approximately linear substituents such as the examples shown in Figure 34, where A, B, D AND E are substituents including C 8 -C 2 _ aromatics, C 1 -C 20 alkyl groups, 2 -C 2Q alkenyl groups, C 2 -C 20 alkynyl groups, halogens, amines, diazo compounds, azide compounds, hydrazines, mercaptans, sulfides, polysulfides, ethers, alcohols, esters, organometallic compounds, amides, anhydrides, carbamates, ureas, imides, sulfonic acids, sulfinic acids, sulfinates, carboxylic acids, nitriles, isonitriles, heterocycles, metals, phosphates, phosphites, borates, ketones, aldehydes, aryl compounds, acid halides, hydrogen, and the reaction products thereof; and n is at least 1. Nonlimiting examples of suitable substituents for the bridgehead Y positions include tetrahedral substituents such as the elements of Group IVB of the Periodic Table of the Elements. Molecules exhibiting tetrahedral bonding arrangements are also useful as Y position substituents. For example, the tetrahedral disposition of the bridgehead positions in an adamantane-like skeleton as shown in Figure 33 may be used to substitute such adamantane-like skeletal structures into the bridgehead and methylene positions of a larger adamantane-like structure. These structures may then be used alone or as monomers to polymerize through the octahedrally disposed methylene positions as described above. An example of Y replacement with adamantane is shown in Figure 35. Nonlimiting examples of suitable substituents for the methylene Z positions include tetrahedral substituents as described with reference to the bridgehead positions. The following nonlimiting examples of X, Y, and Z replacements are provided as illustrations of such substitutions. X Replacement Interposing a benzene ring between each of the bridgehead and methylene positions in the ketone-substituted adamantane skeleton yields the structure shown in Figure 36. Example XIII X and Y Replacement A nonlimiting example of X and Y replacement is shown by substitution of acetylene in the X position o and adamantane in the Y position of an adamantane skeleton. One method by which this substitution may be achieved is the synthesis schematically shown in Figure ' 37. The monomer may then be polymerized through McMurry coupling as shown in Figure 38. 5 Z Replacement The structures illustrated in Figures 39, 40 and 41 show nonlimiting examples of methylene Z position substitutions in an adamantane skeleton. It is to be noted that the monomer of structure shown in Figure 41 0 may be polymerized through single bonds linking octahedrally disposed benzene rings. The substituted and/or expanded adamantane skeleton may be polymerized by linking two or more units as shown in Figures 39, 40 and 41 through the octahedrally disposed moieties. The adamantane skeleton units may bond directly to another monomer unit or may be spaced apart from the adjacent monomer units by the inclusion of substantially linear groups bonded to one or more moieties in the methylene Z positions. These spacing units are schematically illustrated as G in Figure 42. X, Y, and Z have been deleted from Figure 42 for clarity. Non-limiting examples of suitable G substituents are shown in Figure 43, and are designated as 43a-43h, where n is at least 1, where Ad represents a unit having the skeletal structure of adamantane and where A, B, D and E are substituents including C 8 -C 2Q aromatics; linear, branched and cyclic C.-C 20 alkyl groups; linear, branched and cyclic C 2 -C 2 _ alkenyl groups; linear, branched and cyclic 2 -C 2 _ alkynyl groups; halogen; amines; diazo compounds; azide compounds; hydrazines; mercaptans; sulfides; polysulfides; ethers; alcohols; esters; organometallic compounds; amides; anhydrides; carba ates; ureas; imides; sulfonic acids; sulfinic acids; sulfinates; carboxylic acids; nitriles; isonitriles; heterocycles; metals; phosphates; phosphites; borates; ketones; aldehydes; aryl compounds; acid halides; hydrogen, and the reaction products thereof. Example XIV Synthesis of the Linear Polymer From Adamantane 2.6-dione In an argon glove bag, titanium trichloride (9.26 grams, 60 mmole) was weighed into an oven-dried three necked round-bottom flask equipped with a reflux condenser, an argon bubbler, and a magnetic stirrer. The flask was cooled with an ice-water bath, and 1,2-dimethyoxyethane (70 ml, distilled from LiAlH 4 and triphenylmethane) was added with stirring. A purple suspension resulted, and the cooling bath was removed. Lithium wire (3 mm, 1.249 gram, 180 mmole) was etched in methanol until it was shiny, then quickly cut into 2 mm segments, and added to the flask. The mixture was refluxed (oil bath) with stirring under argon for 5 hours, giving a black suspension. The oil bath was removed, and adamantane-2,6-dione (1.217 gram, 7.41 mmole) was added in one portion through the top of the condenser. This mixture was refluxed for 29 hours. The flask was then cooled, and the contents, including the unreacted lithium, were very carefully transferred into ice-cold 2N hydrochloric acid. The solid was collected on a sintered-glass funnel. The solid was then stirred in 2N hydrochloric acid overnight, filtered, washed with saturated aqueous Na 2 EDTA, and washed with water. Drying gave the linear polymer as a gray solid (1.068 gram). The product was stable to 515*C. The product slowly decomposed above this temperature. At 550*C, decomposition occurred more rapidly, but no melting was observed. The density, determined by floatation in carbon tetrachloride-ethyl acetate, was 1.25 g/cm . The infrared spectrum (KBr) Showed bands at 3439, 2951, 2909, 2844, 1446, 1350, 1323, 1306, 1203, 1084, 1037, 976, and 966 cm "1 . The solid-state CP-MAS CMR spectrum showed well-defined narrow signals at 133.4 (C=C) , 74.0 (CHOH, end group), 41.7 (CH 2 ) , and 32.5 (CH) . Integration of the end group versus the other signals gave an average chain length of about 33 units. FAB mass spectrometry showed the highest fragment ion at m/z = 2390 (>18 units) . The linear polymer was not soluble in common organic solvents. Example XV S y nthesis of the Zig-Zag Polymer from Adamantane 2.4-dion Titanium trichloride (1.85 g, 12.0 mmol) was weighed into an oven-dried 50-ml three-necked round-bottom flask in an argon glove-bag. The flask was fitted with a reflux condenser having an Ar bubbler and was cooled with an ice-water bath. After 20 ml of dry 1,4-dioxane was added to the flask with magnetic stirring and cooling, the cooling bath was removed. Sodium (0.828 g, 36.0 mmol) was added into the flask, and the mixture was refluxed for 0.75 hr with stirring to give a black suspension. After adding 0.657 g of (4.0 mmol) adamantane- 2,4-dione from the top of the condenser in one portion, reflux was continued for 17.5 hours. The flask was cooled, and its contents were transferred to 160-ml 0.4 N ice-cold aqueous HCl. Collection of the white solid floating on top of the aqueous layer gave 36 mg product (Fraction 1) . The rest of the aqueous mixture was filtered on a sintered-glass funnel to collect 0.533 g of a grey solid (Fraction 2) after drying. The filtrate was extracted with 150 ml of hexanes; removal of the hexanes from the extract gave 62 mg of a solid (Fraction 3) . Fractions 1 and 3 contained mostly adamantylidene-adamantane, plus compounds judged to be longer oligomers by inspection of their NMR spectra. Fraction 2 was mostly polymer, and was characterized by its solid-state CP-MAS 13 C-NMR: 133.3, 75.1 (small), 39.9, 37.1, 32.5, 29.1 (total olefinic/aliphatic integration: 1.0:6). FAB-MS: the highest m/e at 2596 (20 adamantane monomer units) . All three fractions were combined and their flash chromatography on 40 g of silica gel gave the following fractions: Eluent and TLC R- value Fraction amount fml) (solvent) Residue A hexane (0-50) 0.7 & 0.1 (CC1 4 ) 164 mg semi-so B hexanes (50-250) 0.1 (CC1 4 ) 11 mg semi-so C CC1 4 (0-150) 0.35 * 0.9 (CC1 4 ) 80 mg solid D CC1 4 (150-250) 0.35 (CC1 4 ) 20 mg solid E CHC1 3 (0-100) 0.1 « 0.6 (CHC1-) 125 mg solid F CHC1 3 (100-450) * 0.1 (CHC1 3 ) 108 mg solid Fraction A: ~ E- and 13 C{ 1 H)-NMR (200 MHz, CDC1 3 ) : adamantylidene-adamantane plus unknowns with some sharp and other broad lines in both spectra. It was composed of hydrocarbons because no alcohol carbon signals were observed in the C-NMR. Sublimation of Fraction A at 3mm-Hg/100'C gave 46 mg of oily crystals (Fraction A-l) , which were predominantly the adamantane dimer by ,H-NMR spectrum. The residue was a waxy solid weighing 102 mg (Fraction A-2) . FAB MX (Xe, NOBA) of Fraction A-2 shows the highest m/e signal at 3058, corresponding to a chain length of 23 or more. Fraction B: H-NMR (CDC1 3 ) : unknown(s) with very broad lines. FAB MX shows the highest me/ signal at 3085, corresponding to a chain length of 23. Fraction C; ^- MR and 13 C{ 1 H)NMR (CDC1 3 ) : polymeric alcohol(s) with broad lines in both spectra. FAB-MS: the highest m/e signal at 3099, corresponding to a chain length of 23. Fraction D: X H-NMR (CDC1-): very broad lines indicating polymeric material. FAB-MS: the highest m/e signal at 3093, corresponding to a chain length of 23. Fraction E: Part of the sample gave sharp lines in 13 C-NMR with significant signals at 218.42, 135.88, 130.97, « 96, 74.84, 46.96, 39.25, 36.31, 32.42 and 27.46 ppm, indicating the presence of both ketone and alcohol functional groups. The rest of the sample shows broad signals in olefinic, alcoholic, and aliphatic regions in 13C spectrum. The 1H-NMR spectrum was not informative. FAB-MS: the highest m/e signal at 3084, corresponding to a chain length of 23 or more. Fraction F: Part of the sample gave sharp lines in 13 C{lH)-NMR wi.th si.gni.fi.cant signals at 132.28, 96.12, 74.50, 67.07, 46.92, 40.90, 37.60, 36.52, 34.54, 31.02, 27.54 and 27.08, indicating the presence of alcohol. The rest of the sample shows broad signals in olefinic, alcoholic, and aliphatic regions. The H-NMR spectrum was again not very informative. FAB-MS: the highest m/e signal at 3098, corresponding to a chain length of 23. Example XVI A First Synthesis of the Linear Olioomer In a procedure similar to that used for preparation of the linear polymer of adamantane-2,6-dione, titanium chloride (3.857 grams, 25 mmole), 35 ml (dry) of 1,4-dioxane, and lithium wire (1.552 grams, 67.5 mmole, methanol-etched) were reluxed for 1.75 hours. Adamantane-2,6-dione (0.082 grams, 0.5 mmole) and adamantanone (3.004 grams, 20 mmole) were added and the mixture was refluxed for 19 hours. After cooling, hexanes (35 ml) were added, and the mixture was filtered through a Florisil pad. After washing with hexanes, removal of the solvent gave the linear oligomers as a colorless solid (2.702 grams). Careful flash chromatography of the crude product on silica gel using hexanes eluted first a mixture of dimer and linear trimer and then a fraction (11 mg) containing linear trimer and tetramer. Washing the latter fraction with chloroform gave the linear tetramer (4 mg, m.p.>360'C). The linear tetramer showed the expected parent ion z/e = 532.4037 (calculated 532.4069) in the high-resolution mass spectrum. The low-resolution mass spectrum (70 eV) showed peaks at m/Z Of 534.47, 533.47, 532.46 (base peak), 469, 266.75, [(M=l)/2e], 266.24 (M/2e) . The 500 MHz HMR spectrum (CHC1-) showed broad, overlapping singlets (12H) at 3.01, 2.98, and 2.94 ppm and peaks at 1.94 (broad singlet, 4H) , 1.86 (doublet, 11.9Hz, 8H) , 1.84 (broad singlet, 4H) , 1.79 (broad, singlet, 16H) , and 1.70 (doublet, 11.9 Hz, 8H) ppm. Sublimation of the dimer-trimer fraction at 5 mmHg and 105*C gave pure dimer (2.461grams) , identified by GC/MS comparison and left linear trimer (0.136 grams). The linear trimer begins to sublime above 300'C and melts at 347-351'C. The linear trimer showed the expected parent ion at m/z = 400.3134 (calculated: 400.3130) in the high resolution mass spectrum. The low-resolution mass spectrum showed peaks at m/e = 402, 401, 400 (base peak), 279, 265, 213, 212, 211, 200, 155, 145, 143, 135, and 129. The infrared spectrum (KBr) showed peaks at 2946, 2907, 2845, 1447, 1204, 1087, 1060, 1035, 981, 969, 945, and 692 cm "1 . The 500 MHz HMR spectrum (CHC1 3 ) showed peaks at 2.94 (broad singlet, 8H) , 1.94 (broad singlet, 4H) , 1.86 (doublet, ιι.7 Hz), and 1.83 ppm total 12H) , 1.77 (broad singlet, 8H) , and 1.70 (doublet, 11.7 Hz, 8H) . The 13 C{ 1 H}-NMR/DEPT spectrum (CDC1 3 ) showed peaks at 133.45 (olefinic carbon), 132.80 (olefinic carbon), 41.55 (CH 2 ), 39.66 (CH 2 ) , 37.88 (CH 2 ) , 32.14 (CH) , 31.96 (CH) , and 28.60 (CH) . Example XVII A Second Synthesis of the Linear Olioomer In a very similar procedure as described above in Example XV for the dimerization of adamantanone, titanium trichloride (3.857 g, 25.0 mmol) was refluxed with 1.552 g (67.5 mmol) sodium in 35 ml dry 1,4-dioxane for 1.75 hours. A mixture of 0.082 g (0.50 mmol) adamantane-2,6-dione and 3.004 g (20.0 mmol) adamantanone was added in one portion from the top of the condenser. The mixture was refluxed for another 19 hrs. Hexanes (35 ml) were added to the flask after cooling, and the black mixture was filtered through a pad of Florisil. The Florisil was washed with hexanes. Removal of the solvents from the filtrate gave 2.702 g colorless solid. Careful flash chromatography of the crude product on 100 g of silica gel with hexanes eluted a mixture of the adamantane dimer and the linear trimer first, and later a fraction of 11 mg of a solid, which was a mixture of the linear adamantane trimer and the linear adamantane tetramer. Washing the latter with chloroform gave 4 mg of a solid (0.0075 mmol), which was shown to be the linear adamantane tetramer: M.p.>360'C. ^Η-NMR (CDC1 3 ,500 MH 2 ) : 3.01, 2.98, 2.94 (overlapping br s, 12H total), 1.94 (br s, 4H) , 1.86 (d, 11.9 Hz, 8H) , 1.84 (br s, 4H) , 1.79 (br s, 16H) , 1.70 (d, 11.9 HZ, 8H) . FT-IR (KBr, cm "1 ) 2951 (m) , 2907(s), 2845(S), 1446(m), 1350, 1328, 1308, 1203 (all W) , 1086 (m) , 1061, 1036, 981, 969 (all w) . LRMS (70 ev) : m/e 534.47, 533.47, 532.46 (base peak), 469, 266.75 [(M+l)/2e], 266.24 [M/2e] . HPMS calculated for C 4Q H 52 : 532.4069, found: 532.4037. Sublimation of the dimer/trimer mixture at 5 mm-Hg/lOS'C gave 2.461 g (9.169 mmol) dimer shown to be pure by GC/MS and leaving 0.136 g linear adamantane trimer (0.339 mmol) behind. The linear adamantane trimer was characterized by: m.p. 347-51'C (sublimed partially >300*C). X H-NMR (CDC1 3 , 500 MHz): 2.94 (br s, 8H) , 1.94 (br s, 4H) , 1.86 (d, 11.65 Hz), and 1.83 (br s) these two signals represent 12 protons, 1.77 (br s, 8H) , 1.70 (br d, 11.65 Hz, 8H). 13 C{ 1 H} and DEPT (CDCL 3 , 90MHz): 133.45, 132,80 (both s, C«C) , 41.55 (CH 2 ) , 39.66 (CH 2 ) , 37.38 (CH 2 ), 32.14 (CH) , 31.96 (CH) , 28.60 (CH) . HUMS calculated for C 3Q H 40 : 400.3130, found 400.3134. LRMS 70 eV (m/e): 402, 401, 400 (base peak), 279, 265, 213, 212, 211, 200, 155, 145, 143, 135, 129. FT-IR (KBr, cm "1 ): 294 ' 6(w), 2907(s), 2845(m), 1447, 1204, 1087, 1060, 1035, 981, 969, 945, 692 (all w) . UV in hexanes: a tail absorption up to 235 nm. Example XVIII Synthesis of the Nonlinear Trimer The experimental procedure was identical to that used to prepare the linear dimer and tetramer except that the adamantane-2,4-dione (0.082 gram, 0.50 mmole) was used in place of adamantane-2,6-dione and the final reflux was for 15 hours. The crude product was a white solid (2.694 grams). Sublimation (5 mmHg, 105'C) gave adamantylidieneadamantone (2.495 grams) and left the non-linear trimer (0.061 grams). The non-linear trimer (m.p. 258-260*C) showed the expected HR-MS parent ion at m/z - 400.3135 (calculated: 400.3130). The low resolution mass spectrum (70 eV) showed peaks at z/e = 402, 401, 400 (base peak), 359, 321, 265, 251, 212, 211, 200, 167, 155, 145, 144, 143, 142, 141, 135, and 129. The infrared spectrum (KBr) showed peaks at 3010, 2949, 2906, 2845, 1447, 1350, 1339, 1327, 1260, 1215, 1193, 1181, 1101, 1085, 1072, 1063, 1042, 1008, 996, 971, 959, 943, 929, 809, 801, 790, 762, 706, 683, and 557 cm . The ultraviolet spectrum in hexanes showed maχ (e) at 227 (2850), 224 (5130), and 221 nm (7600). The 500 Mhz HMR spectrum (CDC1 3 ) showed peaks at 3.90 (broad singlet, 1H) , 2.93 (broad singlet, 4H) , 2.86 (broad singlet, 2H) , and 1.92-1.56 (multiplet, ≤a. 33H) ppm. The 13 C{ 1 H}-NMR/DEPT spectrum (CDC1 3 ) showed peaks at 133.65 (olefinic carbon), 132.47 (olefinic carbon), 41.97 (CH 2 ) , 39.74 (CH 2 ) , 39.40 (CH 2 ) , 39.22 (CH 2 ), 39.20 (CH 2 ), 37.36 (CH 2 ) , 39.95 (CH) , 28.81 (CH) , 28.60 (CH) , and 28.52 (CH) . ppm. Example XIX Synthesis of the Expanded Adamantane Skeleton Synthesis of the monomer is carried out by adding 3 parts of phosgene or bis-imidazole carbonyl to 2 parts of 3-ethynyl-l,4-pentadiyne in a suitable solvent such as tetrahydrofuran. The polymer formed is removed and the two isomeric products are separated via chromatography on silica gel and is recognized by its characteristic NMR spectrum. Example XX Synthesis of the Zig-Zag Polymer from Adamantane- 2.4-dio Inside an argon glove-bag, TiCl 3 (1.85 g, 12.0 mmol) in an oven-dried flask equipped with a reflux condenser and an argon bubbler was cooled with an ice-water bath and 1,4-dioxane (20 mL, distilled from sodium) was added with magnetic stirring and cooling. A purple suspension resulted, and the cooling bath was removed. Sodium (0.828 g, 36 mmol) was added, and the mixture was refluxed under argon for three quarters of an hour giving a black suspension. The oil bath was removed and adamantane-2,4-dione (0.657 g. 4,0 mmol) was added from the top of the condenser in one portion. The mixture was then refluxed for 17.5 hours. After cooling, the contents of the flask were transferred to ice-cold HCl (160 mL of 0.4 N) . Collection of the white solid floating on the aqueous layer gave 36 mg of solid (Fraction 1) ; filtration with a sintered-glass funnel gave 0.533 mg of a grey solid (Fraction 2) after drying; extraction of the filtrate with hexanes (150 mL) gave 62 mg of another solid (Fraction 3). NMR analysis of Fractions 1 and 3 showed that they were primarily adamantylidene-adamantane and oligomers. Fraction 2 was very soluble in CC1 4 , CHC1 3 , CH 2 C1 2 and hot dioxane and partially soluble in hexanes, ethyl acetate, and acetone. Solid-state CP-MAS 13 CMR showed peaks at 133.3, 75.1, 39.9, 37.1, 32.5 and 29.1 ppm, and FAB mass spectro etry showed the highest m/z at 2596 indicating a chain length of at least 20 units. All three fractions were combined and flash chromatographed on silica gel giving Fractions A-F. Fraction A consisted of adamantylidene-adamantane and an unknown by proton and carbon NMR analysis. Sublimation (3 mm-Hg at 100*C) gave adamantylidene-adamantane; the residue was a waxy solid (102 mg) . The FAB mass spectrum of this solid showed the highest m/z at 3058 indicating a chain length of at least 23 units. Fraction B showed very broad lines in the proton NMR, and the FAB mass spectrum showed the highest m/z at 3085 corresponding to a chain length of at least 23 units. Fraction C showed broad lines in the proton and carbon NMR spectra; in addition signals due to COH groups were visible. The FAB mass spectrum showed the highest m/z at 3099 indicating a chain of at least 23 units. Fraction D gave a proton NMR spectrum with very broad lines; the FAB mass spectrum showed the highest m/z at 3093 consistent with a chain of at least 23 units. Fraction E showed sharp signals in the carbon NMR specrum at 218.42, 135.88, 130.97, 96, 74.84, 46.96, 39.25, 36.31, 32.42 and 27.46 ppm indicating the presence of both alcohols and ketones; the rest of the spectrum shows broad signals in the olefinic, alcoholic and aliphatic regions. The FAB mass spectrum shows the highest m/z at 3084 consistent with a chain of at least 23 units. Fraction F showed sharp lines in the carbon NMR spectrum at 132.28, 96.12, 74.50, 67.07, 46.92, 40.90, 37.60, 36.52, 34.54, 31.02, 27.54 and 27.08 indicating the presence of COH; the rest of the spectrum showed broad signals in the olefinic, alcoholic and aliphatic regions. The FAB mass spectrum showed the highest m/z at 3098 consistent with a chain of at least 23 units. Example XXI Synthesis of Adamantane Dimer Dichlorides Adamantane dimer (5.369 g, 20.0 mmol) having the structure 44a shown in Figure 44, was dissolved in 150 ml dry CH 2 C1 2 and 5.742 g (43.0 mmol) powdered NCS added in one portion. The mixture was stirred at room temperature for 10 hours, transferred to a separatory funnel, and diluted with CH 2 C1 2 to 200 ml. It was washed with 5 x 100 ml water and 100 ml saturated brine, and dried with anhydrous Na 2 S0 4 . Removal of solvent gave 6.887 g white solid. The GC/MS of this mixture showed five peaks with total ion integration about 2:10:9:55:25. The first peak was the monochloride of the adamantane dimer, shown as 44b in Figure 44. The next two peaks belong to the structures designated as 45a and 45b in Figure 45. The last two peaks represented four dichlorides having structures schematically shown as 45c, 45d, 45e and 45f in Figure 45. A sample prepared similarly shows the following NMR spectra: ~ H NMR (CDC1-, 360 MHz): δ 4.25-4.09 (several br s, the major one at 2.21 ppm, 2H) , 3.03 (br s, 2H), 2.86 (br s, 2H) , 2.57-2.38 (m, 2H) , 2.35-2.31 (m, 2H) , 2.13 (br S, 2H) , 2.05-1.99 (m, 2H) , 1.92-1.83 (m, 4H) , 1.69-1.62 (m, 6H) , 1.51-1.45 (m, 2H) . 13 C{ 1 H) and DEPT (CDC1 3 , 90 MHz): δ 141.69, 141.01, 128.55, 127.23 (C=C for structures 45a and 45b), 134.70, 134.68 (C=C for structures 45c-45f) , 67.91, 67.82, 67.78, 67.70, 67.15, 64.31 (CHC1 for structures 46a-46f) . Example XXII Synthesis of Adamantane Dimer Diketones Ninety-five percent of the dichloride mixture obtained above in Example XXI (19.0 mmol) was treated with 5.707 g (57.0 mmol) KHCO- in 150 ml dry DMSO at 150*C for 5 days with magnetic stir under Ar, at the end of which the GC/MS of the reaction mixture showed very little chloroketone intermediates. The mixture was poured into ~ 400 g crushed ice, neutralized to pH β 7 with aqueous HCl and filtered to collect some yellow solid. Extracting the aqueous layer with 5 x 80 ml ether, washing the combined ether solution with 6 x 100 ml water and 100 ml saturated brine, drying the organic layer with anhydrous NaS0 4 , and removing the organic solvents gave 0.51 g of yellow solid. Both crops of crude product contained some hydroxyketones; therefore, they were combined, dissolved in 150 ml of dry CH 2 C1 2 , and 1.0 g powdered PCC (Aldrich) was added. The mixture was stirred at room temperature for 5 hours. Another 0.50 g PCC was added and stirring continued for 2 more hours. Usual work-up gave 5.44 g of brown solid. Filtering this through 15 g silica gel with EtOAc/hexanes gave 5.32 g yellow solid as crude product. Flash chromatography on 125 g silica gel eluting with a gradient of hexanes to 1:3 (v/v) EtOAc/hexanes gave 0.045 g of adamantane dimer diketones having the structure of 46e and 0.736 g of adamantane dimer diketones having the structure of 46d (13%) together with 3.34 g of other dione fractions containing structures 46a-g, all of which are shown in Figure 46. Total dione yield was 73%. A small amount of dione 46b can be purified by repeated recrystallization in 1:3 (v/v) EtOAc/ hexanes of one fraction obtained similarly during a small scale run. The NMR data for 46f was extracted from a mixture of 46f, 46e and 46b in about 47:40:13 ratio. Similarly, NMR data for 46b and 46c were extracted from two mixtures containing 46f, 46b, 46a and 46c in molar ratio of about 9:29:43:19 and 3:14:59:24. Structure 46a: ^Η NMR (CDC1-, 360 MHZ): <S3.56 (br S, 2H) , 3.06 (br s, 2H) , 2.59 (br s, 2H) , 2.20-1.75 (m, 18H) . 13 c{ 1 H) and DEPT (CDCl 3 , 90 MHz): δ 215.01 (OO) , 134.17 (OC) , 52.83 (CH), 46.25 (CH) , 41.91 (CH 2 ) , 38.84 (CH 2 ), 38.02 (CH 2 ) 37.83 (CH j ) , 31.08 (CH) , 27.59 (CH) . Structure 47b: ~ K NMR (CDC1 3 , 360 MHz):£ 3.56 (br s, 2H) , 3.06 (br s, 2H) , 2.63 (br s, 2H) , 2.16-2.05 (m, 10H) , 2.01-1.94 ( , 4H) , 1.87-1.82 (m, containing a d with J = 12.45 Hz, 2H) , 1.81-1.76 (m, containing a d with J = 12.45 Hz, 2H) . 13 C( 1 H) and DEPT (CDC1-, 90 MHZ): δ 215.38 (C=0) , 134.24 (OC) , 52.95 (CH) , 46.38 (CH) , 41.90 (CH 2 ), 38.88 (CH 2 ) , 38.30 (CH 2 ) , 37.70 (CH 2 ), 31.14 (CH) , 27.54 (CH) . Structure 46c: ~ H NMR (CDC1 3 , 360 MHz): δ 3.56 (br s, 2H) , 3.06 (br s, 2H) , 2.63 (br s, 2H) , 2.20-1.75 (m, 18H) . 13 C{ 1 H} and DEPT (CDC1 3 , 90 MHz): <5 215.15 (OO) , 134.20 (OC) , 52.04 (CH) , 46.29 (CH) , 41.59 (CH 2 ), 38.84 (CH 2 ) , 38.19 (CH 2 ), 38.02 (CH 2 ), 32.09 (CH) , 27.51 (CH) . Structure 46d: m.p. 200-201'C. ^Η NMR (CDC1 3 , 360 MHz): 63.57 (br s, 2H) , 3.06 (br s, 2H) , 2.59 (br s, 2H) , 2.16-1.88 (m, 14H) , 1.90 (br d, J ■ 12.46 Hz, 2H) , 1.75 (br d, J - 12.62 Hz, 2H) . 13 C{ 1 H) and DEPT (CDC1.., 90 MHZ): (5214.26 (OO) , 134.03 (OC) , 51.84 (CH) , 46.20 (CH), 42.38 (CH 2 ), 38.99 (CH. ) , 38.36 (CH j ) , 37.62 (CH 2 ), 32.05 (CH) , 27.73 (CH) . FT-IR (KBr, cm "1 ) 2922, 2855, 1713, 1687 (all s) , 1639 (m) , 1440 (m) , 1345, 1312, 1277 1232, 1219, 1165, 1112, 1105, 1085 (all W) , 1066 (m) , 1043, 1029, 1020, 1003, 995, 973, 965, 935, 927, 908, 897, 881, 875, 868, 844, 788, 538, 502 (all w). UV (1.15 x lθ "4 M in EtOH) _.,,,(€): 233 (7.48 X 10 3 ), 299 (1.05 X 10 3 ) . LRMS (70 eV, 100'C) m/e (assignment, % of base peak) : 298/297/296 (M+ cluster, 0.5/19.7/100), 269/268 (M-CO, 0.2/5.6), 241/240 (5/29), 199 (5), 197 (5), 155(4), 143(6), 141 (4), 129(10), 128 (9), 119(5), 118(3), 117(12), 115(11), 105(10), 103(4), 93(7), 92(6), 91(36). HRMS cacld for C 2Q H 24 0 2 296.1776, found 296.1774. 46e: ~ H NMR (CDC1 3 , 360 MHz): δ 3.79 (br d, J = 1.57 Hz, 2H) , 3.39 (br t, J = 1.57 Hz, IH) , 2.92 (br s, 2H) , 2.50-2.47 (m, 2H) , 2.29 (br d, J = 11.75 Hz, 2H) , 2.23-2.19 (m, IH) , 2.15 (br d, J = 11.75 Hz, 2H) , 1.95-1.81 (m, 8H) , 1.69 (br d, J ■ 11.61 Hz, 2H) , 1.60 (br d, J - 12.50 Hz, 2H) . 13 C{ 1 H) and DEPT (CDC1-, 90 MHz): δ 206.39 (OO) , 146.25 (OC) , 117.39 (OC) , 66.79 (CH) , 50.08 (CH) , 43.95 (CH) , 40.53 (CH 2 ), 39.58 (CH 2 ) , 36.66 (CH 2 ) , 33.58 (CH) , 27.95 (CH) , 27.76 (CH) , 27.61 (CH) . FT-IR (KBr, cm "1 ) 2912 (s) , 2850(m), 1729 (s) , 1703 (S) , 1467 (W) , 1450 (m) , 1384, 1336, 1306, 1251 (all w) , 1235 (m) , 1102 (w) , 1072 (m) , 1035, 1015, 960, 944, 876, 805, 701, 574, 532 (all w) . 46f: ~ K NMR (CDC1 3 , 360 MHz): δ 3.72 (br s, 2H) , 2.89 (br s, 2H) , 2.74 (br s 2H) , 2.33 (br S, 2H) , 2.31-2.27 (m, 2H) , 2.20-1.80 (m, 8H) , 1.69 (br d, J = 12.3 Hz, 2H) , 1.60 (br d, J - 11.1 Hz, 2H) . 13 C{ 1 H) and DEPT (CDC1 3 , 90 MHz): δ 211.97 (OO) , 143.51 (OC) , 125.56 (OC) , 50.30 (CH) , 45.09 (CH) , 40.05 (CH 2 ) , 39.54 (CH 2 ) , 39.45, 39.10 (CH 2 ), 36.69 (CH 2 ) , 33.13 (CH) , 27.90 (CH) .

Claims: IAIMg 1. A polymer comprising at least three monomers bonded through octahedrally disposed non-metallic atoms of the monomers. 2. The polymer of claim 1 wherein said octahedrally disposed atoms have a valence of 4. 3. The polymer of claim 2 wherein said octahedrally disposed atoms comprise carbon. 4. The polymer of any preceding claim wherein the monomers have the skeletal structure of adamantane. 5. The polymer of any preceding claim comprising a pendant substituent group. 6. The polymer of claim 5 wherein said substituent group is selected from the group consisting of C^-C- - aromatics, 1 -C 2Q alkyl groups, C 2 -C 20 alkenyl groups, 2~ C 20 alk n 1 groups, halogens, amines, diazo compounds, azide compounds, hydrazines, mercaptans, sulfides, polysulfides, ethers, alcohols, esters, organometallic compounds, amides, anhydrides, carba ates, ureas, imides, sulfonic acids, sulfinic acids, sulfinates, carboxylic acids, nitriles, isonitriles, heterocycles, metals, phosphates, phosphites, borates, ketones, aldehydes, aryl compounds, acid halides, hydrogen, and the reaction products thereof. 7. The polymer of claim 3 or claim 4 wherein said monomer units bond to form a linear molecular unit. - 0- 8. The polymer of claim 3 or claim 4 wherein said monomer units bond to form a laminar structure. 9. The polymer of claim 8 wherein said laminar structure comprises a sheet. 10. The polymer of claim 3 or claim 4 wherein said monomer units bond to form a three-dimensional framework structure. 11. The polymer of claim 3 or claim 4 wherein said monomer units bond to form a molecular sieve cage structure. 12. The polymer of claim 3 or claim 4 wherein said monomer units bond to form a helical structure. 13. The polymer of claim 4 having the structure of the linear rod compound designated as 3c in Figure 3, where n is at least 1. 14. The polymer of claim 4 having the structure of the compound designated as 7c in Figure 7, wherein X 1 and X 2 have the skeletal structure of adamantane, and n is at least 1. 15. The polymer of claim 4 comprising at least 4 repeating units having the structure of at least of the compounds designated as 16a, 16b, 16c and 16d in Figure 16. The polymer of claim 4 comprising at least 5 repeating units having the structure of at least of the compounds designated as 17a and 17b in Figure 17. 17. The polymer of claim 4 comprising at least 6 repeating units having the structure of at least one of the compounds designated as 17c and 17d in Figure 17. 18. A composition of matter having the structure of at least one of the compounds designated as 5a, 5b, 5c and 5d in Figure 5, wherein Ad has the skeletal structure of adamantane, and repeating adamantane skeletal units are bonded together through octahedrally disposed nonmetallic atoms of the repeating adamantane units, n is at least 2, and wherein R. and R 2 each comprise hydrogen or a nonpolar constituent group having from 1 to 20 carbon atoms, and wherein R 3 and R 4 comprise constituent groups having from 1 to 20 carbon atoms, with at least one of said R 3 and R 4 being polar. 19. The composition of claim 18 wherein at least one of the R and R 4 comprises a carboxyl group.

Inventors: CHAPMAN ORVILLE L, CHAPMAN, ORVILLE, L.
Applicants: MOBIL OIL CORP, MOBIL OIL CORPORATION
Application year: 1991
Main classification: C08G61
IPC codes: C07C49, C08G61, C08G73, C10M107