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WO1992013909A1 - Compositions polymeres en forme de diamant - Google Patents

Compositions polymeres en forme de diamant Download PDF

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Publication number
WO1992013909A1
WO1992013909A1 PCT/US1991/000935 US9100935W WO9213909A1 WO 1992013909 A1 WO1992013909 A1 WO 1992013909A1 US 9100935 W US9100935 W US 9100935W WO 9213909 A1 WO9213909 A1 WO 9213909A1
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Prior art keywords
diamantane
polymer
triamantane
polymers
diamondoid
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Darrell Duayne Whitehurst
Orville L. Chapman
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Mobil Oil AS
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Mobil Oil AS
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Priority to US07/472,530 priority Critical patent/US5019660A/en
Priority claimed from US07/472,530 external-priority patent/US5019660A/en
Application filed by Mobil Oil AS filed Critical Mobil Oil AS
Priority to JP3504556A priority patent/JPH06504981A/ja
Priority to PCT/US1991/000935 priority patent/WO1992013909A1/fr
Priority to AU72470/91A priority patent/AU661654B2/en
Priority to CA002100654A priority patent/CA2100654A1/fr
Priority to EP91904057A priority patent/EP0571377A1/fr
Publication of WO1992013909A1 publication Critical patent/WO1992013909A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
    • C07C13/64—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings with a bridged ring system
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/90—Ring systems containing bridged rings containing more than four rings

Definitions

  • the present invention relates to diamondoid polymeric compositions.
  • Diamondoid compounds represent a class of
  • diamondoid compounds have high melting points and high vapor pressures for their molecular weights.
  • the simplest member of this class is adamantane with principal derivatives including the higher homologs such as diamantane and triamantane.
  • molecules having high melting points and high vapor pressures for their molecular weights.
  • the simplest member of this class is adamantane with principal derivatives including the higher homologs such as diamantane and triamantane.
  • diamondoids molecules having a backbone resembling that of diamond structure consisting of polycyclic carbon rings, such as admantane, diamantane, triamantane, and alkyl substituted derivatives of the higher adamantane homologs will be referred to as "adamantalogs”.
  • the homologous series of adamantalogs can be represented by the formula C 6 H 10 + 4(C n H n ), where n ranges from 1 to >10 and is most commonly from 1 to 3.
  • Alkyl derivatives of these adamantalogs may be represented by adding C m H m to the formula listed above where m represents the number of carbons on the associated alkyl substituent.
  • Adamantane tricyclo-[3.3.3.1 3,7 ]decane, is a polycyclic alkane 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 larger diamondoid molecules such as diamantane and triamantane also contain methylene carbons;
  • adamantalogs exhibit non-octahedral geometries with respect to the center of the molecule. It is believed that the unusual chemical and physical properties exhibited by the higher adamantalog polymers of the present invention may be explained at least in part by the geometry of double bonds extending through the methylene groups.
  • Diamondoid compounds have been found to be useful building blocks 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 and 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 3 -C 4 alkyl chloride or bromide using AlCl 3 or AlBr 3 as the catalyst.
  • the reference describes polymerization through C 3 -C 4 linkages connecting bridgehead carbon atoms in the starting adamantane hydrocarbon via single carbon-carbon bonds.
  • 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 single bonds connecting the tetrahedral bridgehead carbons.
  • the adamantane molecule is bonded to the polymer chain through single bonds linking the tetrahedral bridgehead carbon atoms.
  • U.S. Patent 3,832,332 to Thompson teaches a polyamide polymer prepared from an alkyladamantane diamine.
  • the polymer comprises repeating units which include the backbone structure of adamantane, in which the adamantane structure is bonded to the polymer chain through single bonds extending from the bridgehead positions.
  • the present invention resides in a polymer
  • the polymer of the present invention may include pendant substituent groups replacing one or more hydrogens of the monomer units. These substituent groups may 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.
  • connecting substituent refers to a constituent which connects two or more monomers in a polymer.
  • terminal substituent refers to a constituent other than the repeating monomer unit which ends the polymer chain.
  • 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:
  • A is a repeating monomer unit, and B is a connecting substituent which connects two monomers; T 1 and T 2 are terminal substituents which differ from the repeating monomer and which end the polymer chain; and P 1 and P 2 are pendant substituents attached to the polymer backbone.
  • Non-limiting examples of such substituent groups include C 6 -C 20 aromatics, C 1 -C 20 linear and branched alkyl groups, C 2 -C 20 linear and branched alkenyl groups, C 2 -C 20 linear and branched alkynyl groups,
  • the monomer units comprising the polymer of the present invention may be bonded through one or more atoms occupying the methylene positions in the
  • the resulting polymers may assume linear, zig-zag, laminar, helical, or framework configurations as well as the myriad structures which may be
  • the skeletal structure of the monomer units themselves may be modified and expanded.
  • the positions occupied by the bridgehead and methylene carbons as discussed below with reference to diamantane and triamantane may be occupied not only by atoms other than carbon but also by substituent groups which can be substituted into the skeletal structure.
  • the skeletal structure may be expanded by inserting linear groups of uniform size between each of the bridgehead and each of the methylene positions. In addition to the inherent functionality of the inserted groups, the inserted groups expand the monomer unit while
  • the monomers include atoms at the bridgehead and methylene positions, these atoms suitably have a valance of 4.
  • examples of such atoms include the members of Group IVB of the Periodic Table of the
  • the polymer of the present invention exhibits unusual thermal stabilities and electrical properties indicating its potential utility in heat transfer fluids, specialty lubricants, semiconductors, data storage media, protective coatings, as well as
  • Derivatives of the polymer also find utility as surface active agents, protective coatings, chemical intermediates, and zeolite templates.
  • Such polymers may be suitably synthesized via McMurray coupling of the corresponding ketones as well as by olefin metathesis.
  • Figures 1A-1C are structural diagrams for the diamondoid compounds adamantane, diamantane, and triamantane and indicate the IUPAC numbering system for the positions of the various carbon atoms.
  • FIGS 1D-1I show two approximations of the structural geometry of the diamondoid compounds
  • Figure 2 is a diagrammatic structural
  • triamantane in which the double bonds extending from the methylene groups are shown as three dimensional projections, thus depicting the bonding plane defined by the double bonds connecting diamondoid monomer units of the polymers of the present invention.
  • Figure 3 schematically illustrates a two-step dimerization of diamantane to form endo- and exo-diamantane dimers bonded through double bonds
  • Figure 4 schematically illustrates a two-step synthesis method for coupling diamantane dimers to form four different cyclic diamantane tetramers.
  • Figure 5 schematically illustrates a two-step synthesis method for converting mixtures of diamantane diketone dimers and diamantane monoketones to linear or zig-zag structures.
  • Figures 6A-6C show a two-step synthesis method for converting the cyclic diamantane tetramers of Figure 4, i.e., the (R), (S), (H), and (L) tetramers into
  • the method shown comprises the two steps of oxidation and coupling, and it is to be understood that the synhthesis of relatively large sheet structures may require repetition of these two steps.
  • Figure 7 schematically illustrates a two-step synthesis technique for converting diamantane cyclic tetramers to cyclic diamantane octamers.
  • diamantane cyclic tetramers are first oxidized to tetraketones which are subsequently coupled to form cyclic octamers.
  • the resulting cyclic octamers may be further polymerized via oxidation/coupling reactions to evolve extended framework structures.
  • Figure 8 shows a simplified representation of a synthesis method for converting sheet structures constructed of extended diamantane polymer sheets having (R) aperatures as shown in Figure 6, above, to regular three-dimensional framework rhombohedral polymers.
  • Figure 9 schematically illustrates the reaction of 8-ketotriamantane to form the endo- and exo-triamantane dimers via McMurray coupling of the ketones. The coupling of 16-ketotriamantane molecules to form an exo-dimer is also shown.
  • Figure 10 is a simplified structural
  • Figure 11 is a simplified structural
  • Figure 12 schematically illustrates the further polymerization of the 16,17-triamantane dimer shown in Figure 11. Oxidation of the 16,17-triamantane dimer to the 8,8'-diketone and subsequent coupling of the diketone yields the endo cyclic triamantane tetramer.
  • Figure 13 shows an example of a mixed diamondoid polymer synthesis in which adamantane and diamantane monoketones are first coupled and the resulting mixed diamondoid dimers are chlorinated and substituted to form the monoketones. The monoketones of the mixed dimers are then coupled with an adamantane or
  • Figure 14 similarly shows the preparation of mixed diamondoid dimers of adamantane and triamantane (Eq.
  • Figure 15 illustrates the formation of cyclic mixed tetramers of diamantane and triamantane (Eq.
  • Figure 16 schematically illustrates the structure of a diamantane cyclic trimer.
  • the polymers of the present invention comprise monomers having the backbone structure of diamantane and the higher adamantalogs bonded through double bonds extending from the methylene positions of the monomers.
  • the monomer units comprise diamantane and the diamantane monomer units are
  • adamantane has methylene groups at carbon atoms 2, 4, 6, 8, 9, and 10. All of the methylene groups in adamantane are geometrically equivalent.
  • Diamantane on the other hand, has
  • the methylene groups in the parent diamantane are all chemically equivalent. However, their relative locations in space are more conveniently considered by grouping the six methylene groups into two groups of three adjacent methylenes, i.e., (3, 5, and 14) and (8, 10, and 13). This grouping also facilitates consideration of the diamantane derivatives.
  • triamantane has methylene groups at positions 5, 8, 10, 14, 18, 16, and 17.
  • Positions 8, 10, 14, and 18 are equivalent to one another but are more conveniently considered as two groups of two adjacent positions, i.e., (8 and 10) and (14 and 18). Positions 16 and 17 constitute another pair of methylene groups that are equivalent to each other. Position 5 is unique. Positions (8, 10, 17) and (14, 16, 18) can also be considered as groups of adjacent methylene groups.
  • adamantalogs are suitably polymerized by first
  • adamantalog monomer to a doubly bonded group, such as a ketone.
  • the adamantalog ketones are then reacted to form a double bond between the adamantalog monomer units at the ketone site.
  • two isomers may result from the dimerization of like diamandoid monomer units, which may be envisioned as exo- and endo-isomers.
  • an exo-isomer is defined as a dimer in which the diamondoid monomer units face toward each other as illustrated by structure 3-A of Figure 3
  • an endo-isomer is defined as a dimer in which the diamondoid monomer units face away from each other as illustrated in structure 3-B of Figure 3.
  • adamantalog polymers For example, if adamantane is polymerized through positions 2 and 6, each newly added adamantane will be rotated 90 degrees to its partner. A diamantane homopolymer linked through positions 5 and 13 will produce a polymer in which all diamantane components of the polymer have the same configuration in space or will be rotated 180 degrees to one another. Triamantane exhibits a geometry unlike either
  • each newly added triamantane will be rotated 180 degrees to its adjoining triamantane monomer unit. If, however, the triamantane monomers are linked through positions 5 and 16, all the triamantane monomer units will have the same orientation in space or will be rotated 180 degree to each other.
  • the orientation of the bonding planes dictates which methylene groups can be utilized to form polymers of particular shapes.
  • the diamondoid polymers may be described in terms of the ketones which can be produced at the methylene positions, in that the ketones are reduced to link the diamondoid monomers through double bonds extending through the methylene positions.
  • Nonlimiting examples of these geometrically different positional isomers for diamondoid monomers containing up to four ketones are tabulated in Table 1 with the IUPAC numbered position of each ketone shown in parentheses.
  • the preferred synthetic routes are also set forth at length below. It is to be noted that there is only one positional isomer for the adamantane and diamantane monomers having either five or six ketones. Similarly,
  • heptaketotriamantane has only one positional isomer. From the disclosure of Table 1, one skilled in the art can readily determine the positional isomers for triamantane having five and six ketones by using the unsubstituted positions for the four and three
  • Figures 1G, 1H, and 1I exemplify such two-dimensional views of these adamantalogs with closed circles representing carbon atoms closer to the observer and open circles
  • optical isomers Formation of such dl optical isomers is subject to the limitations of coplanar double bonding as discussed above.
  • One skilled in the art may determine the optical isomers from the rectangular approximations shown in Figures 1G-1I by including the angular line in the center of diamantane for reference.
  • utilities for such optical isomers include chiral chromatography columns, chiral molecular sieves, and components for chiral catalysis.
  • diamandoid molecules may also be represented by hexagonal cylinders as shown in
  • FIGS. 1D, 1E, and 1F This depiction shows three methylenes as a face of the cylinder.
  • Adamantane is somewhat distorted in this view as any three methylene groups define a face.
  • Diamantane and triamantane are more accurately envisioned in this manner as the faces are more clearly separated and different from each other. The significance of such face definition is that diamandoid monomers linked only through faces can provide cyclic four membered diamondoid structures with unique properties, useful in selective sorption and catalysis.
  • the simplest diamantane homopolymer is the dimer which may be formed by coupling two 3-ketodiamantane molecules.
  • the reaction product contains two isomeric dimers as shown in Figure 3.
  • the exo-dimer, structure 3-A is a preferred intermediate for syntheses of linear polymers, certain two-dimensional sheets and one class of three dimensional polymers as will be set forth in greater detail below.
  • structure 3-B can be further dimerized to formed a cyclic tetramer with unique electronic properties.
  • the conductance band of this face-coupled tetramer is easily accessed by exposure to light and/or heat. Dimerization of the endo-isomer 3-B is shown in Figure 4 as discussed below.
  • Figure 4 schematically illustrates a tetramer synthesis, showing that the dimers can be taken
  • these cyclic tetramers may be further polymerized to form larger sheet or framework polymers.
  • the most preferred synthesis technique for constructing the larger diamantane polymers is the progressive coupling of smaller diamantane-containing polymers. Synthesis of the diamantane tetramers via oxidation and coupling is illustrative of one such progressive synthesis technique.
  • the four tetramers 4-A to 4-D are identified herein by the size and/or shape of the aperature defined by the four linked diamondoid units. These abbreviations are R, S, H, and L, signifying rectangular, small square, herringbone, and .large square, respectively as illustrated in Figure 4.
  • the R tetramer is produced by using the diketone made by oxidizing the exo-dimer in the positions indicated in Figure 4. Assuming the exo-dimer was formed by coupling the diamantanes through the IUPAC 3 positions then the respective positions for oxidation are the 14 position in one ring and the 13 position in the other ring.
  • the endo-isomer would be oxidized in the 5 position in one ring and the 14 position in the other ring to produce the diketone which forms the S tetramer.
  • the diketone which couples to from the L tetramer is produced by oxidation of the endo-dimer in the 8 position in one ring and the 13 position in the other ring.
  • the H tetramer is made by cross coupling the two different endo-derived diketones.
  • High molecular weight unidimensional polymers may be synthesized as shown in Figure 5 by selectively oxidizing and subsequently coupling the diketones shown in Figures 3 and 4.
  • Extension of the linear structure (5-A) gives a rigid rod polymer which has very low solubility in organic solvents when more than four (4) diamondoid monomeric units are present in the polymer.
  • Such rod polymers have application where very stable coatings are required.
  • Extension of the various zig-zag structures e.g., 5-B) lead to more soluble polymers which also have application as coating
  • the linear diamantane homopolymer is formed via bonding through opposing methylene carbons.
  • the synthesis includes the McMurray coupling of
  • the diamantane monoketone and diketones may be synthesized from the corresponding chlorinated
  • the diamantane rod polymer may also be synthesized via olefin metathesis of 3-methylene diamantane and 3,10-dimethylene diamantane in the approximate molar ratio of 3,10-dimethylene diamantane: 3-methylene diamantane, which reflects the desired rod length.
  • 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
  • Diamantane monomers can be polymerized into two dimensional polymer sheets via appropriate
  • the cyclic tetramers R, S, H, and L as shown in Figure 4 may be extended to form three (3) uniquely ordered polymeric sheets which may be readily identified by the shape and size of the repeating aperatures as
  • the preferred synthesis technique comprises oxidation to produce the tetraketo-tetramers and subsequent coupling of the tetrako-tetramers.
  • the two-dimensional sheet structures are readily recognizable from their tetramer precursors.
  • the rectangular tetramer (R) gives rise to the sheet polymer shown by structure 6-A in Figure 6.
  • the herringbone tetramer (H) gives riser to the sheet polymer having the structure 6-B of Figure 6.
  • the (S) tetramer and the (L) tetramer lead to the same sheet structure 6-C.
  • This sheet polymer is unique in that is contains isolated 4-face coupled regions which have special electronic properties in that ring system (S) can be excited by light.
  • Diamantane monomers may also be polymerized to form three-dimensional or framework polymers.
  • the simplest such framework polymer is a fully cyclic octamer.
  • Such an octamer can be made by dimerizing the tetraketone tetramer having the structure 7-A or 7-B as shown in Figure 7.
  • three-dimensional polymers may be formed by selective oxidation and coupling. These three-dimensional framework polymers resemble coupled stacks of the regular sheet polymers, which sheet polymers R, S, H, and L are illustrated in Figure 4.
  • 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
  • I/I o the relative intensities of the lines, I/I o.
  • I o 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.
  • 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.
  • Triamantane polymers may be synthesized using techniques similar to those utilized in diamantane polymer synthesis. Dimers of triamantane are readily produced from the corresponding monoketones.
  • Triamantane dimers exhibit the exo and endo
  • Triamantane is polymerized via oxidation and reduction in a manner similar to that used for
  • triamantane can produce cyclic tetramers of the types (R), (S), (H), and (L). Triamantane may also be polymerized to additional cyclic tetramers which exhibit slightly larger aperatures than those formed by diamantane cyclic tetramers but which show
  • Each of the methylene carbons in triamantane is separated from its nearest neighboring methylene carbon by one (1) bridgehead carbon. This differs from the geometry of the diamantane methylene carbons.
  • Diamantane has methylene carbons separated by one (1) bridgehead carbon on the face positions (3, 5, 14) or (8, 10, 13), and methylene carbons separated by two (2) bridgehead carbons across the structure (i.e., 5 and 8, 5 and 10).
  • Triamantane also has methylenes separated by one (1) bridgehead carbon on the faces (8, 10, 17) and (14, 16, 18), methylenes separated by two (2) bridgehead carbons from face methylenes to position 5 (i.e., 5 and 8, 5 and 10), or methylenes separated by three bridgehead carbons horizontally across the structure shown in Figure 1 (i.e. 8 and 14, 10 and 18).
  • the significance of describing structure in this way is that the aperature geometries described above can be abbreviated as shown below where the separation between methylenes is given in terms of the number of
  • Table 1 shows that homopolymers of adamantane bonded through the methylene carbons will have only (S) type tetramer structures.
  • Diamantane on the other hand, can have (S), (R), (H), and (L)-type tetramers.
  • Triamantane can have all of the tetramers mentioned above in Table 1.
  • higher polymers are synthesized from triamantane via oxidation and coupling which include linear and zig-zag one dimensional polymers, sheet-type two dimensional polymers having the tetramer aperature structures described above, and three dimensional polymers having channels composed of sequences of aperatures as described above with reference to
  • the present invention further includes polymers comprising monomers having the structure of at least two selected from the group consisting of molecules having the skeletal structure of adamantane, diamantane, and triamantane, said monomers being double bonded through the methylene positions of said monomers.
  • mixed diamondoid polymers are particularly desirable as it is believed that their properties may be tailored to fit particular applications such as heat transfer fluids useful over wide temperature ranges. Examples of such mixed component diamondoid polymers containing diamantane and triamantane units linked together via double bonds are shown in Figure 13.
  • the preferred synthesis technique for such mixed diamondoid polymers is also illustrated in Figure 13.
  • the preferred synthesis includes a different synthetic route to the ketone intermediate, namely, chlorination/substitution-oxidation. This route is particularly preferred for improving
  • Mixed polymers of the type shown in structure 13-C of Figure 13 are intermediate in molecular weight and boiling point between homopolymers of adamantane and diamantane.
  • the present invention provides heat transfer fluids which can be tailored to a particular application by adjusting the boiling range of the mixed diamondoid polymer.
  • Linear or zig-zag mixed polymers are produced by sequential oxidation/coupling reactions. Multiketo derivatives of the various diamondoids are readily co-polymerized by the methods set forth above to yield a wide variety of useful mixed polymers.
  • structure 15-A and of adamantane and diamantane, structure 15-B.
  • the precursor diketones for these structures are suitably synthesized from the endo diamantane dimer and the 16, 17-triamantane dimer via the chlorination/substitution-oxidation route
  • the present invention further includes polymers comprising at least one substituted diamondoid monomer.
  • substituted diamondoid polymers are particularly preferred.
  • methyl and ethyl derivatives are particularly desirable as they lower the freezing point of the diamondoid polymer and thus extend the utility of diamondoid polymers to lower temperature liquid phase applications.
  • Certain natural gas wells comprise the preferred source for these methyl- and ethyl-substituted
  • a particularly preferred mixed diamonoid polymer is synthesized from the naturally occuring mixture of diamondoid monomers found in natural gas deposits (see Example 8 below).
  • the mixture of diamondoid compounds recovered from the natural gas well may be treated as a single species.
  • the crude diamondoid mixture is oxidized to provide a mixture of mono, di, tri, and higher ketones and the resultant ketone mixture is cross-coupled to produce a mixture of mixed diamondoid polymers.
  • Such mixtures have particular utility in heat transfer application as they are useful over a wide range of temperatures, expecially lower
  • diamondoid polymers would be crystalline solids.
  • diamondoid monomers having propyl and longer alkyl groups, branched aliphatic groups, as well as cyclic alkyl or aromatic substituent groups are
  • FIG. 16 The structure of a diamantane cyclic trimer is shown in Figure 16. This polymer may be synthesized by first oxidizing diamantane to diamantanone and then chlorinating and oxidizing to the 3,5-diamantanone. The next step may be accomplished by either of two routes. The 3,5-diamantanone may be coupled via
  • 3,5-diamantanone may be dimerized via coupling and then chlorinated and oxidized to the diketo-dimer.
  • the diketo-dimer is then reduced with 3,5-diketodiamantane to yield a mixture containing the cyclic diamantane trimer.
  • the most preferred synthesis technique for all of the diamondoid polymers of the present invention is a two-step synthesis involving a first oxidation step to form at least one ketone at a methylene position of a diamondoid monomer.
  • a first oxidation step to form at least one ketone at a methylene position of a diamondoid monomer.
  • the hydrocarbon can initially be halogenated, for example with N-chlorosuccinimide (NCS), and the resultant halogenated derivative
  • the second step consists of coupling two or more ketones to produce the desired polymer. This can be
  • coupling can be effected by reacting the ketones in the presence of TiCl 3 , Na and 1,4-dioxane.
  • the chloro derivative is convertable to the desired
  • ketone derivative by substitution of the chlorine by a hydroxyl group and further oxidation by a reagent such as sodium bicarbonate in dimethylsulfoxide (DMSO).
  • a reagent such as sodium bicarbonate in dimethylsulfoxide (DMSO).
  • 3-Diamantanone (I) is prepared by adding 2.0 g of diamantane to 100 ml of 96.6% sulfuric acid; the
  • reaction mixture is then heated for four hours at 75o C with vigorous stirring. Stirring is continued at room temperature for one additional hour.
  • reaction mixture is poured over ice and steam
  • the ketone derivatives of triamantane are prepared by mixing 16 g of triamantane with 96% sulphuric acid (160 ml), and the mixture is stirred vigorously at 75oC in a loosely stoppered flask (to allow escape of sulphur dioxide) with occasional shaking to redissolve sublimed material. After 5 hours the principle
  • Chloroadamantylidenediamantanes are prepared as follows. To a solution of 1 mmol (322 mg) of
  • the intermediate chlorides are converted to a mixture of the corresponding alcohols and ketones by heating them to around 100oC in solution of sodium bicarbonate in dimethylsulfoxide for several hours.
  • the product mixture is partitioned between hexane and water and the hexane layer evaporated to yield the product mixture.
  • High selectivity for ketone introduction adjacent to double bonds can also be accomplished by selective bromination as shown in this example.
  • Diketones of diamondoids can be produced by more vigorous oxidation than in Examples 1 and 2 using strong oxidizing agents such as H 2 SO 4 or CrO 3 /Ac 2 O but are preferably produced by a sequence of oxidations; first to monoketones or hydroxy ketones followed by further oxidation or rearrangement-oxidation, depending on the intermediates involved.
  • oxidizing agents such as H 2 SO 4 or CrO 3 /Ac 2 O
  • the monoketone (I) is then treated with a solution of CrO 3 in acetic anhydride at near room temperature for about 2 days.
  • the reaction is quenched with dilute aqueous caustic (NaOH), and the product isolated by extraction with diethyl ether.
  • NaOH dilute aqueous caustic
  • the product diketones, 3,5-diketodiamantane (XIII), 3,8-diketodiamantane (XIV) and 3,10-diketodiamantane (XV) are then separated and used for polymer preparations.
  • One particularly useful oxidation procedure to produce adjacent ketones on the same diamondoid face is to selectively oxidize an intermediate ketone with
  • the mixed lactone products are isolated by dilution of the reaction solution with water, extraction with hexane and removal of the hexane by evaporation.
  • the lactones are hydrolized and rearranged by heating with 50%
  • a natural gas condensate having the following composition is oxidized to produce a mixture of ketones by treatment with 96% H 2 SO 4 at 70oC for about 10 hr or by treating with CrO 3 /Ac 2 O at near room temperature for about one day.
  • Isolation of the product ketones is accomplished using the procedures described above and are used to prepare mixed diamondoid polymers.
  • Polymers of diamondoids can be made by coupling their keto derivatives using several procedures.
  • One very useful procedure is the McMurray coupling reaction as described below.
  • the TiCl 3 /THF mixture is cooled to 0oC, and the desired amount (generally .015 to .05 mol) of LiAlH 4 is added in small portions to keep the vigorous reaction (H 2 evolution) under control. After the addition, the reaction mixture is stirred at 0oC for 30 min. If hydrogenation as a side reaction is to be minimized, the black suspension of [M] is refluxed for an
  • ketone generally 0.01 to 0.02 mol of ketone groups
  • [M] aqueous reducing agent
  • the mixture is stirred at room temperature for 6 to 20 hr. depending on the particular diamondoid being coupled. During the reaction a gentle stream of argon is maintained.
  • ketodiamondoids of Example 8 can be polymerized in high yield to produce dimers in the case of I-IV, VIII and IX. Mixed dimers result if two different diamondoids are co-polymerized. Mixed polymers are also produced from the diamondoids of Example 8.
  • multisubstituted diamondoids such as XIII-XVII.
  • intermediate XV linear rigid rod polymers are formed which have lower solubility and higher melting points than the corresponding zig-zag polymers which are formed from XIII, XIV and XVII.
  • Mixed higher polymers can also be produced from mixtures of these diketodiamondoids.
  • cyclic polymers can be formed from the diketones that allow ring closure such as endo polymers of XIII, xiv and XVIII. Generally tetramers are preferred in these cyclizations but cyclic trimers also form in special cases such as with XIII and XVII.
  • Another very useful polymer can be formed from XVI when polymerized at high dilution. This is the cyclic dimer of triamantane having two linkages between the 16 and 17 positions of the two respective triamantane structures (XIV).
  • Two dimensional sheet polymers can be formed from diamondoids bearing more than 2 ketone groups. Such precursors can be formed by extended oxidations of the parent diamondoids, or by sequential
  • Cyclic tetramers are particularly useful as intermediates in the production of two dimensional sheets through additional oxidation/coupling sequences as described in the previous examples.
  • the cyclic dimer of triamantane (XIV) described in Example 9 is useful in producing an unusual cyclic tetramer and cyclic octamer by selective production of ketone intermediates from methylene groups adjacent to the double bonds which link the diamondoid structures. Selective ketone production can be achieved using the procedures described in Examples 4, 5 and 7.
  • Hydrogen sulfide is bubbled through a solution of the azine (XIX) (13.2 g, 41.1 mmol), and 5 mg of p-toluenesulfonic acid in 300 ml of 1:3 acetone-benzene at ambient temperature. Conversion is complete after about 12 hours. The solvent is removed on a rotary evaporator to give >90% of the thiadiazolidine (XX). This material is used in the subsequent step without further purification.
  • This material is used in the subsequent step without further purification.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

Cette invention concerne une composition polymère comprenant au moins un monomère qui présente la structure du diamantane, du triamantane ou d'un 'adamantalogue' (homologue d'adamantane) supérieur et qui est fixé par au moins une double liaison traversant une position méthylène dudit monomère.
PCT/US1991/000935 1990-01-30 1991-02-12 Compositions polymeres en forme de diamant Ceased WO1992013909A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US07/472,530 US5019660A (en) 1990-01-30 1990-01-30 Diamondoid polymeric compositions
JP3504556A JPH06504981A (ja) 1990-01-30 1991-02-12 ダイアモンド類似重合体組成物
PCT/US1991/000935 WO1992013909A1 (fr) 1990-01-30 1991-02-12 Compositions polymeres en forme de diamant
AU72470/91A AU661654B2 (en) 1990-01-30 1991-02-12 Diamondoid polymeric compositions
CA002100654A CA2100654A1 (fr) 1990-01-30 1991-02-12 Compositions polymeriques diamantoides
EP91904057A EP0571377A1 (fr) 1990-01-30 1991-02-12 Compositions polymeres en forme de diamantan

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US07/472,530 US5019660A (en) 1990-01-30 1990-01-30 Diamondoid polymeric compositions
PCT/US1991/000935 WO1992013909A1 (fr) 1990-01-30 1991-02-12 Compositions polymeres en forme de diamant
CA002100654A CA2100654A1 (fr) 1990-01-30 1991-02-12 Compositions polymeriques diamantoides

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003050066A1 (fr) * 2001-12-07 2003-06-19 Chevron U.S.A. Inc. Diamantoides superieurs fonctionnalises
US6783589B2 (en) 2001-01-19 2004-08-31 Chevron U.S.A. Inc. Diamondoid-containing materials in microelectronics
US6858700B2 (en) 2001-01-19 2005-02-22 Chervon U.S.A. Inc. Polymerizable higher diamondoid derivatives
EP1637187A1 (fr) 2004-09-09 2006-03-22 L'oreal Composition cosmétique comprenant au moins un diamantoïde, destinée à renforcer les propriétés mécaniques de certains matériaux
US7224532B2 (en) 2002-12-06 2007-05-29 Chevron U.S.A. Inc. Optical uses diamondoid-containing materials
US7273598B2 (en) 2001-01-19 2007-09-25 Chevron U.S.A. Inc. Diamondoid-containing materials for passivating layers in integrated circuit devices
US7304190B2 (en) 2003-10-01 2007-12-04 Chevron U.S.A. Inc. Photoresist compositions comprising diamondoid derivatives
US7306674B2 (en) 2001-01-19 2007-12-11 Chevron U.S.A. Inc. Nucleation of diamond films using higher diamondoids
US7312562B2 (en) 2004-02-04 2007-12-25 Chevron U.S.A. Inc. Heterodiamondoid-containing field emission devices
US7402835B2 (en) 2002-07-18 2008-07-22 Chevron U.S.A. Inc. Heteroatom-containing diamondoid transistors
US7795468B2 (en) 2001-01-19 2010-09-14 Chevron U.S.A. Inc. Functionalized higher diamondoids
US7884256B2 (en) 2001-01-19 2011-02-08 Chevron U.S.A. Inc. Polymerizable higher diamondoid derivatives

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US3560578A (en) * 1969-05-08 1971-02-02 Sun Oil Co Reaction for linking nuclei of adamantane hydrocarbons
US5019660A (en) * 1990-01-30 1991-05-28 Mobil Oil Corporation Diamondoid polymeric compositions

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US3560578A (en) * 1969-05-08 1971-02-02 Sun Oil Co Reaction for linking nuclei of adamantane hydrocarbons
US5019660A (en) * 1990-01-30 1991-05-28 Mobil Oil Corporation Diamondoid polymeric compositions

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7276222B2 (en) 2001-01-19 2007-10-02 Chevron U.S.A. Inc. Diamondoid-containing thermally conductive materials
US7306674B2 (en) 2001-01-19 2007-12-11 Chevron U.S.A. Inc. Nucleation of diamond films using higher diamondoids
US6858700B2 (en) 2001-01-19 2005-02-22 Chervon U.S.A. Inc. Polymerizable higher diamondoid derivatives
US8420768B2 (en) 2001-01-19 2013-04-16 Chevron U.S.A. Inc. Polymerizable higher diamondoid derivatives
US7061073B2 (en) 2001-01-19 2006-06-13 Chevron U.S.A. Inc. Diamondoid-containing capacitors
US7160529B2 (en) 2001-01-19 2007-01-09 Chevron U.S.A. Inc. Diamondoid-containing field emission devices
US7884256B2 (en) 2001-01-19 2011-02-08 Chevron U.S.A. Inc. Polymerizable higher diamondoid derivatives
US7273598B2 (en) 2001-01-19 2007-09-25 Chevron U.S.A. Inc. Diamondoid-containing materials for passivating layers in integrated circuit devices
US6783589B2 (en) 2001-01-19 2004-08-31 Chevron U.S.A. Inc. Diamondoid-containing materials in microelectronics
US7795468B2 (en) 2001-01-19 2010-09-14 Chevron U.S.A. Inc. Functionalized higher diamondoids
US7306671B2 (en) 2001-01-19 2007-12-11 Chevron U.S.A.. Inc. Diamondoid-containing low dielectric constant materials
WO2003050066A1 (fr) * 2001-12-07 2003-06-19 Chevron U.S.A. Inc. Diamantoides superieurs fonctionnalises
US7402835B2 (en) 2002-07-18 2008-07-22 Chevron U.S.A. Inc. Heteroatom-containing diamondoid transistors
US7224532B2 (en) 2002-12-06 2007-05-29 Chevron U.S.A. Inc. Optical uses diamondoid-containing materials
US7304190B2 (en) 2003-10-01 2007-12-04 Chevron U.S.A. Inc. Photoresist compositions comprising diamondoid derivatives
US7488565B2 (en) 2003-10-01 2009-02-10 Chevron U.S.A. Inc. Photoresist compositions comprising diamondoid derivatives
US7312562B2 (en) 2004-02-04 2007-12-25 Chevron U.S.A. Inc. Heterodiamondoid-containing field emission devices
EP1637187A1 (fr) 2004-09-09 2006-03-22 L'oreal Composition cosmétique comprenant au moins un diamantoïde, destinée à renforcer les propriétés mécaniques de certains matériaux

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