US20020022708A1 - Compositions and methods for thermosetting molecules in organic compositions - Google Patents

Compositions and methods for thermosetting molecules in organic compositions Download PDF

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US20020022708A1
US20020022708A1 US09/897,936 US89793601A US2002022708A1 US 20020022708 A1 US20020022708 A1 US 20020022708A1 US 89793601 A US89793601 A US 89793601A US 2002022708 A1 US2002022708 A1 US 2002022708A1
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aryl
polymer
arylene ether
branched
dielectric constant
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US09/897,936
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Kreisler Lau
Feng Liu
Boris Korolev
Emma Brouk
Ruslan Zherebin
David Nalewajek
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Honeywell International Inc
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Honeywell International Inc
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Priority claimed from US09/618,945 external-priority patent/US6469123B1/en
Application filed by Honeywell International Inc filed Critical Honeywell International Inc
Priority to US09/897,936 priority Critical patent/US20020022708A1/en
Priority to CN01815765A priority patent/CN1458945A/zh
Priority to KR1020037000737A priority patent/KR100620207B1/ko
Priority to EP01958944A priority patent/EP1309639A4/en
Priority to PCT/US2001/022204 priority patent/WO2002008308A1/en
Priority to AU2001280549A priority patent/AU2001280549A1/en
Priority to JP2002514210A priority patent/JP2004504455A/ja
Priority to TW090117706A priority patent/TWI241310B/zh
Priority to US10/466,651 priority patent/US7307137B2/en
Priority to CNA018231160A priority patent/CN1643030A/zh
Priority to JP2002579926A priority patent/JP2005501131A/ja
Priority to CA002441901A priority patent/CA2441901A1/en
Priority to EP01983172A priority patent/EP1373358A4/en
Priority to KR10-2003-7013030A priority patent/KR20040011494A/ko
Priority to PCT/US2001/032569 priority patent/WO2002081546A1/en
Priority to TW090128725A priority patent/TWI295673B/zh
Priority to MYPI20015668A priority patent/MY134260A/en
Publication of US20020022708A1 publication Critical patent/US20020022708A1/en
Priority to US10/267,380 priority patent/US6803441B2/en
Priority to JP2007153763A priority patent/JP2007332373A/ja
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/60—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing acetylenic group

Definitions

  • the field of the invention is reduction of dielectric constants.
  • Insulator materials having low dielectric constants are especially desirable, because they typically allow faster signal propagation, reduce capacitive effects and cross talk between conductor lines, and lower voltages to drive integrated circuits.
  • air has a dielectric constant of about 1.0
  • a major goal is to reduce the dielectric constant of insulator materials down towards a theoretical limit of 1, and several methods are known in the art for including air into the insulator materials to reduce the dielectric constant of such materials.
  • air is introduced into the insulator material by generating nanosized voids in a composition comprising an adequately crosslinked thermostable matrix and a thermolabile (thermally decomposable) portion, which is either separately added to the thermostable matrix material (physical blending approach), or built-in into the matrix material (chemical grafting approach).
  • the matrix material is first crosslinked at a first temperature to obtain a three-dimensional matrix, then the temperature is raised to a second, higher temperature to thermolyze the thermolabile portion, and cured at a third, still higher temperature to anneal and stabilize the desired nanoporous material that has voids corresponding in size and position to the size and position of the thermolabile portion.
  • thermolabile portion and thermostable matrix generally limits processing temperatures to relatively narrow windows which must distinguish the crosslinking (cure) temperature, thermolysis temperature and glass transition temperature, thereby significantly limiting the choice of available materials.
  • air or other gas i.e. voids
  • voids air or other gas
  • the nanosized spheres acts as a “void carriers”, which may or may not be removed from the matrix material.
  • U.S. Pat. No. 5,458,709 to Kamezaki et al. the inventors teach the use of hollow glass spheres in an insulator material.
  • the distribution of the glass spheres is typically difficult to control, and with increasing concentration of the glass spheres, the dielectric material loses flexibility and other desirable physico-chemical properties.
  • glass spheres are generally larger than 20 nm, and are therefore not suitable for nanoporous materials where pores smaller than 2 nm are desired.
  • the present invention is directed to a method of producing a low dielectric constant polymer.
  • a star-shaped thermosetting monomer having a core structure and a plurality of arms is provided, and in a subsequent step the thermosetting monomer is incorporated into a polymer, wherein the incorporation into the polymer comprises a reaction of a triple bond that is located in at least one arm.
  • the core structure is a cage compound or aryl, and preferred arms are aryl, branched aryl or arylene ether. It is also preferred that where the core structure is a cage compound, at least one of the arms has a triple bond. Where the core structure is an aryl compound, it is preferred that all of the arms have a triple bond.
  • Especially contemplated core structures include adamantane, diamantane, a phenyl, and a sexiphenylene, and especially contemplated arms include a tolanyl, a phenylethynylphenylethynylphenyl, a p-tolanylphenyl, a 1,2-bis(phenylethynyl)phenyl, and a p-tolanylphenyl ether.
  • the incorporation of the thermosetting monomer includes a reaction on more than one triple bond, preferably on three triple bonds located on three arms, and more preferably on all triple bonds located in all arms.
  • the incorporation takes place without participation of an additional molecule and preferably comprises a cyclo-addition reaction.
  • thermosetting monomer is incorporated in a backbone of a polymer, other positions including the termini and side chains are also appropriate.
  • Preferred polymers include poly(arylene ethers) and polymers comprising, or consisting of contemplated thermosetting monomers. It is especially contemplated that by increasing the length of the arms of the thermosetting monomers, the monomers will define an increased void volume between the monomers after crosslinking, thereby decreasing the density of the crosslinked structure and decreasing the dielectric constant of the polymer.
  • FIGS. 1 A- 1 C are exemplary structures for star shaped thermosetting monomers having an adamantane, a diamantane, and a silicon atom as a cage compound, respectively.
  • FIGS. 2 A- 2 B are exemplary structures for star shaped thermosetting monomers having a sexiphenylene as an aryl group.
  • FIGS. 3 A- 3 C are exemplary synthetic schemes for star shaped thermosetting monomers according to the inventive subject matter.
  • FIG. 4 is an exemplary scheme for the synthesis of substituted adamantanes with aryl arms of varying length.
  • the term “low dielectric constant polymer” refers to an organic, organometallic, or inorganic polymer with a dielectric constant of approximately 3.0, or lower.
  • the term “cage compound” refers to a molecule in which a plurality of rings formed by covalently bound atoms define a volume, such that a point located within the volume can not leave the volume without passing through a ring.
  • adamantane-type structures including adamantane and diamantane are considered a cage compound.
  • ring compounds with a single bridge such as norbornane (bicyclo[2.2.1]heptane) are not considered a cage compound, because the rings in a single bridged ring compound do not define a volume.
  • thermosetting monomer having a general structure as shown in Structure 1,
  • thermosetting monomer is incorporated into a polymer thereby forming the low dielectric constant polymer, wherein the incorporation into the polymer comprises a chemical reaction of the at least one triple bond.
  • aryl without further specification means aryl of any type, which may include, for example a branched aryl, or an arylene ether.
  • Exemplary structures of thermosetting monomers that include an adamantane, a diamantane, and a silicon atom are shown in FIGS. 1A, 1B, and 1 C, respectively, wherein n is an integer between zero and five, or more.
  • thermosetting monomer having a general structure as shown in Structure 2,
  • thermosetting monomer is incorporated into a polymer thereby forming a low dielectric constant polymer, wherein the incorporation into the polymer comprises a chemical reaction of the at least one triple bond.
  • Exemplary structures of thermosetting monomers that include a tetra-, and a hexasubstituted sexiphenylene are shown in FIGS. 2A and 2B, respectively.
  • Thermosetting monomers as generally shown in Structures 1 and 2 may be provided by various synthetic routes, and exemplary synthetic strategies for Structures 1 and 2 are shown in FIGS. 3 A- 3 C.
  • FIG. 3A depicts a preferred synthetic route for the generation of star shaped thermosetting monomers with an adamantane as a cage compound, in which a bromoarene is phenylethynylated in a palladium catalyzed Heck reaction.
  • adamantane (1) is brominated to tetrabromoadamantane (TBA) (2) following a procedure previously described ( J. Org. Chem. 45, 5405-5408 (1980) by Sollot, G. P. and Gilbert, E.
  • TBA is reacted with phenyl bromide to yield tetrabromophenyladamantane (TBPA) (4) as described in Macromolecules, 27, 7015-7022 (1990) by Reichert, V. R, and Mathias L. J.
  • TBPA tetrabromophenyladamantane
  • TBPA is subsequently reacted with a substituted ethynylaryl in a palladium catalyzed Heck reaction following standard reaction procedures to yield tetraarylethynylphenyladamantane (TAEPA) (5).
  • the palladium-catalyzed Heck reaction may also be employed for the synthesis of a star shaped thermosetting monomer with a sexiphenylene as the aromatic portion as shown in FIG.
  • FIG. 2C and FIG. 2D in which a tetrabromosexiphenylene and a hexabromosexiphenylene, respectively, is reacted with an ethynylaryl to yield the desired corresponding star shaped thermosetting monomer.
  • TBA can be converted to a hydroxyarylated adamantane, which is subsequently transformed into a star shaped thermosetting monomer in a nucleophilic aromatic substitution reaction.
  • TBA (2) is generated from adamantane (1) as previously described, and further reacted in an electrophilic tetrasubstitution with phenol to yield tetrakis(hydroxyphenyl)adamantane (THPA) (7).
  • THPA tetrakis(hydroxyphenyl)adamantane
  • TBA can also be reacted with anisole to give tetrakis(4-methoxyphenyl)adamantane (TMPA) (6), which can further be reacted with BBr 3 to yield THPA (7).
  • standard procedures e.g., Engineering Plastics—A Handbook of Polyarylethers by R. J. Cotter, Gordon and Breach Publishers, ISBN 2-88449-112-0
  • a standard aromatic substitution reaction
  • thermosetting monomers may also be employed.
  • nucleophilic aromatic substitution reaction may also be utilized in a synthesis of a star shaped thermosetting monomer with a sexiphenylene as the aromatic portion as depicted in FIG. 2D, in which sexiphenylene is reacted with 4-fluorotolane to produce a star shaped thermosetting monomer.
  • phloroglucinol may be reacted in a standard aromatic substitution reaction with 1-(4-fluorophenylethynyl-4-phenylethynyl)-4-benzene to yield 1,3,5-tris(phenylethynylphenylethynylphenoxy)benzene.
  • cage compound is a silicon atom
  • an exemplary preferred synthetic scheme is depicted in FIG. 3C, in which bromo(phenylethynyl)aromatic arms (2) are converted into the corresponding lithium(phenylethynyl)aromatic arms (10), which are subsequently reacted with silicon tetrachloride to yield the desired star shaped thermosetting monomer with a silicon atom as a cage compound.
  • the cage compound is an adamantane or diamantane
  • various cage compounds other than an adamantane or diamantane are also contemplated.
  • the molecular size and configuration of the cage compound in combination with the overall length of the arms R 1 -R 4 or R′ 1 -R′ 6 will determine the size of voids in the final low dielectric constant polymer (by steric effect). Therefore, where relatively small cage compounds are desirable, substituted and derivatized adamantanes, diamantanes, and relatively small, bridged cyclic aliphatic and aromatic compounds (with typically less than 15 atoms) are contemplated. In contrast, in cases where larger cage compounds are desirable, larger bridged cyclic aliphatic and aromatic compounds (with typically more than 15 atoms) and fullerenes are contemplated.
  • contemplated cage compounds need not necessarily be limited to carbon atoms, but may also include heteroatoms such as N, S, O, P, etc. Heteroatoms may advantageously introduce non-tetragonal bond angle configurations, which may in turn enable covalent attachment of arms R 1 -R 4 or R′ 1 -R′ 6 at additional bond angles.
  • substitutents and derivatizations of contemplated cage compounds it should be recognized that many substituents and derivatizations are appropriate. For example, where the cage compounds are relatively hydrophobic, hydrophilic substituents may be introduced to increase solubility in hydrophilic solvents, or vice versa.
  • polar side groups may be added to the cage compound.
  • appropriate substituents may also include thermolabile groups, nucleophilic and electrophilic groups.
  • functional groups may be employed in the cage compound (e.g., to facilitate crosslinking reactions, derivatization reactions, etc.) Where the cage compounds are derivatized, it is especially contemplated that derivatizations include halogenation of the cage compound, and a particularly preferred halogen is fluorine.
  • the cage compound may be replaced by a non-carbon atom with a polygonal, more preferably tetragonal configuration.
  • Contemplated atoms include a silicon atom, and particularly contemplated atoms include atoms that exhibit polygonal ligand configuration and form covalent bonds with a resistance to oxidation greater than a carbon-carbon bond.
  • alternative atoms may also include cationic and anionic species of a particular atom.
  • appropriate atoms are Ge, and P.
  • thermosetting monomer has an aryl coupled to the arms R′ 1 -R′ 6 as shown in Structure 2, it is preferred that the aryl comprises a phenyl group, and it is even more preferred that the aryl is a phenyl group or a sexiphenylene.
  • various aryl compounds other than a phenyl group or a sexiphenylene are also appropriate, including substituted and unsubstituted bi- and polycyclic aromatic compounds. Substituted and unsubstituted bi- and polycyclic aromatic compounds are particularly advantageous, where increased size of the thermosetting monomer is preferred.
  • alternative aryls extend in one dimension more than in another dimension
  • naphthalene, phenanthrene, and anthracene are particularly contemplated.
  • polycyclic aryls such as a coronene are contemplated.
  • contemplated bi- and polycyclic aryls have conjugated aromatic systems that may or may not include heteroatoms.
  • substitutions and derivatizations of contemplated aryls the same considerations apply as for cage compounds (vide supra).
  • R 1 -R 4 and R′ 1 -R′ 6 are individually selected from an aryl, a branched aryl, and an arylene ether, and R′ 1 -R′ 6 are individually selected from an aryl, a branched aryl, and an arylene ether, and nothing.
  • aryls for R 1 -R 4 and R′ 1 -R′ 6 include aryls having a tolanyl, a phenylethynylphenylethynylphenyl, and a p-tolanylphenyl moiety, and tolanyl, phenylethynylphenylethynylphenyl, and p-tolanylphenyl moieties.
  • Especially preferred branched aryls include a 1,2-bis(phenylethynyl)phenyl, and particularly contemplated arylene ethers include p-tolanylphenyl ether.
  • appropriate arms need not be limited to an aryl, a branched aryl, and an arylene ether, so long as alternative arms R 1 -R 4 and R′ 1 -R′ 6 comprise a reactive group, and so long as the incorporation of the thermosetting monomer comprises a reaction involving the reactive group.
  • the term “reactive group” as used herein refers to any element or combinations of elements having sufficient reactivity to be used in incorporating the monomer into a polymer.
  • contemplated arms may be relatively short with no more than six atoms, which may or may not be carbon atoms.
  • Such short arms may be especially advantageous where the size of voids incorporated into the final low dielectric constant polymer need to be relatively small.
  • the arms may comprise a oligomer or polymer with 7-40, and more atoms.
  • the length as well as the chemical composition of the arms covalently coupled to the contemplated thermosetting monomers may vary within one monomer.
  • a cage compound may have two relatively short arms and two relatively long arms to promote dimensional growth in a particular direction during polymerization.
  • a cage compound may have two arms chemically distinct from another two arms to promote regioselective derivatization reactions.
  • a cage compound may have 4 arms, and only 3 or two of the arms carry a reactive group.
  • an aryl in a thermosetting monomer may have three arms wherein only two or one arm has a reactive group. It is generally contemplated that the number of reactive groups in each of the arms R 1 -R 4 and R′ 1 -R′ 6 may vary considerably, depending on the chemical nature of the arms and of the qualities of the desired end product.
  • thermosetting monomers may have only one or two reactive groups, which may or may not be located in one arm.
  • a relatively high degree of crosslinking is required, three or more reactive groups may be included into the monomer.
  • Preferred reactive groups include electrophilic and nucleophilic groups, more preferably groups that may participate in a cyclo addition reaction and a particularly preferred reactive group is an ethynyl group.
  • thermosetting monomers can be incorporated into a polymer by a large variety of mechanisms, and the actual mechanism of incorporation predominantly depends on the reactive group that participates in the incorporation. Therefore, contemplated mechanisms include nucleophilic, electrophilic and aromatic substitutions, additions, eliminations, radical polymerizations, and cycloadditions, and a particularly preferred incorporation is a cycloaddition that involves at least one ethynyl group located at least one of the arms.
  • the incorporation of the monomer into the polymer may comprise a cycloaddition reaction (i.e. a chemical reaction) of at least three triple bonds.
  • the incorporation of the monomer into the polymer may comprise a cycloaddition (i.e. a chemical reaction) of all of the triple bonds.
  • thermosetting monomers may be incorporated into a polymer without participation of an additional molecule (e.g., a crosslinker), preferably as a cyclo addition reaction between reactive groups of thermosetting monomers.
  • additional molecule e.g., a crosslinker
  • crosslinkers may be employed to covalently couple a thermosetting monomer to a polymer. Such covalent coupling may thereby either occur between a reactive group and a polymer or a functional group and a polymer.
  • thermosetting monomer Depending on the mechanism of incorporation of the thermosetting monomer into the polymer, reaction conditions may vary considerably. For example, where a monomer is incorporated by a cycloaddition employing a triple bond of at least one of the arm, heating of the thermosetting monomer to approximately 250° C. for about 45 min is generally sufficient. In contrast, where the monomer is incorporated into a polymer by a radical reaction, room temperature and addition of a radical starter may be appropriate. A preferred incorporation is set forth in the examples.
  • thermosetting monomers may be incorporated into the backbone, a terminus or a side chain of the polymer.
  • backbone refers to a contiguous chain of atoms or moieties forming a polymeric strand that are covalently bound such that removal of any of the atoms or moiety would result in interruption of the chain.
  • Contemplated polymers include a large variety of polymer types such as polyimides, polystyrenes, polyamides, etc. However, it is especially contemplated that the polymer comprises a polyaryl, more preferably a poly(arylene ether). In an even more preferred aspect, the polymer is fabricated at least in part from the thermosetting monomer, and it is particularly contemplated that the polymer is entirely fabricated from the thermosetting monomer.
  • the size of the cage compound or the aryl, and (2) the overall length of the arms R 1 -R 4 and R′ 1 -R′ 6 that are covalently coupled to the cage compound will determine the nanoporosity imparted by a steric effect. Therefore, where a thermosetting monomer with a cage compound or a silicon atom is part of a low dielectric constant polymer, and wherein the arms R 1 -R 4 have a total length L and the low dielectric constant polymer has a dielectric constant K, the dielectric constant K will decrease when L increases.
  • thermosetting monomer with an aryl is part of a low dielectric constant polymer, and wherein the arms R′ 1 -R′ 6 have a total length L and the low dielectric constant polymer has a dielectric constant K, the dielectric constant K will decrease when L increases. Consequently, the size of the cage compound, the aryl, and particularly the size of the arms in a thermosetting monomer can be employed to fine tune or regulate the dielectric constant of a low dielectric constant polymer harboring the thermosetting monomer.
  • the dielectric constant may be reduced in an amount of up to 0.2, preferably of up to 0.3, more preferably of up to 0.4 and most preferably of up to 0.5 dielectric constant units.
  • Phenylacetylene is a starting molecule that is reacted (A1) with TBA (supra) to yield tetrakis(mono-tolanyl)-adamantane.
  • TBA trimethylsilylacetylene
  • TBA can then be reacted (A2) with tolanylacetylene to tetrakis(bis-tolanyl)-adamantane.
  • tolanylacetylene is reacted (B2) with 1-bromo-4-iodobenzene to bistolanylbromide that is further converted (C2) to bistolanylacetylene.
  • the so formed bistolanylacetylene may then be reacted (A3) with TBA to yield tetrakis(tristolanyl)-1-adamantane.
  • thermosetting monomers according to the inventive subject matter may be employed in a dielectric layer of an electronic device, wherein preferred dielectric layers have a dielectric constant of less than 3, and preferred electric devices include an integrated circuit. Therefore, a contemplated electrical device may include a dielectric layer, wherein the dielectric layer comprises a polymer fabricated from a thermosetting monomer having the structures
  • Y is selected from a cage compound and a silicon atom
  • Ar is preferably an aryl
  • R 1 -R 4 are independently selected from an aryl, a branched aryl, and an arylene ether
  • R′ 1 -R′ 6 are independently selected from an aryl, a branched aryl, and an arylene ether and nothing, and wherein at least one of the aryl, the branched aryl, and the arylene ether has a triple bond.
  • thermosetting molecules according to the inventive subject matter, and preparation of a low dielectric constant film.
  • TBA was reacted with bromobenzene to yield tetrakis(3/4-bromophenyl)adamantane (TBPA) as described in Macromolecules, 27, 7015-7022 (1990) by Reichert, V. R. and Mathias L. J.
  • TBPA tetrakis(3/4-bromophenyl)adamantane
  • HPLC-MS analysis showed that the yield of the desired TBPA was approximately 50%, accompanied by 40% of the tribrominated tetraphenyl adamantane and about 10% of the dibrominated tetraphenyladamantane.
  • TBPA tetrakis(3/4-bromophenyl)adamantane
  • TTA Tetrakis(tolanyl)adamantane
  • TBPA was reacted with phenylacetylene to yield the final product tetrakis(tolanyl)adamantane following a general reaction protocol for a palladium-catalyzed Heck ethynylation.
  • a TTA prepared by the preceding process was dissolved in cyclohexanone to obtain a 15-20% (by weight) solution, 5 ml of which were spun onto two silicon wafers using standard procedures well known in the art.
  • the TTA was polymerized on the wafer by heating to a temperature of about 150° C. and holding for one minute under N 2 , heating to a temperature of about 200° C. and holding for one minute under N 2 , and heating to a temperature of about 250° C. and holding for one minute under N 2 , and by curing at 400° C. for one hour in N 2 after ramping up from 250° C. at 5° K./minute.
  • the k value was obtained by coating a thin film of aluminum on the cured TTA film and then doing a capacitance-voltage measurement at 1 MHz and calculating the k value based on the film thickness.
  • Step 1 Trimethylsilylethynylation of 4-bromotolane: 4-Bromotolane (10.285 g, 40.0 mMol), ethynyltrimethylsilane (5.894 g, 60.0 mMol), 0.505 g (0.73 mMol) of dichlorobis(triphenylphosphine)-palladium[II] catalyst, 40 mL of anhydrous triethylamine, 0.214 g (1.12 mMol) of copper[I] iodide, and 0.378 g (1.44 mMol) of triphenylphosphine were placed into the N 2 purged, 5-Liter 4-neck round-bottom flask, equipped with an overhead mechanical stirrer, condenser, and positioned inside a heating mantle.
  • Step 2 Conversion of 4-(Trimethylsilyl)ethynyltolane to 4-Ethynyltolane: To a 1-Liter 3 neck round-bottom flask equipped with a nitrogen inlet, an overhead mechanical stirrer, was charged 800 mL of anhydrous methanol, 12.68 g (46.2 mMol) of 4-(trimethylsilyl)ethynyltolane, and 1.12 g of anhydrous potassium carbonate. The mixture was heated to 50° C. Stirring continued until no starting material is detected by HPLC analysis (about 3 hours). The reaction mixture was cooled. The crude solids were stirred in 40 mL of dichloromethane for 30 min and filtered.
  • the filtered suspended solids by HPLC showed mainly impurities.
  • the dichloromethane filtrate was dried and evaporated to yield 8.75 g of a solid. On further drying in an oven, the final weight was 8.67 g, which represented a yield of 92.8%.
  • TBPA tetrakis(bis-tolanyl)adamantane
  • the so prepared TBTA was dissolved in cyclohexanone to obtain a 10% (by weight) solution, 5 ml of which were spun onto two silicon wafers using standard procedures well known in the art.
  • the TBTA was polymerized on the wafer by heating to a temperature of about 300° C., and cured at a temperature of 400° C. for 1 hour.
  • the k-value was determined to be 2.57. It should be especially appreciated that when the k-value was compared to the k-value of TTA, (which is a structural analog to TBTA with a shortened length of the arms) the k-value of TTA was higher at about 2.60. Thus, the contemplated decrease in the k-value due to an increased length of the arms extending from the cage compound has been experimentally confirmed.

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Priority Applications (19)

Application Number Priority Date Filing Date Title
US09/897,936 US20020022708A1 (en) 2000-07-19 2001-07-05 Compositions and methods for thermosetting molecules in organic compositions
CN01815765A CN1458945A (zh) 2000-07-19 2001-07-13 用于热固化有机组合物中的分子的组分和方法
KR1020037000737A KR100620207B1 (ko) 2000-07-19 2001-07-13 유기 조성물중에 열경화성 분자가 혼입된 조성물 및 이의제조 방법
EP01958944A EP1309639A4 (en) 2000-07-19 2001-07-13 COMPOSITIONS AND METHODS FOR THERMOSETTING MOLECULES IN ORGANIC COMPOSITIONS
PCT/US2001/022204 WO2002008308A1 (en) 2000-07-19 2001-07-13 Compositions and methods for thermosetting molecules in organic compositions
AU2001280549A AU2001280549A1 (en) 2000-07-19 2001-07-13 Compositions and methods for thermosetting molecules in organic compositions
JP2002514210A JP2004504455A (ja) 2000-07-19 2001-07-13 有機組成物における熱硬化性分子の組成物および方法
TW090117706A TWI241310B (en) 2000-07-19 2001-07-19 Compositions and methods for thermosetting molecules in organic compositions
PCT/US2001/032569 WO2002081546A1 (en) 2001-04-06 2001-10-18 Low dielectric constant materials and methods of preparation thereof
US10/466,651 US7307137B2 (en) 2001-07-05 2001-10-18 Low dielectric constant materials and methods of preparation thereof
CNA018231160A CN1643030A (zh) 2001-04-06 2001-10-18 低介电常数材料及其制备方法
JP2002579926A JP2005501131A (ja) 2001-04-06 2001-10-18 低誘電率材料およびその調製方法
CA002441901A CA2441901A1 (en) 2001-04-06 2001-10-18 Low dielectric constant materials and methods of preparation thereof
EP01983172A EP1373358A4 (en) 2001-04-06 2001-10-18 MATERIALS WITH SMALL DIELECTRICITY CONSTANT AND METHOD FOR THEIR PRODUCTION
KR10-2003-7013030A KR20040011494A (ko) 2001-04-06 2001-10-18 저유전율 재료 및 이의 제조 방법
TW090128725A TWI295673B (en) 2001-07-05 2001-11-20 Low dielectric constant materials and methods of preparation thereof
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EP1309639A1 (en) 2003-05-14
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MY134260A (en) 2007-11-30
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WO2002008308A1 (en) 2002-01-31
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US20030096938A1 (en) 2003-05-22
US6803441B2 (en) 2004-10-12

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