KR20000047306A - Polyphenylene oligomer and polymer - Google Patents

Abstract

PURPOSE: A polyphenylene oligomer and a polymer are provided which have high dielectric constant, heat stability and glass transition temperature so that they are useful as a dielectric body in microelectronic manufacturing industry. CONSTITUTION: A polyphenylene oligomer is produced through Diels-Alder reaction where not less than one compounds with more than two diene functional groups and not less than one compounds with more than two dienephilic functional groups are reacted wherein more than one compounds have three functional group. In the reaction, dienephilic functional group is acetylene group and diene group is cyclopentadienone group and both ratio between cyclopentadienone and acetylene is 1:1-1:3.

Description

Polyphenylene oligomers and polymers

The present invention relates to polyphenylene oligomers and polymers, methods of making and using the same. Such oligomers and polymers may be useful as dielectric resins in microelectronic manufacturing.

Polymer dielectrics can be used as the insulating layer between various circuits and layers within circuits in microelectronic devices such as integrated circuits, multi-chip modules and stacked circuit boards. The microelectronics manufacturing industry is oriented towards smaller geometries in the device, requiring less power and becoming faster. As conductor lines become finer and more tightly packed, the need for dielectrics between these conductors becomes more urgent.

Polymer dielectrics sometimes offer lower permittivity than inorganic dielectrics such as silicon dioxide, while in some cases attempting process integration during manufacturing. For example, to replace silicon dioxide as a dielectric in integrated circuits, the dielectric must be able to withstand the processing temperature during metallization and the annealing step in the method. Preferably, the dielectric should have a glass transition temperature higher than the processing temperature. The dielectric should also possess desirable properties under the conditions of use of the device. For example, the dielectric should not absorb water, which can increase the dielectric constant and potential corrosion of the metal conductor.

In some integration schemes, the oligomer should preferably be planarized and the gap should fill the patterned surface when applied by conventional application techniques such as spin coating.

Currently, polyimide resins are a type of material used as thin film dielectrics in the electronics industry. However, polyimide resins can absorb water and hydrolyze, resulting in corrosion of the circuit. Metal ions can migrate into the dielectric polyimide layer requiring a barrier layer between the metal line and the polyimide dielectric. Polyimides can exhibit poor planarization and gap filling properties. Non-fluorinated polyimides may undesirably have high permittivity.

See, Kumar and Nienan; Macromolecules, 1995, 28, pp 124-130 describe a number of polyphenylenes made from biscyclopentadienone and bisacetylene. They teach that polyphenylene has the potential as a photodefinable organic dielectric. See Wirasidlo and Augl; J. Polym. Sci., Part B (1969), 7 (7), 519-523, wherein 1,4-bis (phenylethynyl) benzene and 3,3 '-(1,4-phenylene) -bis (2, 4,5-triphenylpentadienone) is described. They record that an insoluble polymer that is soluble and yellow is obtained.

The materials described by Kumar and Urashidlo are soluble, but may not be suitable in some applications, such as spin coating to fill gaps, because the materials polymerize and consume relatively high molecular weight cyclopentadienone residues. . The molecular weight is too high to allow application by spin coating on the patterned surface containing the gap to be filled by the dielectric. Based on the published glass transition temperature, these materials are unable to withstand the desired processing of the inner layer dielectric in integrated circuits.

See, US Pat. No. 5,334,668; 5,236,686; 5,236,686; 5,169,929 and 5,338,823, Taur describes several methods for preparing crosslinkable polyphenylene compositions for producing glassy carbon. Polyphenylenes are prepared by polymerizing 1-bromo-4-rithiobenzene to form brominated polyphenylenes and then coupling substituted phenylacetylenes such as phenylacetylenyl phenyl acetylene to the residue bromine. Polyphenylene has a melting point of about 200 ° C. prior to crosslinking.

It may be desirable to provide the microelectronics manufacturing industry with a polymer dielectric that provides significantly low dielectric constant, high thermal stability and high glass transition temperature, and is preferably applied by spin coating to planarize and fill gaps on the patterned surface. .

In a first aspect, the present invention provides an oligomer, uncured polymer comprising a reaction product of at least one multifunctional compound containing at least two cyclopentadienone groups with at least one multifunctional compound containing at least two aromatic acetylene groups. Or a cured polymer, wherein some or all of the multifunctional compound contains three or more reactive groups.

Reactive groups used in the present invention are defined as cyclopentadienone or acetylene groups. The oligomers used in the present invention are defined as the reaction product of two or more monomer units of the present invention which fill the gap, i.e. when cured, fill a rectangular trench of 1 μm in depth and 0.5 μm in diameter without voids. Uncured polymers used in the present invention are defined as reaction products of monomers of the present invention that no longer fill gaps but contain significant unreacted cyclopentadienone or acetylene functionality. Cured polymers used in the present invention are defined as reaction products of the monomers of the present invention that contain no significant unreacted cyclopentadienone or acetylene functionality. Significant unreacted cyclopentadienone or acetylene functionality requires that these moieties to be reactive and further promote polymerization.

A feature of the present invention includes the reaction product of at least one multifunctional compound containing at least two cyclopentadienone groups with at least one multifunctional compound containing at least two aromatic acetylene groups, wherein a portion of the multifunctional compound or All contain at least three reactive groups. The advantage of this reaction product is that it can have high thermal stability, high glass transition temperature and low permittivity when filling the gaps and planarizing the patterned surface.

In a second preferred aspect, the invention comprises oligomeric, uncured products comprising the reaction product of at least one multifunctional compound containing at least two cyclopentadienone groups with at least one multifunctional compound containing at least two aromatic acetylene groups. Polymers or cured polymers, wherein some or all of the multifunctional compounds containing aromatic acetylene groups contain three or more acetylene groups.

A second aspect of the invention is that the reaction product comprises at least one multifunctional compound containing at least two cyclopentadienone groups and at least one multifunctional compound containing at least two aromatic acetylene groups, wherein the aromatic acetylene Some or all of the multifunctional compounds containing groups contain three or more acetylene groups. The advantage of this reaction product is that it has high thermal stability, high glass transition temperature and low permittivity when filling the gaps and planarizing the patterned surface.

High thermal stability, high glass transition temperature, low dielectric constant, and the ability to fill gaps and planarize patterned surfaces make the compositions of the present invention suitable as polymer dielectrics in microelectronic manufacturing. In particular, the combination of low dielectric constant, high thermal stability and high glass transition temperature allows the composition of the present invention to be used as an inner layer dielectric in integrated circuits.

Preferably, the oligomers, polymers and corresponding starting monomers of the invention are as follows:

I. Oligomers and Polymers of Formula 1

[A] _w [B] _z [EG] _v

Where

A is Has the structure of

B is Has the structure of

EG is a chemical formula

, , , , And A terminal group having one of

Wherein R ¹ and R ² are independently H or an unsubstituted or inertly substituted aromatic moiety, Ar ¹ , Ar ² and Ar ³ are independently an unsubstituted aromatic moiety or an inertly substituted aromatic moiety, M is a bond, y is an integer of at least 3, p is the number of unreacted acetylene groups in the given monomeric unit, r is less than the number of reacted acetylene groups in the given monomeric unit and p + r = y-1 And z is an integer of 0 to 1000, w is an integer of 0 to 1000, and v is an integer of 2 or more.

Such oligomers and polymers can be prepared by reacting biscyclopentadienone, aromatic acetylene containing three or more acetylene residues and, optionally, multifunctional compounds containing two aromatic acetylene residues. This reaction is a chemical formula Of biscyclopentadienone, chemical formula Of polyfunctional acetylene and optionally It can be represented by the reaction of the diacetylene compound (wherein R ¹ , R ² , Ar ¹ , Ar ² , Ar ³ and y are as defined above).

Aromatic moieties include phenyl, polyaromatic and fused aromatic moieties. Inertly substituted means a group of substituents which are essentially inert to cyclopentadienone and acetylene polymerization reactions and which do not readily react with environmental elements such as water under the conditions of use of the cured polymer in the microelectronic device. Such substituent groups include, for example, a cycloalkyl of _{F, Cl, Br, -CF 3} , -OCH 3, -OCF 3, -O-Ph and alkyl of 1 to 8 carbon atoms, having 3 to 8 carbon atoms. For example, residues that may not be substituted or inactively substituted aromatic residues are , , , , , , , , , , , , , , , , , , , , , , , , or Wherein Z is -O-, -S-, alkylene, -CF _2- , -CH _2- , -O-CF _2- , perfluoroalkyl, perfluoroalkoxy, , , , , , , , , or Wherein each R ³ is independently —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ or Ph). ph is phenyl.

II. Polyphenylene oligomers and polymers of the formula

Where

R ¹ , R ² , Ar ¹ and Ar ² are as defined above,

x is an integer from 1 to 1000. Preferably, x is 1 to 50, more preferably 1 to 10. Such oligomers and polymers Of biscyclopentadiene and It can be prepared by the reaction of diacetylene (wherein R ¹ , R ² , Ar ¹ and Ar ² are as defined above).

III. Polyphenylene oligomers and polymers of formula (5) which may be prepared by reaction of cyclopentadienone functional groups and acetylene functional groups of the multifunctional compound of formula (6)

Where

Ar ⁴ is an aromatic moiety or an inertly substituted aromatic moiety,

R ¹ , R ² and x are as defined above.

Ⅳ. Polyphenylene oligomers and polymers of formula (7) which may be prepared by reaction of cyclopentadienone functional groups and acetylene functional groups of the multifunctional compound of formula (8).

Where

EG is a chemical formula or or One of the

R ¹ , R ² , Ar ⁴ and x are as defined above.

Multifunctional compounds containing two or more aromatic cyclopentadienone residues can be prepared by condensation of benzyl and benzyl ketones using conventional methods. Exemplary methods are described in Kumar et al. Macromolecules, 1995, 28, 124-130; Ogliaruso et al., J. Org. Chem., 1965, 30, 3354; Ogliaruso et al., J. Org. Chem., 1963, 28, 2725; And US Pat. No. 4,400,540.

Multifunctional compounds containing two or more aromatic acetylene moieties can be prepared by conventional methods. The aromatic compound can be halogenated and then replaced with a substituted acetylene compound by reaction with a suitable substituted acetylene in the presence of an aryl ethynylation catalyst.

Once the multifunctional compound monomers are prepared, they are preferably purified. In particular, metal and ionic species are removed during manufacture for use as organic polymer dielectrics. For example, a multifunctional compound containing an aromatic acetylene group can be contacted with wash water, aliphatic hydrocarbon solvent and then dissolved in aromatic solvent and filtered through purified silica gel. This treatment can remove residual ethynylation catalyst. Further recrystallization can also remove unwanted impurities.

Without wishing to be bound by theory, polyphenylene oligomers and polymers are formed through the Diels Alder reaction of cyclopentadienone and acetylene groups upon heating of a mixture of cyclopentadienone and acetylene in solution. Is considered. Such oligomers may contain cyclopentadienone and / or acetylene end groups and / or pendant groups. Further heating of the solution or the product coated with the solution may further extend the chain through the Dielder reaction of the remaining cyclopentadienone end group and the remaining acetylene group to increase the molecular weight. Depending on the temperature used, reactions between acetylene groups can also occur.

Oligomers and polymers are represented by structures having cyclopentadienone and / or acetylene end groups and / or pendant groups. Generally, the end groups are combined with a stoichiometric excess of cyclopentadienone functional groups to provide more cyclopentadienone end groups and a stoichiometric excess of die elder reactive acetylene functional groups to provide more fractions of acetylene end groups. It will depend on the relative concentration of cyclopentadienone relative to the die elder reactive acetylene functional group used in the reaction.

A feature of a preferred embodiment of the present invention is to stop the polymerization reaction prior to the reaction of all cyclopentadienone residues. The oligomers can then be applied to the surface and reacted with the same amount of cyclopentadienone residues prior to developing the polymerization. In this oligomerization state, the oligomer can be planarized and fill gaps upon application to the patterned surface. Preferably, at least 10% of the cyclopentadienone residues are unreacted. Most preferably, at least 20% of the cyclopentadienone residues are unreacted. We can determine the percentage of unreacted cyclopentadienone residues by spectral analysis. Cyclopentadienone residues can be highly colored with a distinct red or purple color that fades as cyclopentadienone residues react in the visible spectrum.

As used herein, planarization means that the separated product can be planarized at least 70%, preferably at least 80%, most preferably at least 90%. When the oligomer layer is coated on separate square lines of 1 μm in diameter and 1 μm in height with an average thickness of 2 μ, the percentage or degree of planarization is calculated by the following equation:

% Planarization = (1-t _s / t _m ) × 100

Where

t _s is the height of the oligomer or polymer on the product above the average height of the oligomer or polymer,

t _m is the height of the product (1 μm). Uses according to this definition are described, for example, in Proceedings of IEEE, Vol. 80, no. 12, December, 1992, p. 1948.

While not wishing to be bound by theory, the preparation of polyphenylene polymers can typically be represented by Scheme 1 below.

Where

R ¹ , R ² , Ar ¹ , Ar ² and x are as defined above.

In addition, although not specifically shown as a structure, some carbonyl bridged species may be present in the oligomers prepared according to the particular monomers and reaction conditions used. Upon further heating, the carbonyl bridged species will essentially convert to an aromatic ring system. When using one or more acetylene containing monomers, the oligomers and polymers formed are random while structures are formed that can present blocks as shown. Dielder reactions between cyclopentadienone and acetylene functional groups can occur to form p- or m- bonds to the phenylenated ring.

Inert organic solvents may be used which can dissolve the monomers to a suitable degree and which can be heated to a suitable temperature at atmospheric, negative or overpressure. Examples of suitable solvents are mesitylene, pyridine, triethylamine, N-methylpyrrolidinone (NMP), methyl benzoate, ethyl benzoate, butyl benzoate, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctan Paddy, cyclohexylpyrrolidinone, and dibenzyl ether, diglyme, triglyme, diethylene glycol ethyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, propylene glycol phenyl ether, propylene glycol Ethers such as methyl ether, tripropylene glycol methyl ether or hydroxy ether, toluene, mesitylene, xylene, benzene, dipropylene glycol monomethyl ether acetate, dichlorobenzene, propylene carbonate, naphthalene, diphenyl ether, butyrolactone, dimethyl Acetamide, dimethylformamide and mixtures thereof The. Preferred solvents include mesitylene, N-methylpyrrolidinone (NMP), γ-butyrolactone, diphenyl ether and mixtures thereof.

The monomers can also be reacted in one or more solvents at elevated temperatures and the resulting oligomer solution can be cooled and combined with one or more additional solvents, for example to assist in processing. In another approach, the monomers can be reacted in one or more solvents at elevated temperature to form oligomers which can then be precipitated in the nonsolvent or separated by some other method for solvent removal to yield essentially solvent free oligomers. This separated oligomer can then be redissolved in one or more different solvents and the resulting solution can be used for processing.

The conditions under which the polymerization reaction is carried out most advantageously depend on various factors, including the specific reactants and solvents. In general, the reaction is carried out under a non-oxidizing atmosphere such as a nitrogen blanket or other inert gas. The reaction can be carried out purely (without solvent or other diluent). However, in order to ensure a homogeneous reaction mixture and to facilitate exothermic reactions at these temperatures, it may sometimes be desirable to use an inert organic solvent as mentioned above for the reactants.

The time and temperature most advantageously used may vary depending on the specific monomers used, in particular their reactivity, the particular oligomers or polymers and solvents desired. In general, the formation reaction of the oligomers is carried out at a temperature of 150 ° C. to 250 ° C. for a time span of 60 minutes to 48 hours. At this point, the oligomer can be used to separate from the reaction mixture or to coat the surface. Additional chain extension (development) can be carried out over a temperature of from 100 ° C. to 475 ° C., preferably from 200 ° C. to 450 ° C. over 1 minute to 10 hours, more preferably 1 minute to 1 hour. Uncured or cured polymers can be used to coat the surface by casting from solvent. While such polymers cannot fill gaps or planarize sufficiently, they can be useful in the damascence process.

The concentration at which the monomer is most advantageously used in the organic liquid reaction medium depends on a variety of factors including the particular monomer and organic liquid used and the oligomer and polymer to be produced. Generally, monomers are used in stoichiometric ratios of cyclopentadienone to acetylene in 1: 1 to 1: 3, preferably 1: 1 to 1: 2.

The oligomers or polymers can be cast directly as a film, applied as a coating or poured into non-solvents to precipitate the oligomers or polymers. Water, methanol, ethanol and other similar polar liquids are typical nonsolvents that can be used to precipitate the oligomers. Solid oligomers or polymers may be dissolved or treated from a suitable solvent. When the oligomers or polymers are obtained in solid form, they can be further processed using conventional compression molding techniques or melt spinning, casting or extrusion techniques, provided that the solid precursor has a sufficiently low glass transition temperature.

More typically, the oligomers or polymers are processed directly from the organic liquid reaction solution, and the advantages of the present invention are more fully realized in this example. Since the oligomer or polymer is soluble in the organic liquid reaction medium, the organic solution of the oligomer can be cast or applied and the solvent can be evaporated. The molecular weight increases (chain extension or development), and in some instances, the crosslinks that form the final polymer occur upon subsequent exposure to sufficient high temperatures.

The polymers of the present invention can be used as one or more insulators or dielectric layers in single or multilayer electrical interconnect structures for integrated circuits, multiple chip modules or flat panel displays. The polymers of the present invention can be used in such applications as a single dielectric or in combination with other organic polymers or inorganic dielectrics such as silicon dioxide, silicon nitride or silicon oxynitride.

For example, coatings of oligomers and polymers of the present invention, such as electrically insulating coatings used to fabricate interconnect structures on electronic wafers, can be used to spin-cast or otherwise form films of organic liquid solutions of oligomers or polymers. The substrates are coated together and then quickly evaporated by evaporating the solvent and exposing the oligomers or polymers to a high molecular weight and, in the most preferred example, to a temperature sufficient to develop the polymers as crosslinked polymers having a high glass transition temperature. It can manufacture.

The polymers of the present invention are particularly useful as low dielectric insulators in interconnect structures of integrated circuits such as made of silicon or gallium arsenide. Integrated circuits may typically have multiple layers of metal conductors separated by one or more insulating materials. The polymeric material of the present invention may be used as an insulator between discontinuous metal conductors in the same layer and / or between conductor levels of an interconnect structure. The polymers of the invention can also be used in combination with other materials such as SiO ₂ or Si ₃ N ₄ in the composite interconnect structure. For example, oligomers and polymers of the invention are described in US Pat. No. 5,550,405; US Pat. No. 5,591,677 and Hayashi et al., 1996 Symposium on VLSI Technology Digest of Technical Papers, pg 88-89. The oligomers and polymers of the present invention may be substituted for BCB or other resins set forth in the methods described.

Patterned metals partially or wholly separated by layers or regions of active substrates containing transistors and compositions of the present invention using oligomers, uncured polymers or polymers of the present invention as dielectrics in the above taught or similar methods Integrated circuit products can be fabricated that include electrical interconnect structures containing lines.

The polymers of the present invention are also useful for planarizing materials such as silicon wafers used in inductors in order to produce smaller (high density) circuitry. To achieve the desired top view, coatings of oligomers or polymers are applied from solution, such as by spin coating or spray coating, to flow to even the specific roughness of the surface of the substrate. Such methods are described in Jenekhe, S.A., Polymer Processing to Thin Films for Microelectronic Applications in Polymers for High Technology, Bowden et al. ed., American Chemical Society 1987, pp. 261-269.

In the manufacture of microelectronic devices, relatively thin, generally 0.01 to 20 μm, relatively 0.1 to 2 μm thick, films of relatively defect-free members may be prepared from substrates such as silicon, silicon-containing materials, silicon dioxide, alumina, copper, It is possible to deposit on the surfaces of silicon nitride, aluminum nitride, aluminum, quartz and gallium arsenide. The coatings are conveniently prepared in various organic solvents such as xylene, mesitylene, NMP, γ-butyrolactone and n-butyl acetate, for example from oligomeric solutions having a molecular weight of 3000 Mn or less and 5200 Mw or less. The dissolved oligomers or polymers can be cast onto the substrate by conventional spin or spray coating techniques. The thickness of the coating can be controlled by changing the solids%, molecular weight, not only the viscosity of the solution, but also the spin rate.

The polyphenylene oligomers or polymers of the invention can be applied by dip coating, spray coating, extrusion coating or more preferably by spin coating. In all cases, the environment around the substrate and coating prior to curing can be controlled in terms of temperature and humidity. In particular, NMP can absorb moisture from water vapor in the atmosphere. When dissolved in NMP, we must protect the solution from moisture and cast the film under low humidity environment. When using NMP as the solvent, the relative humidity is preferably controlled to less than 30% and the temperature to 27 ° C or higher. The coating may be cured after application with one or more hotplates, ovens or a combination of such tools.

An adhesion promoter, such as based on silane chemistry, may be applied to the substrate or added directly to the solution prior to application of the polyphenylene oligomer or polymer solution.

The oligomers and polymers of the present invention can be used in "damasense" metal tops or subtractive metal patterning schemes for the manufacture of integrated circuit interconnect structures. Methods of making damascene lines and biases are known in the art. See, eg, US Pat. Nos. 5,262,354 and 5,093,279.

Patterning of metals is a typical reactive ion etching method using oxygen, argon, nitrogen, helium, carbon dioxide, fluorine-containing compounds or mixtures thereof and other gases, such as photoresist "softmasks" or SiO ₂ , such as epoxy novolacs. And a photoresist incorporating an inorganic "hard mask" such as Si ₃ N ₄ or metal.

Oligomers and polymers are Al, Al alloys, Cu, Cu alloys, gold, silver, W and other conventional metal conductor materials (conductive) deposited by physical vapor deposition, chemical vapor deposition, evaporation, electroplating, electroless deposition and other deposition methods. Line and plug). Basic metal conductors, such as tantalum, titanium, tungsten, chromium, cobalt, alloys thereof, or nitrides thereof, use additional metal layers to fill holes, improve metal filling, improve adhesion, and provide barriers. Or to modify the metal reflectance.

Depending on the fabrication structure, the metal or dielectric material of the present invention may be removed or planarized using chemical-mechanical polishing techniques.

Multi-chip modules on active or passivated substrates such as silicon, silicate glass, silicon carbide, aluminum, aluminum nitride or FR-4 can be assembled using the polyphenylene polymer of the present invention as a dielectric material.

Flat panel displays on active or passivated substrates such as silicon, silicate glass, silicon carbide, aluminum, aluminum nitride or FR-4 can be assembled using the polyphenylene polymer of the present invention as a dielectric material.

The oligomers and polymers of the present invention may further be used as protective coatings on integrated circuit chips for protection against α-particles. The semiconductor device is sensitive to minor errors when the α particles are released from radioactive trace contaminants in the package or other adjacent materials that strike the active surface. It is possible to provide an integrated circuit having a protective coating of the polymer of the present invention. Typically, integrated circuit chips can be mounted on a substrate and placed in place using a suitable adhesive. The coating of the polymer of the invention provides an α particle protective layer for the active surface of the chip. Optionally, further protection, for example by capsules made of epoxy or silicone.

The polymer of the present invention can also be used as a substrate (dielectric material) in a circuit board or printed wiring board. Circuit boards made of the polymers of the present invention are mounted on their surface patterns for various electrical conductor circuits. In addition to the polymer of the present invention, the circuit board may include various reinforcing agents such as woven non-conductive fibers, for example glass fabrics. Such circuit boards may be single sided as well as double sided or multiple layers.

The polymers of the present invention may also be useful in reinforced compositions that reinforce the resin matrix polymer with one or more reinforcing materials such as reinforcing fibers or mats. Exemplary reinforcements include fiber glass, especially fiber glass mats (woven or nonwoven); Graphite, in particular graphite mats (woven or nonwoven); Kevlar ^™ ; Nomex ^™ and free spheres. Composites can be prepared from immersion mats and pre-molding mats in preforms, monomers or oligomers, where the mat is placed in a mold and polymerized by addition of monomers or oligomers and heating.

Polymer layer (s) of the present invention are described in Polymers for Electronic Applications, Lai, CRC Press (1989) pp. 42-47, can be patterned by methods such as wet-etching, plasma-etching, reactive-ion etching (RIE), dry etching or optical laser melting. Patterning can be carried out by a multi-step technique, in which the pattern is etched into the base layer after contouring to lithographically in a resist layer coated on the polymeric dielectric layer. Particularly useful techniques include masking some of the oligomers or polymers not to be removed, removing the unmasked oligomers or polymer moieties and then curing the remaining oligomers or polymers, for example thermally.

In addition, the oligomers of the present invention can also be used to make molded articles, films, fibers and foams. In general, techniques well known in the art for casting oligomers or polymers from solution can be used to prepare such products.

In the manufacture of shaped polyphenylene oligomers or polymer products, additives such as fillers, pigments, carbon black, conductive metal particles, abrasives and lubricious polymers can be used. The method of introducing the additives is not critical and they can conveniently be added to the oligomer or polymer solution prior to producing the molded article. Liquid compositions containing oligomers or polymers alone or liquid compositions also containing fillers may be prepared by a number of conventional techniques (drilling, rolling, dipping, brushing, spraying, spin coating, extrusion coating or meniscus coating). It can be applied to different substrates. When polyphenylene oligomers or polymers are prepared in solid form, additives can be added to the melt prior to processing into shaped articles.

The oligomers and polymers of the present invention may be prepared by solution deposition, liquid epitaxy, screen printing, melt-spinning, dip coating, roll coating, spinning, brushing (eg as varnish), spray coating, powder coating, plasma- Explosions including welding, dispersion-spraying, solution-casting, slurry-spraying, dry-powder-spraying, fluidized bed techniques, welding, wire explosion spraying and explosion bonding, compression bonding by heat, plasma polymerization, subsequent dispersion media Application to a variety of substrates by a number of methods such as dispersion in a dispersion medium, pressure bonding, pressurized heat bonding, gaseous environment vulcanization, extrusion melt polymers, hot-gas welding, baking, coating sintering, with removal of Can be. Single- and multilayer films may also be deposited on the substrate at atmospheric-water or other interfaces using Langmuir-Blodgett technology.

When the oligomers or polymers of the present invention are applied from solution, the particular conditions of the polymerization and other processing parameters most advantageously used, together with the solvents selected subsequently, are dependent on various factors, in particular the particular oligomers or polymers deposited, coating conditions, coatings. It depends on the quality and thickness of the water and on the end-use application. Representative solvents that can be used are those described above.

Substrate (s) that may be coated with the oligomers or polymers of the present invention may be certain materials having sufficient shelf life to be coated with monomers, oligomers or polymers. Representative examples of substrates include wood, metals, ceramics, glass, other polymers, paper, cardboard fabrics, wovens, nonwoven mats, synthetic fibers, Kevlar ^™ , carbon fibers, gallium arsenide, silicon, and other inorganic substrates and oxides thereof do. The substrate used is selected based on the desired application. Exemplary materials include glass fibers (woven, non-woven or strands), ceramics, aluminum, manganese, titanium, copper, chromium, gold, silver, tungsten, stainless steel, and Stahl to one (Hastalloy) ^TM, carbon steel, other metal alloys And thermoplastic polymers such as metals such as oxides thereof, thermoset and epoxy resins, polyimides, perfluorocyclobutane polymers, benzocyclobutane polymers, polystyrenes, polyamides, polycarbonates, polyarylene ethers and polyesters do. The substrate may be the polymer of the invention in cured form.

The substrate may be in any shape, the shape depending on the end use application. For example, the substrate may be in the form of disks, plates, wires, tubes, boards, spheres, rods, pipes, cylinders, bricks, fibers, woven or nonwovens, yarns (blends), sequential polymers, and woven or nonwoven mats. . In each case, the substrate can be hollow or solid. In the case of a hollow object, the polymer layer (s) can be either inside or outside the substrate, or both. The substrate may comprise a porous layer such as graphite mat or fabric, glass mat or fabric, scrim and particulate material.

The oligomers or polymers of the invention are compatible polymers, polymers with conventional solvents, metals, in particular textured metals, silicon or silicon dioxide, in particular silicon etched or silicon dioxide, glass, silicon nitride, aluminum nitride, alumina, gallium arsenide, It is directly bonded to many materials such as quartz and ceramic. However, for the purpose of increasing the adhesion, it is possible to improve the adhesion by introducing a substance.

Representative examples of such adhesion promoter materials are silanes, such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane [(CH ₃ ) ₃ -Si-NH-Si (CH ₃ ) ₃ ] An aminosilane binder such as organosilane, or γ-aminopropyltriepoxysilane, or aluminum monoethylacetoacetatediisopropylate [((isoCH ₃ H ₇ O) ₂ Al (OCOC ₂ H ₅ CHCOCH ₃ )] In some cases, the adhesion promoter is applied in a 0.01% to 5% by weight solution and the polyphenylene is applied after removing the excess solution, in other cases, for example, aluminum monoethylacetoacetate di-. The chelate of isopropylate is sprayed onto the substrate with a solution of chelate toluene, followed by baking the coated substrate for 30 minutes at 350 ° C. in oxygen to promote adhesion of very thin (eg 5 nm) aluminum oxide onto the substrate. Floor And other methods for depositing aluminum oxide may also be suitable, and additionally, for example, from 0.05% to 5% by weight of adhesion promoter, based on the weight of the monomers. It may be blended with the monomer prior to polymerization without formation of a layer.

Adhesion may also be texturing (eg, scratching, etching, plasma treatment or buffing) or cleaning (eg degreasing or ultrasonic cleaning), or treatment (eg plasma, solvent, SO ₃ , plasma incandescence). Discharge, corona discharge, sodium, wet etching or ozone treatment) or sandblasting of the substrate surface or 6MeV fluorine ions; Electrons of 50-2000 V intensity; Hydrogen cations at 0.2-500 eV to 1MeV; Helium cation at 200 KeV to 1MeV; Fluorine or chlorine ions at 0.5 MeV; Neon at 280 KeV; Oxygen rich flame treatment; Or by surface preparation using electron beam techniques such as accelerated argon ion treatment.

Oligomer of Reaction of 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) with 1,3,5-tri (phenylethynyl) benzene For the application of the oxidized product, a more preferred embodiment of the present invention is a silane-based adhesion promoter containing 3-aminopropyl silane dissolved in methoxy propanol [VM-652 from DuPont, The Dow Chemical Company AP8000 from The Dow Chemical Company is first applied to the wafer surface and then slowly rotated to spread over the entire surface, left for 2 seconds and finally dry rotated at 3000 rpm for 10 seconds. 4 ml of oligomer solution for a 200 mm wafer is dispersed on the wafer surface by rotating the wafer at 750 rpm by Millipore Gen-2, a highly precise pump / filtration system. Immediately after accelerating the wafer rotation to 2000 rpm, the polymer solution is dispersed and left at this spin rate for 20 seconds. A continuous stream of mesitylene is applied to the backside of the wafer for 5 seconds during the dispersion of the oligomer solution. After spin coating, the film is dried at 70 ° C. for 20 seconds on a hot plate. After the dry-baking step, the 2 mm to 5 mm edge beads of the coating are removed by direct application from the top of the back or near the corners with a continuous stream of methylsilane while rotating the wafer at 2000 rpm. After removing the edge beads, the oligomer is further polymerized under nitrogen blanket at 325 ° C. for 90 seconds on a hot plate. The film is crosslinked for 2 minutes at 450 ° C. on a hotplate under nitrogen or at 450 ° C. for 6 minutes in a nitrogen purged oven.

The oligomers or polymers of the present invention may be applied in combination with other additives to obtain specific results. Examples of such additives include magnetic particles such as barium ferrite, iron oxides, metal containing compounds such as mixtures with any cobalt, or other metal containing particles for use in magnetic media, optical media or other recording media; Conductive seals, conductive adhesives, conductive coatings, electromagnetic interference (EMI) / high frequency interference (RFI) shielding coatings, conductive particles such as metal or carbon for use as electrostatic dissipation and electrical contacts. When using such subscripts, the oligomers or polymers of the present invention may act as binders.

Metals, inverts, using the oligomers or polymers of the present invention also as protective against environmental conditions such as coatings (i.e., protective against one or more substances or forces in the object environment, including conditions of manufacture, storage, and use). Surface passivation can be imparted to conductors, capacitors, inductors, conductors, solar cells, glass and glass fibers, quartz and quartz fibers.

The following examples are intended to illustrate the invention and should not be construed as limiting the scope thereof. In the examples, all parts and percentages are by weight unless otherwise indicated.

Example 1

Preparation of Cyclopentadienone Compound and Acetylene Compound

Some cyclopentadienone compounds and acetylene compounds are prepared as follows. The structures of these compounds are shown in Table 1 below.

A. 4- (4- (phenylethynyl) phenyl) -2,3,5-triphenylcyclopentadienone (Compound A)

(a) Preparation of 4-bromophenylacetyl chloride

4-bromophenylacetic acid (100 g, 0.465 mol), thionyl chloride (300 mL) and DMF (about 2 mL) are charged to a 1 L round bottom three necked flask equipped with a reflux cooler and a mechanical stirrer. The reaction mixture is heated to 50 ° C. for 2 hours using a charcoal scrubber for gas evolution under nitrogen. Thionyl chloride is evaporated and the product 4-bromophenylacetyl chloride is added to the addition funnel with benzene (30 mL).

(b) Preparation of 4-bromodeoxybenzoin

Benzene (200 mL) and aluminum chloride (74 g, 0.558 mol) are mixed in a flask and a mixture of 4-bromophenylacetyl chloride and benzene in step (a) is added dropwise to allow HCl release reaction. The reaction mixture is stirred for 1-1.5 hours at room temperature and poured into ice water. Ethyl acetate (1 L) is added to dissolve the precipitated solid. The layers are separated and the organic layer is washed successively with 1M aqueous HCl, saturated aqueous NaHCO ₃ , brine and then dried over Na ₂ SO ₂ . The solvent is then evaporated to give a solid material and recrystallized from ethyl acetate / hexanes to give the title compound as a yellow solid in 84% yield.

(c) Preparation of 4-bromobenzyl

Perchloric acid (250 mL), water (250 mL), ethylene glycol dimethyl ether (glim) (500 mL), thallium nitrate (III) trihydrate (222.0 g, 0.5 mol) and 4-bromodeoxybenzoin (68.75 g, 0.25 mol) is charged to a 2 liter round bottom three necked flask equipped with a reflux condenser and a mechanical stirrer. The reaction mixture is heated to reflux for 6 hours under nitrogen. After cooling to ambient temperature, methylene chloride (500 mL) is added. The bilayer obtained is released to form the precipitated Tl (I) salt. After separating the layers and washing the organic layer with water, saturated aqueous NaHCO ₃ and brine, the obtained solid is recrystallized from 2-propanol to give the title compound.

(d) Preparation of 4- (phenylethynyl) benzyl

4-bromobenzyl (10.0 g, 0.0346 mol), phenylacetylene (3.88 g, 0.0380 mol) and (PPh ₃ ) ₂ PdCl ₂ (0.121 g, 0.0002 mol) in diethylamine (950 mL) at 72 ° C. After stirring for hours, it is concentrated to dryness. The residue is then dissolved in methylene chloride. Recrystallization from 2-propanol after standard aqueous workup affords the title compound.

(e) Preparation of Compound A

4- (phenylethynyl) benzyl (20 g, 0.0644 mol), 1,3-diphenylacetone (14.2 g, 0.0677 mol) and ethanol (150 mL) are heated to 75 ° C. Potassium hydroxide (KOH) (1.8 g, 0.0322 mol) dissolved in ethanol (15 mL) was added dropwise over 15 minutes. The reaction mixture is heated to reflux for 30 minutes, then cooled to 40 ° C. and the precipitated product is filtered off, washed with cold ethanol and dried. Recrystallization from 2-propanol affords the title compound.

B. 3,3 '-(1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (Compound B)

1,4-bis (phenylglyoxaloyl) benzene, commercially available as 1,3-diphenylacetone (1.23 g, 0.00584 mol), Bis-PGB (manufactured by Ken Seika Corporation), (1.000 g , 0.00292 mol) and ethanol (50 mL) are added to a 100 mL three neck round bottom flask equipped with a reflux condenser / nitrogen inlet. The reaction mixture is heated to reflux and an aqueous KOH solution (0.112 g, 0.002 mol) in water (2.25 mL) is added. Additional KOH is added until the solution turns black and is black. The mixture is refluxed for 45 minutes and then cooled. The precipitated black solid is collected by filtration and analyzed by ¹ H-NMR, ¹³ C-NMR, HPLC and FT-IR. All data are consistent with the formation of compound B.

C. 4,4'-bis (4- (phenylethynyl) phenoxy) -2,2 ', 3,3', 5,5 ', 6,6'-octafluorobiphenyl (Compound C)

(a) Preparation of 4-iodophenyl acetate

4-iodophenol (25.00 g, 0.114 mol) and methylene chloride (100 mL) are added to a 250 mL round bottom flask equipped with a cooler / nitrogen inlet, thermometer and dropping funnel. The slurry is stirred and pyridine (10.11 mL, 0.125 mol) is added via syringe. The reaction mixture is cooled to 10 ° C. using an ice bath and acetyl chloride (8.89 mL, 0.125 mol) is added dropwise. The mixture is stirred at 10 ° C. for 1 hour, then warmed to room temperature and stirred for 2 hours. The reaction mixture is filtered and the filtrate is washed four times with water. The organic layer is dried (MgSO ₄ ) and the solvent is removed in vacuo to give 27.3 g of orange oil. NMR analysis is consistent with the structure of the desired product.

(b) Preparation of 4- (phenylethynyl) phenyl acetate

250 ml round bottom flask with 4-iodophenyl acetate (50.00 g, 0.191 mol), phenylacetylene (23.40 g, 0.229 mol) and triethylamine (54 ml) with cooler / nitrogen inlet, thermometer and stopper Add to PdCl ₂ (PPh ₃ ) ₂ (0.200 g, 0.286 mmol) and PPh ₃ (1.50 g, 5.73 mmol) are then added and the mixture is heated to reflux. CuI (0.054 g, 0.286 mmol) is added until the reaction mixture reaches 40 ° C. After 2 hours, the reaction is cooled. The mixture is diluted with methylene chloride and poured into water (500 mL). The aqueous layer is extracted with methylene chloride (100 mL). The combined organic layers are washed three times with 300 ml of water each time, dried (MgSO ₄ ) and filtered. The solvent is removed in vacuo to yield 49 g of a yellow solid. The material is recrystallized from hexane to give pale yellow crystals (melting point: 104.5 ° C. to 105.5 ° C.).

(c) Preparation of 4- (phenylethynyl) phenol

4- (phenylethynyl) phenyl acetate (60.6 g, 0.256 mol), 20% aqueous sodium hydroxide (400 mL) and tetrahydrofuran (400 mL) are added to a 2 L Erlenmeyer flask and stirred at room temperature for 5 hours. The mixture is acidified with glacial acetic acid (120 mL) until the pH reaches 7. The aqueous layer is removed and extracted with tetrahydrofuran. The organic layers are combined and concentrated by rotary evaporation to give a tan solid. The solid is heated with hexane (700 mL) in a steam bath and the hot solution is decanted from the solid. This is repeated with a second volume of hexane (700 mL). The white solid is crystallized from the hexane solution upon cooling, separated by filtration and dried under vacuum to yield 18 g of white solid (melting point: 126 ° C. to 127 ° C.). NMR analysis is consistent with the structure of the material of interest.

(d) Preparation of Compound C

Decafluorobiphenyl (5.00 g, 14.96 mmol), 4- (phenylethynyl) phenol (5.81 g, 29.93 mmol), potassium carbonate (16.54 g, 0.1197 mol) and dimethylacetamide (150 mL) Add to a 250 ml round bottom flask equipped with nitrogen inlet, thermometer and stopper. The mixture is stirred and heated to 70 ° C. for 16.5 h. The reaction mixture is filtered to remove solids. The filtrate is added to water (500 mL) and extracted with methylene chloride. The emulsion is triturated by addition of brine, the organic layer is separated and washed twice with water and then filtered through a plug of silica gel. The solvent is removed in vacuo to give an oil. Methanol is added, filtered off, separated and dried under vacuum to form a white solid. NMR spectra match the structure of the title compound.

D. 4- (4-ethynylphenyl) -2,3,5-triphenylcyclopentadienone (Compound D)

Compound D is prepared as in Example 1A using triphenylsilylacetylene instead of phenylacetylene and the dimethyl base is used to remove the trimethylsilyl protecting group.

E. 3,4-bis- (4- (phenylethynyl) phenyl) -2,5-diphenylcyclopentadienone (Compound E)

(a) Preparation of 4,4'-dibromobenzoin

4-bromobenzaldehyde (25.0 g, 0.135 mol), 3-ethyl-5- (2-hydroxyethyl) -4-methylthiazolium bromide (1.70 g, 0.0068 mol) and triethylamine in ethanol (125 mL) A solution of (4.10 g, 0.0405 mol) is stirred at room temperature for 60 hours. The reaction mixture is dried and concentrated, dissolved in CH ₂ Cl ₂ (150 mL), washed with 1M HCl and saturated aqueous NaHCO ₃ , dried (Na ₂ SO ₄ ), then concentrated to solidify on standing at room temperature. 25.2 g (100%) of a viscous yellow oil are obtained.

¹ H NMR (CDCl ₃ ) δ7.73 (d, J = 8.5Hz, 2H), δ7.52 (d, J = 8.5Hz, 2H), 7.44 (d, J = 8.2Hz, 2H), 7.17 (d , J = 8.2 Hz, 2H); ¹³ C NMR (CDCl ₃ ) δ 197.33, 137.56, 132.33, 132.13, 131.90, 130.43, 129.46, 129.31, 122.93, 75.68.

(b) Preparation of 4,4'-dibromobenzyl

Of 4,4'-dibromobenzoin (20.2 g, 0.055 mol), ammonium nitrate (4.6 g, 0.0575 mol) and copper (III) acetate (0.100 g, 0.0005 mol) in 80% aqueous acetic acid (200 mL) The solution is heated to reflux for 3 hours. The reaction mixture is cooled to room temperature and the crystallized product is filtered off, washed with ethanol and dried to give 13.0 g (64%) of the product as a pale yellow solid (melting point: 226 ° C. to 228 ° C.).

¹ H NMR (CDCl ₃ ) δ 7.83 (d, J = 8.5 Hz, 4H), 7.66 (d, J = 8.5 Hz, 4H); ¹³ C NMR (CDCl ₃ ) δ192.25, 132.44, 131.45, 131.22, 130.7.

(c) Preparation of 4,4'-bis (phenylethynyl) benzyl

4,4'-bromobenzyl (15.8 g, 0.0431 mol) in diethylamine (150 mL), phenylacetylene (5.06 g, 0.0495 mol), (PPh ₃ ) ₂ PdCl ₂ (0.151 g, 0.0002 mol) and CuI A solution of (0.820 g, 0.0043 mol) is heated to reflux overnight. The reaction mixture is dried and concentrated, dissolved in CH ₂ Cl ₂ (150 mL), washed with 1M HCl, 10% Na ₂ CO ₃ / H ₂ O, brine, dried (Na ₂ SO ₄ ) and concentrated. . Crystallization from 2-propanol yields 7.92 g (45%) as a pale yellow solid (melting point: 168 ° C to 170 ° C).

¹ H NMR (CDCl ₃ ) δ 7.97 (d, J = 8.2 Hz, 4H), 7.64 (d, J = 8.2 Hz, 4H), 7.55 (m, 4H), 7.37 (m, 6H); ¹³ C NMR (CDCl ₃ ) δ193.03, 132.46, 132.03, 131.82, 130.21, 129.84, 129.06, 128.47, 122.37, 94.28, 88.55.

(d) Preparation of Compound E

A solution of KOH (0.34 g, 0.0061 mol) in ethanol (5 mL) was added to 4,4'-bis (phenylethynyl) benzyl (5.0 g, 0.0122 mol) and 1,3- in ethanol (75 mL) at 75 ° C. It is added dropwise to a solution of diphenylacetone (2.69 g, 0.0128 mol). The resulting solution is heated to reflux for 1 hour, cooled to room temperature and the precipitate is filtered off and dried. Dipping the product from boiling ethanol to give 5.26 g (74%) of the product as a reddish brown solid (melting point: 222 ° C. (DSC));

¹ H NMR (CDCl ₃ ) δ7.5 (bd, J = 3.6 Hz, 4H), 7.34 (m, 5H), 7.25 (bs, 5H), 6.93 (d, J = 8.0 Hz, 4H); ¹³ C NMR (CDCl ₃ ) δ199.02, 152.72, 132.31, 131.14, 130.83, 129.93, 129.67, 128.99, 128.04, 127.93, 127.71, 127.28, 125.31, 123.12, 122.46, 90.60, 88.71; MS (EI) 585 (28), 584 (M +, 56), 556 (19), 378 (36), 278 (100).

F. 3,4-bis- (3- (phenylethynyl) phenyl) -2,5-diphenylcyclopentadienone (Compound F)

(a) Preparation of 3,3'-dibromobenzoin

3-bromobenzaldehyde (25.0 g, 0.135 mol), 3-ethyl-5- (2-hydroxyethyl) -4-methylthiazolium bromide (1.70 g, 0.0068 mol) and triethylamine in ethanol (125 mL) Except for (4.10 g, 0.0405 mol), it prepared as in Example 1E (a) and obtained 24.8 g (99%) of a viscous yellow oil.

¹ H NMR (CDCl ₃ ) δ 8.04 (s, 1H), 7.75 (d, J = 7.8 Hz, 1H), 7.61 (d, J = 8.0 Hz, 1H), 7.47 (s, 1H), 7.26-7.15 ( m, 4H), 5.87 (s, 1 H); ¹³ C NMR (CDCl ₃ ) δ 196.96, 140.48, 136.86, 134.94, 131.93, 131.86, 130.69, 130.63, 130.26, 127.57, 126.33, 123.19, 75.76.

(b) Preparation of 3,3'-dibromobenzyl

From 3,3'-dibromobenzoin (24.8 g, 0.067 mol), ammonium nitrate (5.63 g, 0.070 mol) and copper (III) acetate (0.12 g, 0.0007 mol) in 80% aqueous acetic acid (200 mL) Prepared as in Example 1E (b), except to yield 17.0 g (69%) of the product as a pale yellow solid.

¹ H NMR (CDCl ₃ ) δ 8.12 (s, 2H), 7.88 (d, J = 7.8 Hz, 2H), 7.79 (d, J = 7.9 Hz, 2H), 7.40 (dd, J = 8.0, 8.0 Hz, 2H); ¹³ C NMR (CDCl ₃ ) δ 191.58, 137.87, 134.27, 132.53, 130.60, 128.59, 123.39.

(c) Preparation of 3,3'-bis (phenylethynyl) benzyl

A solution of 3,3'-dibromobenzyl (5.0 g, 0.0136 mol) and phenylacetylene (3.47 g, 0.0340 mol) in triethylamine (30 mL) was degassed by bubbling nitrogen through the solution for 10 minutes. Then (PPh ₃ ) ₂ PdCl ₂ (0.067 g, 0.0001 mol) is added and the reaction mixture is heated to reflux overnight. After the mixture was concentrated to dryness, it was dissolved in CH ₂ Cl ₂ (100 mL), subsequently washed with 1M HCl, saturated aqueous NaHCO ₃ and dried (Na ₂ SO ₄ ), then concentrated to give the product 3.67 as a white solid. g (66%) is obtained (melting point of 144 ° C to 145 ° C);

¹ H NMR (CDCl ₃ ) δ 8.12 (s, 2H), 7.96 (d, J = 7.9 Hz, 2H), 7.81 (d, J = 7.7 Hz, 2H), 7.52 (m, 6H), 7.36 (m, 6H); ¹³ C NMR (CDCl ₃ ) δ 192.83, 137.40, 132.82, 131.52, 129.04, 128.58, 128.25, 124.50, 122.37, 91.11, 87.62.

(d) Preparation of Compound F

A solution of KOH (0.25 g, 0.0045 mol) in ethanol (5 mL) was treated with 3,3'-bis (phenylethynyl) benzyl (3.67 g, 0.0089 mol) and 1,3- in ethanol (100 mL) at 75 ° C. It is added dropwise to a solution of diphenylacetone (2.07 g, 0.0098 mol). The resulting solution is heated to reflux for 1 hour and then cooled to room temperature. The precipitate obtained is filtered off and dried. The product was immersed from boiling ethanol to yield 2.0 g (38%) of product as a reddish brown solid (melting point: 208 ° C.) (DSC)).

¹ H NMR (CDCl ₃ ) δ 7.45 (bm, 6H), 7.31-7.21 (bm, 20H), 6.9 (d, J = 7.9 Hz, 2H); ¹³ C NMR (CDCl ₃ ) δ 199.38, 152.83, 132.87, 131.48, 131.25, 131.12, 129.80, 129.60, 128.53, 127.99, 127.92, 127.84, 127.70, 127.29, 125.03, 122.96, 122.47, 90.60, 88.

G. 1,3,5-tris (phenylethynyl) benzene (Compound G)

Triethylamine (375 g), triphenyl phosphine (4.7865 g), palladium acetate (1.0205 g) and N, N-dimethyl formamide (2000 mL) were added to a thermocouple, overhead mechanical stirrer, cooler, addition funnel, and temperature controller. Fill a 5 L three-neck round bottom flask equipped with a heating mantle with. This mixture is stirred for 5 minutes to dissolve the catalyst. Then, diethylhydroxylamine (5 g), 1,3,5-tribromobenzene (190 g) and phenylacetylene (67.67 g) are added. After purging the reactor for 15 minutes with nitrogen, it is heated to 70 ° C. while maintaining a nitrogen atmosphere. After heating at 70 ° C. for 30 minutes, phenylacetylene (135.33 g) is slowly added dropwise over about 1 hour and the temperature is raised to 80 ° C. Heat continuously for an additional 9 hours. The reaction is then cooled to room temperature and water (1 L) is added to precipitate the crude product. The product is filtered and washed three times with 500 ml of water each time and then once with 500 ml of cyclohexane. The crystals were vacuum dried at 75 ° C. overnight to give 226.40 g (99.1% yield) of 97.25 area% pure by gas chromatography. The crystals are dissolved in toluene (1800 mL), refiltered through silica gel and the solvent is removed on a rotary evaporator to give 214.2 g (94.2% yield) of 99.19 area% pure by gas chromatography. The residue is then recrystallized from a mixture of toluene (375 mL) and 2-propanol (696 mL). The white crystals were filtered off, washed with a mixture of toluene (100 mL) and 2-propanol (400 mL), and dried in vacuo at 75 ° C. overnight to give 1,3,5-tris (99.83 area% pure water) by gas chromatography. Phenylethynyl) benzene (190.0 g, 83.91% yield) is obtained. Further recrystallization from toluene / isopropanol yields materials with organic and ionic purity as permitted.

H. 4,4'-bis (phenylethynyl) diphenyl ether (Compound H)

Triethylamine (111.5 g), triphenyl phosphine (1.158 g), palladium acetate (0.2487 g), in a 1 liter three-necked round bottom flask with a thermocouple well equipped with a heating mantle with an overhead mechanical stirrer, cooler and temperature controller, Charge diethylhydroxylamine (1.24 g), 4,4'-dibromodiphenyl ether (68.6 g), phenylacetylene (67.74 g), N, N-dimethyl formamide (136 mL) and 72 mL water . The reactor is purged with nitrogen for 15 minutes and then heated to 90 ° C. while maintaining a nitrogen atmosphere for 19 hours. The reaction is then cooled to room temperature and water (80 mL) is added. The crude product was filtered off, and the solid was washed once with 120 ml of toluene and four times with 160 ml of water each time and dried overnight in vacuo by gas chromatography to give 99.64 area% pure 4,4′-bis (phenylethynyl ) 66.37 g (85.6% yield) of fine white needles of ether are obtained.

I. 4,4 "-bis (phenylethynyl) -o-terphenyl (Compound I)

(a) Preparation of 4,4 "-Dibromo-o-terphenyl

o-terphenyl (100 g), Fe (5 g) and CHCl ₃ (475 mL) are charged to a 1 L three-necked flask equipped with a mechanical stirrer, a cooler connected to an HBr trap and an addition funnel. The mixture is stirred and the temperature is maintained by a water bath. Br ₂ (47.5 mL) in CHCl ₃ (150 mL) is added dropwise over 2.5 hours. The mixture is further stirred at room temperature for 2 hours. GC represents 5% monobromo-o-terphenyl, 81% dibromo-o-terphenyl and 9% tribromo-o-terphenyl.

Ice and 2N NaOH solution are added to the solution until basic. Drain the top layer and wash the CHCl ₃ solution with additional water. Sodium sulfate is then added to the CHCl ₃ solution and then filtered through a Buchner funnel filled with celite. Remove chloroform. 750 ml of glacial acetic acid is added to the white solid and the slurry is heated in a water bath at 95 ° C. Dissolve about half of the solid. Pour the hot solution into a 1000 ml beaker. Remaining solids were 71 g, 1.4% monobromo-o-terphenyl, 93% 4,4 "-dibromo-o-terphenyl and 6% 4,4 ', 4" -tribromo-o- It consists of terphenyl. The acetic acid solution is cooled to room temperature. Collect white crystals. GC represents 1% monobromo-o-terphenyl, 83% 4,4 "-dibromo-o-terphenyl and 13% 4,4 ', 4" -tribromo-o-terphenyl. This material is used in the preparation of 4,4 "-bis (phenylethynyl) -o-terphenyl.

(b) Preparation of Compound I

4,4 "-dibromo-o-terphenyl (40 g, 0.0103 mol), phenylacetylene (50 mL), triethylamine (500 mL) and pyridine (300 mL) were charged with a mechanical stirrer, cooler, N ₂ inlet and Fill a 1000 ml four necked flask equipped with a thermometer Purge the system for 20 minutes with nitrogen.

After dissolving the solid, 2.783 g of Pd (PPh ₃ ) ₂ Cl _2, 2.538 g of CuI and 5.545 g of PPh ₃ are added. Nitrogen is bubbled through the solution with stirring for 30 minutes. Heat to reflux the mixture. Continue to reflow overnight. White solids are formed during the reaction.

The solution is placed in a 2 L beaker with ice. The flask is washed several times with water and poured into the beaker. The solid formed is filtered through a Buchner funnel and washed several times with water. Toluene is used to dissolve the solids in a 2 L beaker. Pour the top layer into a 1 L flask. The bottom layer containing undissolved material is washed with toluene and combined with the top layer drained off toluene solution to form a dark brown solution. The dark brown solution is decolorized with charcoal. The solution is heated in a water bath while stirring. Then Na ₂ SO ₄ is added.

The solution is filtered through a sintered glass filter and the solvent is evaporated off. The solid is dissolved in a 2 L beaker with 350 ml of hot toluene and once dissolved, 1300 ml of isopropanol is added to crystallize the solid. After placing the 2 L beaker in the refrigerator overnight, the crystals are collected and washed with isopropanol. Yellow solid is 25 g. The yellow solid is washed with acetone and then crystallized twice in ethyl acetate. The yield of a white piece is 12g.

J. 4,4'-diethynyldiphenyl ether (compound J)

4,4'-dibromodiphenyl ether (9.8 g, 0.030 mol) in triethylamine (40 mL), Pd (OAc) ₂ (0.05 g, 0.0002 mol), copper (I) iodide (0.15 g, 0.0008 mol) ) And a slurry of triphenylphosphine (1.0 g, 0.0038 mol) is sparged with nitrogen for 30 minutes with slow reflux heating to reflux.

2-Methyl-3-butyn-2-ol (7.6 g, 0.090 mol) sparged with nitrogen for 30 minutes is quickly added to the reflux solution over 5 minutes. The reaction mixture obtained is heated to reflux for 14 hours, cooled to ambient temperature and concentrated to dryness. The residue is dissolved in CH ₂ Cl ₂ , washed with water and brine and then concentrated. The residue is dissolved in toluene (200 mL) and sodium hydride (0.10 g, 0.20 mol) is added. The reaction mixture is heated to reflux and about 100 ml of solvent is distilled off. After cooling the solution, it is concentrated. The residue is dissolved in CH ₂ Cl ₂ , washed with 1N HCl, water, saturated aqueous NaHCO ₃ and brine, then dried (Na ₂ SO ₄ ) and concentrated to give a black oil. The residue is filtered through a pad of silica gel, eluted with CH ₂ Cl ₂ and concentrated to give a viscous oil that slowly solidifies upon standing.

¹ H NMR (CDCl ₃ ) δ 7.45 (d, J = 8.6 Hz, 4H), 6.93 (d, J = 8.7 Hz, 4H), 3.04 (s, 2H); ¹³ C NMR (CDCl ₃ ) δ 157.02, 133.93, 119.20, 118.94, 117.16, 83.16. The reaction scheme is shown in the following scheme 2.

K. 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (Compound K)

(a) Preparation of 4,4'-diphenylacetyldiphenyl ether

To a slurry of aluminum chloride (97.9 g, 0.734 mol) in methylene dichloride (200 ml) at 0 ° C. diphenyl ether (50.0 g, 0.294 mol) and phenylacetyl chloride (102 g, 0.661 mol) in methylene chloride (50 ml) Solution is added dropwise over 30 minutes. When the addition is complete, the reaction mixture is warmed to ambient temperature and stirred overnight. The reaction mixture is carefully poured into 1.5 kg of ice / water while stirring. Methylene chloride (1500 mL) is added to dissolve the solids and separate the layers. The organic layer is filtered through celite and then concentrated to dryness. Recrystallization from toluene yields 110 g (92%) of the title compound as a pale yellow prism.

(b) Preparation of 4,4'-bis (phenylglyoxaloyl) diphenyl ether

Aqueous HBr (97 mL of 48 wt% solution) was added to a slurry of 4,4′-diphenylacetyldiphenyl ether (50.0 g, 0.123 mol) in DMSO (400 mL) and the resulting mixture was brought to 100 ° C. for 2 h. After heating, it is cooled to ambient temperature. The reaction mixture is partitioned between toluene (500 mL) and water (750 mL). The organic layer is washed with water (3 x 250 mL), then brine and concentrated to give a viscous pale yellow oil which solidifies upon standing at ambient temperature. Recrystallization from ethanol affords 35.9 g (67%) of the title compound as a pale yellow cube.

(c) Preparation of Compound K

195.4 g (0.4498 mol, 1.0) of 4,4'-bis (phenylglyoxaloyl) diphenyl ether in a nitrogen purged 5 l Morton flask equipped with a thermocouple, reflux condenser with nitrogen inlet, mechanical stirrer and addition funnel eq), 193.9 g (0.9220 mol, 2.05 eq) of diphenylacetone and 2.5 L of deoxygenated ethanol are added. The mixture is heated to reflux, whereby a homogeneous solution is obtained, which is sparged with nitrogen for 30 minutes. To the addition funnel is added a solution containing 25.2 g of KOH (0.4498 mol, 1.0 eq), 200 ml of ethanol and 25 ml of water. The temperature is reduced to 74 ° C. and the KOH solution is added quickly over 5 minutes. The exothermic reaction is quickly set and maintained at reflux until 3/4 of the solution is added, after which the temperature is reduced. Dark purple is observed immediately after base addition and solids are observed before the addition is complete. After completion of the addition, the homogeneous solution is heated strongly reflux for 15 minutes, forming much more solid product. The mixture is cooled to 25 ° C. and 29.7 g (0.4948 mol, 1.1 eq) of glacial acetic acid are added and stirred for 30 minutes. The crude product was isolated by filtration, washed with 1 liter of water, 3 liters of EtOH and 2 liters of MeOH in a filtration funnel and dried for 12 hours at 60 ° C. to 90 ° C. under vacuum to give 323 g (92%) of crude DPO-CPD 94% pure by LC. ). The crude material is dissolved in HPLC grade methylene chloride (10% by weight) and transferred to a 5L moton flask equipped with a bottom flush valve and a mechanical stirrer, with 2 to 2 volumes of the same volume of low ion water for 10 to 90 minutes. Wash vigorously seven times. The CH ₂ Cl ₂ solution is then fired through a 5 cm column containing 75 g of silica gel in CH ₂ Cl ₂ . The column is washed with 1 L of additional CH ₂ Cl ₂ , wherein the filtrate is essentially transparent. The solution is dried and evaporated, redissolved in THF and evaporated again to remove the bulk of methylene chloride remaining. The powder is transferred to a 5 L flask equipped with an addition funnel and a Friedrichs reflux cooler and dissolved in deoxygenated HPLC THF at reflux (0.07 to 0.12 g / ml). Then, additional 1 liter of THF is added and a nitrogen sparger tube is injected into the solution. The solution is sparged with nitrogen for 3 hours and the THF is cooled at 45 ° C. to 50 ° C. while distilling off the remaining methylene chloride. The distillation head is attached and 700 mL to 1 L of THF is removed. The solution is then slowly cooled to room temperature over several hours and then cooled to 10 ° C. or less with an ice bath during which crystallization occurs. The crystals are separated using a 5 mm PTFE filter in a 4 L Millipore clamp-frit suction filtration flask. The crystals are then washed with 1 L of MeOH and dried under vacuum at 80 ° C. to 90 ° C. overnight to give 70% to 85% yield of DPO-CPD with a 99% LC purity (melting point: 270 ° C.).

L. 2,4,4'-tris (phenylethynyl) diphenyl ether (compound L)

(a) Preparation of 2,4,4'-tribromodiphenyl ether

Bromine (57.3 g, 0.358 mol) is slowly added dropwise to purely stirred diphenyl ether (20.0 g, 0.118 mol) at 40 ° C. During the addition, the temperature is slowly raised to 60 ° C. and the reaction is held at this temperature for 2 hours. The mixture is then heated to 70 ° C. for 30 minutes and then cooled to ambient temperature. The mixture was dissolved in CH ₂ Cl ₂ (100 mL), washed with 10% aqueous Na ₂ CO ₃ , then dried (Na ₂ SO ₄ ) and concentrated to give a product as a viscous oil that slowly solidified on standing at ambient temperature 44.8 g (100%) is obtained.

(b) Preparation of Compound L

2,4,4'-tribromodiphenyl ether (44.3 g, 0.116 mol) in triethylamine (300 mL), Pd (OAc) ₂ (0.182 g, 0.00081 mol), copper iodide (I) (574 g, 0.00302) Mol) and triphenylphosphine (3.95 g, 0.0151 mol) are sparged with nitrogen for 30 minutes with slow reflux heating.

Phenylacetylene (41.4 g, 0.406 mol) sparged with nitrogen for 30 minutes is quickly added to the reflux solution over 5 minutes. The reaction mixture obtained is heated to reflux for 14 hours. The solution is cooled to ambient temperature and concentrated. The residue is dissolved in CH ₂ Cl ₂ and washed with 1N HCl, water, saturated aqueous NaHCO ₃ and brine and then concentrated to 100 ml volume. This solution is filtered through a pad of silica gel, eluted with methylene chloride and the filtrate obtained is shrunk. The residue is crystallized from EtOAc / hexanes to give 39.0 g (73%) as a pale brown solid (melting point: 123 ° C. to 126 ° C.).

¹ H NMR (CDCl ₃ ) δ 7.77 (bs, 1H), 7.53-7.44 (m, 14H), 7.34-7.26 (m, 20H), 6.98 (dd, J = 8.0, 8.0, 2H); ¹³ C NMR (CDCl ₃ ) δ 156.81, 156.00, 136.49, 132.93, 132.57, 131.31, 131.22, 128.23, 128.10, 128.06, 127.99, 127.87, 123.04, 122.74, 122.51, 119.63, 119.09, 118.67, 118.67, 117. 89.47, 88.72, 87.79, 83.87.

M. 3,3 '-(1,4-phenylene) bis (2,5-di- (4-fluorophenyl) -4-phenylcyclopentadienone) (Compound M)

1,4-bis (phenylglyoxaloyl) sold as 1,3-bis (4-fluorophenyl) -2-propanone (1.476 g, 0.006 mol) and Bis-PGB (manufactured by Ken Seika Corporation) Benzene (1.026 g, 0.003 mol) is added to 90 ml of 1-propanol and benzyltrimethylammonium hydroxide (0.32 g, 40% in methanol). The solution turns purple in a flash. Reflux is continued for 2 hours. The mixture is cooled to room temperature and then to 0 ° C. The solid is collected and washed with cold methanol. The yield is 1.92 g. The solid has a metallic luster and melts at 316 ° C. as measured by DSC.

1,3-bis (4-fluorophenyl) -2-propanone is described in E. Elce, A.S. Hay, J. Poly. Sci .: Part A: Polymer Chemistry, 33, 1143-1151 (1995).

N. 4,4 ', 4 "-tris (phenylethynyl) -o-terphenyl (Compound N)

(a) Preparation of 4,4 ', 4 "-tribromo-o-terphenyl

o-terphenyl (36.9 g), Fe (3.3 g) and CHCl ₃ (450 mL) are charged to a 1 L three-necked flask equipped with a mechanical stirrer, a cooler connected to an HBr trap and an addition funnel. The mixture is stirred and the temperature is maintained by a water bath. Br ₂ (26.5 mL) in CHCl ₃ (100 mL) is added dropwise over 1.5 hours. The mixture is further stirred at room temperature for 2 hours and then at 65 ° C. for 2 hours. GC represents 14% dibromo-o-terphenyl, 85% tribromo-o-terphenyl and 0.7% tetrabromo-o-terphenyl.

Ice and 2N NaOH solution are added to the solution until the solution is basic. Drain the top layer and wash the CHCl ₃ solution with additional water. Sodium sulfate is added to the CHCl ₃ solution and then filtered through a Buchner funnel filled with celite. Remove chloroform. The white solid is mixed with 750 ml of glacial acetic acid and the slurry is heated at 95 ° C. with a water bath. Solid yield after removal of all acetic acid is 42.5 g, 11% 4,4 "-dibromo-o-terphenyl, 88% 4,4 ', 4" -tribromo-o-terphenyl and 0.6% tetra Consisting of bromo-o-terphenyl. The solid is used to prepare 4,4 ', 4 "-tris (phenylethynyl) -o-terphenyl. The acetic acid solution is 56% 4,4" -dibromo-o-terphenyl, 36% 4, 4 ', 4 "-tribromo-o-terphenyl and 1.8% tetrabromo-o-terphenyl.

(b) Preparation of Compound N

4,4 ', 4 "-tribromo-o-terphenyl (24.7 g. 0.053 mol), phenylacetylene (22 ml), triethylamine (280 ml) and pyridine (180 ml) were added to a mechanical stirrer, cooler and Fill a 1000 ml four-necked flask with N ₂ inlet and thermometer Purge the system for 20 minutes with nitrogen.

After dissolving the solid, Pd (PPh ₃ ) ₂ Cl ₂ (1.113 g), CuI (1.005 g) and PPh ₃ (2.218 g) are added. Nitrogen is bubbled through the solution with stirring for 30 minutes. Heat and reflux the mixture overnight. White solids are formed during the reaction.

The solid is placed in a 2 L beaker containing ice. The flask is washed several times with water and poured into the beaker. The sticky solid formed is filtered through a Buchner funnel and then washed several times with water. Toluene is used to dissolve the solids in a 2 L beaker. Pour the top layer into a 1 L flask. The lower layer containing undissolved material is washed with toluene and the toluene solution is combined to form a dark brown solution and then decolorized with charcoal. The solution is heated in a water bath while stirring. Then Na ₂ SO ₄ is added. The solution is filtered through a sintered glass filter and the solvent is evaporated off. The sticky solid is dissolved in a 2 L beaker with 600 ml of hot acetone. The crystals are then collected and washed with acetone. Pale yellow solid is 11 g. The solid is crystallized twice from ethyl acetate. The yield of white powder is 8 g.

O. 1,3-bis (phenylethynyl) benzene (Compound O)

Phenylacetylene (8.0 g, 78.3 mmol), 1,3-dibromobenzene (6.24 g, 26.5 mmol), bis (triphenylphosphine) palladium (II) chloride (0.557 g, 0.794 mmol), triphenyl Phosphine (1.11 g, 4.23 mmol), copper iodide (I) (0.503 g, 2.64 mmol), pyridine (73 mL, 0.93 mol), triethylamine (110 mL, 0.783 mol) were mixed and under nitrogen Stir for 30 minutes. The mixture is then refluxed overnight. Pour the solution into a water / ice bath. The solid formed is collected and washed with water. The solid is dissolved in toluene and the insoluble material is filtered off. The toluene solution is decolorized with charcoal. Isopropanol is added to form yellow crystals. The crystals are separated by filtration and weighed 4.0 g (13.1 mmol, 50% yield). Melting point is 109 ° C (DSC). NMR and mass spectroscopic analysis are consistent with the shown structure of 1,3-bis (phenylethynyl) benzene.

P. 1,4-bis (phenylethynyl) benzene (Compound P)

Compound P is prepared like compound O, except that 1,4-dibromobenzene is used instead of 1,3-dibromobenzene.

Q. 1,2,4-tris (phenylethynyl) benzene (Compound Q)

A slurry of 1,2,4-tribromobenzene in triethylamine (250 mL) is degassed by sparging with N ₂ for 30 minutes. Triphenylphosphine (2.2 g, 0.00836 mol) is followed by Pd (OAc) ₂ (0.100 g, 0.000445 mol) and CuI (0.315 g, 0.00165 mol) and the resulting mixture is heated to reflux. Phenylacetylene (20.1 g, 0.197 mol) sparged with N ₂ for 30 minutes is added dropwise over 10 minutes. The reaction mixture is heated to reflux overnight. The reaction mixture is cooled to ambient temperature, dried and concentrated. The residue is dissolved in acetone (200 mL) and water (300 mL) is added slowly with stirring. The precipitate was filtered off, washed with methyl alcohol (500 mL) followed by water (200 mL) and dried to give a pale brown solid, which was then further recrystallized from acetone / methanol to further refine the white solid to 60% yield. Obtained as It is consistent with the structure of the material for NMR analysis. The reaction scheme is shown in the following scheme 3.

Example 2

Preparation of Polymer from Mixture of Compound M and 1,3-bis (phenylethynyl) benzene (Compound O) and 1,3,5-tris (phenylethynyl) benzene (Compound G)

Compound (M) (316 mg, FW = 762, 0.415 mmol), Compound (O) (72 mg, FW = 278, 0.259 mmol) and Compound (G) (44 mg, 0.116 mmol) were used for 42 hours. Reflux in 1,3-diisopropylbenzene (4 mL). The black solution turns red and becomes viscous. The solution is spin-coated onto a wafer and cured at 400 ° C. for 1 hour to form a film. The reaction scheme is shown in Scheme 4 below.

Example 3

Compound M and mixture of 4,4'-bis (phenylethynyl) -o-terphenyl (Compound I) with 4,4 ', 4 "-tris (phenylethynyl) -o-terphenyl (Compound N) Polymer Preparation from

Compound (M) (316 mg, 0.415 mmol), Compound (I) (107 mg, FW = 430, 0.249 mmol) and Compound (N) (88 mg, FW = 530, 0.166 mmol) for 48 hours. Reflux in 5 ml of 1,3-diisopropylbenzene. The yellow viscous solution is cooled to room temperature and spin-coated onto the wafer. The polymer is cured at 400 ° C. for 1 hour to form a film. The reaction scheme is shown in Scheme 5 below.

Example 4

3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (compound K) and 4,4'-bis (phenylethynyl) diphenyl ether Polymer Preparation from (Compound H)

3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (15.0000 g, 0.019158 mol), 4,4'-bis (phenylethynyl) Diphenyl ether (7.0974 g, 0.019158 mol) and N-methylpyrrolidone (51.06 g) are added to a 250 ml round bottom flask. The flask is attached to a nitrogen inlet and the mechanically stirred solution is heated to 200 ° C. in an oil bath. After 19.5 hours at 200 ° C., gel permeation chromatography shows Mn 1551 and Mw 2383 compared to polystyrene standards. Cool the solution and place in a bottle. A fraction of the solution is dissolved in a syringe and filtered through a 1.0 μ scanning filter on a 4 "silicon wafer. The wafer is spin-coated at 2000 rpm for 60 seconds under a heating lamp that warms the wafer. The coated wafer is then several minutes On a hotplate set at 90 ° C. The wafer is then placed in a nitrogen purged oven where it is cured by purging at room temperature for 45 minutes and then heated to 400 ° C. at 10 ° C./min and 400 for 1 hour. After standing at < RTI ID = 0.0 > C, < / RTI > the resulting wafer is coated with polyphenylene polymer The solution was found to completely fill the gap when applied and cured to a gap filling structure having a submicron gap. .

Example 5

3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (compound K), 4,4'-bis (phenylethynyl) diphenyl ether Preparation of Polymers from (Compound H) and 1,3,5-tris (phenylethynyl) benzene (Compound G)

3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (10.0000 g, 0.01277 mol), 4,4' in a 100 ml three-neck round bottom flask -Bis (phenylethynyl) diphenyl ether (2.3660 g, 0.006386 mol), 1,3,5-tris (phenylethynyl) benzene (2.4170 g, 0.006386 mol) and N-methylpyrrolidinone (34.5 ml) Add. The flask is attached to the vaginal inlet and the mechanically stirred solution is heated to 200 ° C. in an oil bath. After 11 hours at 200 ° C., the solution is cooled and bottled. A fraction of the solution is dissolved in a syringe and filtered through a 1.0 μ scan filter on a 4 inch silicon wafer. The wafer is spin-coated at 2000 rpm for 60 seconds. The coated wafer is then left on a hot plate set at 90 ° C. for 2 minutes. The wafer is then left in a nitrogen purged oven where it is cured by purging at room temperature for 45 minutes, then heated to 400 ° C. at 10 ° C./min, left at 400 ° C. for 1 hour and then cooled to room temperature. Thus, the obtained wafer is coated with polyphenylene polymer. It has been found that when applied and cured to a gap filled structure having a submicron gap, the solution completely fills the gap. The cured polymer is insoluble in N-methylpyrrolidinone.

Example 6

3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (compound K), 1,3-bis (phenylethynyl) benzene (compound O ) And polymers from 1,3,5-tris (phenylethynyl) benzene (compound G)

3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (2.0000 g, 0.002554 mol), 1,3-bis (phenylethynyl) benzene (0.4740 g, 0.001703 mol), 1,3,5-tris (phenylethynyl) benzene (0.4834 g, 0.001277 mol) and N-methylpyrrolidinone (6.9 ml) were added to a 25 ml Schlenk tube do. The tube is attached to the nitrogen inlet and the mechanically stirred solution is heated to 200 ° C. in an oil bath. After 20 hours at 200 ° C., gel permeation chromatography shows Mn 1463 and Mw 2660 in relation to polystyrene standards. The solution is cooled to room temperature and placed in a bottle. A fraction of the solution is dissolved in a syringe and filtered through a 1.0 μ scan filter on a 4 "silicon wafer. The wafer is spin-coated at 2000 rpm for 60 seconds under a heat ramp to warm the wafer. The coated wafer is then 2 minutes The wafer is then placed in a hot plate set at 90 ° C. The wafer is then left in a nitrogen purged oven where it is cured by purging at room temperature for 45 minutes and then heated to 400 ° C. at 10 ° C./min and 400 ° C. for 1 hour. After standing in, it is cooled to room temperature, thus the obtained wafer is coated with polyphenylene polymer.

Example 7

3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (compound K) 1,3-bis (phenylethynyl) benzene and 1,3 Preparation of Oligomeric Solution from, 5-tris (phenylethynyl) benzene (Compound G)

Low ionic 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (100.0 g, 0.128 mol), low ionic 1,3,5-tris (Phenylethynyl) benzene (48.3 g, 0.128 mol) and electronic grade N-methylpyrrolidinone (346 g) were added to a washed and dried Pyrex ^R 1L three-neck round bottom flask with deionized water and HPLC grade acetone. do. The flask is attached to a nitrogen / vacuum inlet. The mechanically stirred solution is degassed by applying vacuum and refilling with nitrogen five times. Nitrogen gas is then flowed through the flask's headspacer and released through an inorganic oil foamer. The solution is then heated to an internal temperature of 200 ° C. After heating for 8.5 hours, the solution is cooled and transferred to a bottle made of tetrafluoroethylene. Analysis of the final solution by gel permeation chromatography shows Mn 1498 and Mw 2746 in relation to polystyrene standards. Analysis of the final solution by reverse phase chromatography showed residual 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) at 1.8% weight concentration. . Analysis of the final solution by neutron activation showed 52 ppm sodium, 190 ppm potassium, 90 ppm palladium, 2.4 ppm bromine, 0.6 ppm iodine and 2.4 ppm chlorine.

Example 8

Coating and Curing of Oligomeric Solution from Example 7

A silane adhesion promoter AP8000 [manufacturer: The Dow Chemical Company] was first applied to the surface of the wafer 3 ml for a 200 mm wafer; Rotate slowly to spread over the entire surface; Allow to stand for 2 seconds and finally spin dry at 3000 rpm for 10 seconds. The polyphenylene oligomer solution prepared in Example 7 was placed on a wafer surface coated with an adhesion promoter while rotating 4 ml for a 200 mm wafer by Millipore Gen-2, a high precision pump / filtration system, at 750 rpm. Apply. Immediately after accelerating the wafer rotation to 2000 rpm, the oligomer solution is applied and left at that spin speed for 20 seconds. During application of the oligomer solution, a continuous stream of mesitylene is applied to the backside of the wafer for 5 seconds. After spin coating the wafer with an oligomer solution, the film is dried on a hotplate at 70 ° C. for 20 seconds. After the dry baking step, the 2 mm to 5 mm corner beads of the coating are removed with a continuous stream of mesitylene while rotating by applying the wafer directly from the top of the back or near the corners at 2000 rpm. After removing the corner beads, the oligomer is further polymerized on a hotplate at 325 ° C. for 90 seconds under a blanket of nitrogen. The film is then crosslinked under nitrogen in a hotplate at 450 ° C. for 2 minutes or in a nitrogen purged oven at 450 ° C. for 6 minutes. The glass transition temperature of the film is above 450 ° C. as measured by kinetic analysis.

The process for preparing compounds described above uses standard chemistry practices, and because it is known that somewhat different reactants may require somewhat different reaction parameters than other reactants, for example, the use of excess reactants, the use of catalysts, room temperature It may be understood that slight modifications to reaction variables such as the use of slightly higher or lower temperatures and / or high speed mixing and other such conventional modifications are within the scope of the present invention.

Polyphenylene oligomers and polymers prepared according to the process of the present invention are useful as dielectrics in the microelectronic manufacturing industry because of their low dielectric constant, high thermal stability and high glass transition temperature.

Claims (14)

Diels-Elder reaction between at least one compound having at least two diene functional groups and at least one compound having at least two parent diene functional groups, wherein at least one of these compounds has three functional groups -Alder reaction) A crosslinked or crosslinkable polyphenylene product. The polyphenylene according to claim 1, wherein the diene diene functional group is an acetylene group. The diene functional group according to claim 2, wherein the diene functional group is a cyclopentadienone group and is an oligomer, uncured polymer or cured polymer having a ratio of cyclopentadienone group to acetylene group in the range of 1: 1 to 1: 3. Polyphenylene. The polyphenylene according to claim 3, wherein at least 10% of the cyclopentadienone groups remain unreacted. The solvent according to any one of claims 1 to 4 in a solvent selected from N-methylpyrrolidinone, a mixture of N-methylpyrrolidinone and cyclohexanone and a mixture of γ butyrolactone and mesitylene. A composition comprising polyphenylene. The process for preparing the polyphenylene according to any one of claims 1 to 4, including heating the diene functional compound and the diene diester functional compound at a temperature of 150 to 250 ° C for 1 to 48 hours. . The method of claim 6 comprising coating an oligomer or uncured polymer on the substrate and heating the coating to a temperature of 100 to 475 ° C. for 1 minute to 10 hours. 8. The method of claim 7, wherein the polyphenylene fills the gap with a depth of 1 탆 and a diameter of 0.5 탆 without leaving voids when cured. The method of claim 7, further comprising patterning the coating using a chemical mechanical polishing technique, planarizing the surface of the cured polymer, or both. An article comprising a substrate and a material on a substrate comprising a cured polyphenylene according to any one of claims 1 to 3. The article of claim 10, wherein the material is a foam. The article of claim 10, wherein the substrate is an active substrate containing a transistor and the material is an integrated circuit product that partially or wholly separates the patterned metal lines forming the electrical interconnect structure. 13. The article of claim 12, wherein the metal line is copper. The article of claim 12, wherein the material further comprises an adhesion promoter or an adhesion promoter layer is found between the material and the substrate.