JP2000191752A - Polyphenylene oligomer and polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyphenylene oligomer or polymer useful for filling spaces and for flattening patterned surfaces and giving cured articles having high thermal stability, high glass transition temperature and low dielectric constant by the Diels-Alder reaction of a compound having dienic functional groups with a compound having dienophilic functional groups. SOLUTION: This crosslinked or crosslinkable polyphenylene is obtained by the Diels-Alder reaction of at least one compound having two or more dienic functional groups with one or more compounds having two or more dienophilic functional groups (preferably acetylene groups), wherein at least one of the compounds has three or more functional groups. The polyphenylene is its oligomer, non-cured polymer or cured polymer. The dienic functional groups are preferably cyclopentadienone groups, and the ratio of the cyclopentadienone groups : acetylene groups is preferably 1:1 to 1:3. At least 10% of the cyclopentadienone groups are preferably not reacted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to polyurethane oligomers and polymers, methods for their preparation, and methods for their use.
These oligomers and polymers are effective as dielectric resins in microelectronics.

[0002] Polymer dielectrics are used in microelectronic devices such as integrated circuits, multichip modules, and laminated circuit boards as insulating layers between many circuits and the layers within the circuits. The microelectronics industry is moving toward smaller geometries in its devices in order to be able to reduce power and increase speed. As conductor lines become finer and more tightly packed, dielectric requirements between the conductors are becoming more stringent.

[0003] While polymer dielectrics often provide lower dielectric constants than inorganic dielectrics such as silicon dioxide, attempts have been made to integrate during processing. For example, to use silicon dioxide as a dielectric in integrated circuits, the dielectric must be able to withstand the processing temperatures during the deposition and annealing steps. Preferably, the dielectric material should have a glass transition temperature higher than the processing temperature. The dielectric must also retain desirable properties under the conditions of use of the device. For example, the dielectric should not absorb water that would cause corrosion of the metal conductor and increase the dielectric constant.

In some integration methods, the oligomer should preferably be planar when applied in a conventional manner such as spin coating and fill the gaps in the patterned surface.

[0005] At present, polyimide resin is used in the electronics industry as one type of thin film dielectric material. However, the polyimide resin may absorb water and hydrolyze, causing corrosion of the circuit. Metal ions may migrate to the dielectric polyimide layer which requires a barrier layer between the metal lines and the polyimide dielectric. Polyimide is difficult to flatten and is inferior in filling gaps. Non-fluorinated polyimides will exhibit an undesirably high dielectric constant.

[0006] Kumar and Neeenan are described in Macromolecules, 199.
5,28, pp. 124-130, disclose a number of polyphenylenes prepared from biscyclopentadiene and bisacetylene. They teach that polyphenylene is possible as a photoformable organic dielectric. Wr
asidlo and Augl are described in J. Polym. Sci. Part B (1969), 7 (7), 5
19-523, discloses the copolymerization of 1,4-bis (phenylethynyl) benzene with 3,3 '-(1,4-phenylene) -bis (2,4,5-triphenylpentadienone). ing. They report that a soluble yellow non-melting polymer was obtained.

The materials described in Kumar and Wrasidlo are soluble but not suitable for applications such as spin coating to fill gaps. This is because this material polymerizes and depletes the cyclopentadienone moiety, resulting in a relatively high molecular weight. This molecular weight will be too high to be applied by spin coating on a patterned surface that contains gaps to be filled by the dielectric. Based on the reported glass transition temperatures, this material will not be able to withstand the desired processing of the dielectric monolayer in integrated circuits.

US Patent Nos. 5,334,668, 5,236,686,
In 5,169,929, and 5,338,823, Tour describes a number of methods for making crosslinkable polyphenylene compositions for the production of glassy carbon. The polyphenylene is prepared by polymerizing 1-bromo-4-lithiobenzene to form a brominated polyphenylene, and then coupling a substituted phenylacetylene, for example, phenylacetylenylphenylacetylene, to residual bromine. This polyphenylene has a melting point of approximately 200 ° C. before crosslinking.

A polymer dielectric material which provides a relatively low dielectric constant, a high thermal stability and a high glass transition temperature, and which is preferably applied by spin coating and which makes it possible to flatten and fill gaps in the patterned surface To the microelectronics industry.

[0010] In a first aspect, the invention relates to at least one polyfunctional compound comprising two or more cyclopentadienone groups and at least one polyfunctional compound comprising two or more aromatic acetylene groups.
A reaction product of at least one polyfunctional compound, wherein at least a portion of the polyfunctional compound includes three or more reactive groups;
An oligomer, an uncured polymer or a cured polymer.

Here, the reactive group means a cyclopentadienone or acetylene group. Oligomers are intended to fill gaps, i.e. fill irregular grooves 1 micron deep and 1.5 microns wide without leaving voids when cured.
It means the reaction product of two or more monomer units of the present invention. By uncured polymer is meant the reaction product of the monomer of the present invention that no longer fills the gap but contains sufficient unreacted cyclopentadienone or acetylene functionality. By cured polymer is meant the reaction product of the monomers of the present invention that is substantially free of unreacted cyclopentadienone or acetylene functionality. Sufficient unreacted cyclopentadienone or acetylene functionality requires that this moiety react to drive the polymerization further.

A feature of the present invention is the reaction formation of one or more polyfunctional compounds containing two or more cyclopentadienone groups and at least one polyfunctional compound containing two or more aromatic acetylene groups. And that at least a part of the polyfunctional compound contains three or more reactive groups. The advantage of such a reaction product is that it fills gaps, flattens the patterned surface, and when cured has high thermal stability, high glass transition temperature and low dielectric constant.

In a second preferred embodiment, the present invention provides
One or more polyfunctional compounds containing two or more cyclopentadienone groups and one containing two or more aromatic acetylene groups
A reaction product of at least one kind of polyfunctional compound, wherein at least a part of the polyfunctional compound containing an aromatic acetylene group is 3
Oligomers, uncured polymers or cured polymers containing one or more acetylene groups.

A feature of the second aspect of the present invention is that at least one polyfunctional compound containing two or more cyclopentadienone groups and at least one polyfunctional compound containing two or more aromatic acetylene groups.
And at least a portion of the polyfunctional compound containing an aromatic acetylene group contains three or more acetylene groups. The advantage of this reaction product is that it fills gaps, flattens patterned planes, and when cured has high thermal stability, high glass transition temperature and low dielectric constant.

The high thermal stability, high glass transition temperature, low dielectric constant, and the ability to fill gaps and flatten patterned surfaces make the compositions of the present invention suitable as polymer dielectrics in the microelectronics industry. . In particular, the combination of low dielectric constant, high thermal stability and high glass transition temperature allows the use of the composition of the present invention as an integral dielectric layer in integrated circuits.

Preferably, the oligomers and polymers according to the invention and the corresponding starting monomers are: I Oligomers and polymers of the following formula [A] _w [B] _z [EG] _{v In the} above formula, A has the structure of the following formula,

Embedded image B has the following structure,

Embedded image EG is a terminal group having one or more of the following structures:

Embedded image

Wherein R ¹ and R ² are independently H or an unsubstituted or inertly substituted aromatic moiety;
r 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 3 or more; p is the number of unreacted acetylene groups in the monomer unit; r is a number one less than the number of reacted acetylene groups in the monomer unit;
r = y−1, z is an integer from 0 to 1000, w is 0
Is an integer of 10001000, and v is an integer of 2 or more.

The oligomers and polymers are prepared by reacting biscyclopentadienone, an aromatic acetylene containing at least three acetylene groups, and optionally a polyfunctional compound containing two aromatic acetylene moieties. You. This reaction is represented by the reaction of a compound of the following formula:

(A) biscyclopentadienone of the following formula

Embedded image

(B) a polyfunctional acetylene of the formula

Embedded image (c) optionally a diacetylene of the formula

Embedded image (Wherein R ¹ , R ² , Ar ¹ , Ar ² , Ar ³ and y
Is the same as the above definition)

The definition of aromatic moiety includes phenyl, polyaromatic and fused aromatic moieties. Inert substitution means that the substituent is essentially inert to the cyclopentadienone and acetylene polymerization reaction and is readily accessible to environmental substances, such as water, under the conditions of use of the cured polymer in the microelectronic device. Does not respond to
Such substituents are, for example, F, Cl, Br, -C
F ₃ , —OCH ₃ , —OCF ₃ , —O—Ph, and alkyl having 1 to 8 carbons and cycloalkyl having 3 to 8 carbons are included. For example, unsubstituted or inertly substituted aromatic moieties include:

[0022]

Embedded image

In the above formula, Z is -O-, -S-, alkylene
, -CF_Two-, -CH_Two-, -O-CF _Two-, Perfluoro
Alkyl, perfluoroalkoxy,

Embedded imageAnd each R^ThreeIs independently H, -CH_Three, -CH_Two
CH_Three,-(CH_Two)_TwoCH _ThreeOr Ph. Ph is Fe
Nil.

II. Polyphenylene oligomers and polymers of the formula

Embedded image In the above formula, R ¹ , R ² , Ar ¹ and Ar ² are the same as those defined above, and x is an integer of 1 to 1000. Preferably,
x is 1 to 50, more preferably 1 to 10.

These oligomers and polymers are produced by the reaction of biscyclopentadienone with diacetylene of the following formula.

Embedded image (Wherein R ¹ , R ² , Ar ¹ and Ar ² are the same as defined above)

III. Polyphenylene oligomers and polymers of the formula

Embedded imageIn the above formula, Ar^FourIs an aromatic moiety or an aromatic with an inert substitution
Part and R¹, R ^TwoAnd x are the same as defined above.
You.

It is prepared by the reaction of the acetylene function and the cyclopentadienone function of a polyfunctional compound of the formula

Embedded image (Wherein R ¹ , R ² and Ar ⁴ are the same as defined above)

IV. Polyphenylene oligomers and polymers of the formula

Embedded image In the above equation, EG is represented by one of the following equations.

Embedded image (Wherein R ¹ , R ² , Ar ⁴ and x are the same as defined above)

It is prepared by reacting the acetylene function and the cyclopentadienone function of a polyfunctional compound of the formula

Embedded image (Wherein R ¹ , R ² and Ar ⁴ are the same as defined above)

Polyfunctional compounds containing two or more aromatic cyclopentadienone moieties are prepared by condensation of benzyl and benzyl ketone using conventional methods. Examples of such methods are described in Kumar et al., Macromolecules, 1995, 28, 124-130.
Ogliaruso et al., J. Org. Chem., 1965, 30, 3354, Og.
liaruso et al., J. Org. Chem., 1963, 28, 2725 and U.S. Pat. No. 4,400,540.

Polyfunctional compounds containing two or more aromatic acetylene moieties are prepared by conventional methods. The aromatic compound is halogenated and then reacted with a suitable substituted acetylene in the presence of an arylethynylation catalyst,
Replace the halogen with a substituted acetylene compound.

Once the polyfunctional compound has been prepared, it is preferably purified. In particular, when used as an organic polymer dielectric, metals and ionic substances are removed. For example, a polyfunctional compound containing an aromatic acetylene group is contacted with a water wash and an aliphatic hydrocarbon solvent, then dissolved in the aromatic solvent and filtered through pure silica gel. This treatment removes residual ethynylation catalyst. Further recrystallization also facilitates the removal of unwanted impurities.

Without being bound by theory, polyphenylene oligomers and polymers are formed by the Diels-Alder reaction of cyclopentadienone and acetylene groups when a mixture of cyclopentadienone and acetylene is heated in solution. it is conceivable that. The oligomer may contain cyclopentadienone and / or acetylene end groups and / or side groups. When this solution or a product coated with this solution is further heated, the Diels-Alder reaction between the remaining cyclopentadienone terminal groups and the remaining acetylene groups causes further chain elongation, increasing the molecular weight. Depending on the temperature used, the acetylene groups will also react with each other.

The oligomers and polymers are structurally shown to have either cyclopentadienone and / or acetylene end groups and / or side groups. Normal,
This end group is determined by the relative concentration of cyclopentadienone relative to the Diels-Alder reactive acetylene function used in the reaction, and a theoretical excess of cyclopentadienone function gives more cyclopentadienone end groups, Excess Diels-Alder reactive acetylene functionality gives more acetylene end groups.

It is a feature of a preferred embodiment of the present invention that the polymerization reaction is stopped before the reaction of all cyclopentadienone moieties. The oligomer is then applied to the surface before the polymerization proceeds and the remaining cyclopentadienone moieties react. In such an oligomerized state, when applied to a patterned surface, the oligomer flattens and fills gaps. Preferably, at least 10 percent of the cyclopentadienone moiety is unreacted. Most preferably, at least 12 percent of the cyclopentadienone moiety is unreacted. Spectroscopic analysis could determine the percentage of unreacted cyclopentadienone moiety. The cyclopentadienone moiety is fairly red or purple in the visible spectrum and is considerably colored, and the color fades when the cyclopentadienone moiety reacts.

Here, “flattening” means that the isolated surface is 17
This degree of flattening, which means that the surface is flattened by not less than percent, preferably not less than 18 percent, more preferably not less than 19 percent, is calculated by the following equation. Flattening percentage _{= (1-t s / t} m) × 100 width 1 micron, when applying the layer of the oligomer with an average thickness of 2 microns in height 1 micron square line on, t _s is the average of the oligomer or polymer The height of the oligomer or polymer on the surface above the height, where t _m is the surface height (1 micron). The use of this provision is, for example, Pr
oceedings of IEEE, Vol. 80, No. 12, December 1992, 1948
Page.

Without being bound by theory, the preparation of a polyphenylene polymer is represented by the following formula:

Embedded image In the above formula, R ¹ , R ² , Ar ¹ and Ar ² are the same as those defined above.

Further, although not specifically shown in this structure, there is a carbonyl-crosslinked substance in the produced oligomer depending on the monomer used and the reaction conditions. Upon further heating, essentially all of the carbonyl bridging material is converted to an aromatic ring. When one or more acetylene-containing monomers are used, the structure shown indicates that blocks are formed, but the oligomers and polymers formed are random. A Diels-Alder reaction between the cyclopentadienone and the acetylene function occurs, forming a para or meta bond on the phenylated ring.

An inert organic solvent which can dissolve the monomer to an appropriate extent and heat to an appropriate polymerization temperature at any of atmospheric pressure, reduced pressure or overpressure may be used. Examples of suitable solvents are mesitylene, pyridine, triethylamine, N-methylpyrrolidinone (NMP), methyl benzoate, ethyl benzoate, butyl benzoate,
Cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclohexylpyrrolidinone,
And ethers or hydroxy ethers such as 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 methyl ether, tripropylene glycol methyl ether, Includes toluene, mesitylene, xylene, benzene, dipropylene glycol monomethyl ether acetate, dichlorobenzene, propylene carbonate, naphthalene, diphenyl ether, butyrolactone, dimethylacetamide, dimethylformamide, and mixtures thereof. Preferred solvents are mesitylene, N-methylpyrrolidinone (NMP), gamma-butyrolactone, diphenyl ether and mixtures thereof.

Alternatively, the monomer may be reacted at an elevated temperature in one or more solvents, and the resulting oligomer solution may be cooled and mixed with one or more other solvents, for example, to facilitate processing. In another method, the monomer is reacted at an elevated temperature in one or more solvents to form an oligomer, which is then isolated by precipitation in a non-solvent or by other solvent removal means and is essentially solvent free. An oligomer may be provided. The isolated oligomer may then be redissolved in one or more different solvents and the resulting solution used for processing.

The conditions under which the polymerization reaction occurs most liberally depend on various factors including the reactants and the solvent. Normal,
The reaction is performed in a non-oxidizing atmosphere, for example, nitrogen or other inert gas. This reaction may be performed as is (without using a solvent or other diluent). However, in order to ensure a homogeneous reaction mixture and to reduce heat generation at such temperatures, it is desirable to use, for example, the above-mentioned inert organic solvents.

The time and temperature used most advantageously vary greatly depending on the monomers used, in particular their reactivity, the desired oligomer or polymer, and the solvent. Usually, the reaction to form the oligomer is carried out at a temperature of 150 ° C to 250 ° C for 60 minutes to 48 hours. At this point, the oligomer may be isolated from the reaction mixture or may be used as is for coating a surface. 100 ° C to 475 ° C,
Further chain extension may be carried out at a temperature of preferably 200 ° C. to 450 ° C. for 1 minute to 10 hours, more preferably 1 minute to 1 hour. An uncured or cured polymer may be used to coat the surface by casting from a solvent. Such polymers do not fill gaps or flatten sufficiently, but do not
(damascene) Effective in processing.

The concentration at which the monomers in the organic liquid reaction medium are most advantageously used depends on a number of factors, including the monomers and organic liquids used and the oligomers and polymers to be prepared. Usually, this monomer is used in a stoichiometric ratio of cyclopentadienone: acetylene of 1: 1 to 1: 3, preferably 1: 1 to 1: 2.

The oligomer or polymer may be cast directly as a film, applied as a coating, or poured into a non-solvent to precipitate the oligomer or polymer. Water, methanol, ethanol and other similar polar liquids are examples of non-solvents that can be used to precipitate the oligomer. The solid oligomer or polymer may be dissolved and processed from a suitable solvent. If the oligomer or polymer is obtained in solid form, it may be further processed using conventional compression molding or melt spinning, casting or extrusion methods. However, it is necessary that the solid precursor has a sufficiently low glass transition temperature.

More generally, the oligomer or polymer is processed directly from the organic liquid reaction solution, and the advantages of the present invention are fully realized in this case. Since the oligomer or polymer is soluble in the organic liquid reaction medium, an organic solution of the oligomer can be cast or applied to remove the solvent. Subsequent exposure to higher temperatures increases the molecular weight (chain extension or advancement), and in some cases, crosslinks to form the final polymer.

The polymers of the present invention can be used as one or more insulating or dielectric layers in single or multi-layer electrical connection structures for integrated circuits, multi-chip modules, or flat panel displays. The polymers of the present invention can be used as the sole dielectric in these applications, or with other organic polymers or inorganic dielectrics such as silicon dioxide, silicon nitride or silicon oxynitride.

The oligomer and polymer coatings of the present invention, such as, for example, insulating coatings used in the fabrication of interconnect structures on wafers, can be obtained by spin coating a film of an organic liquid solution of the oligomer or polymer or based on the solution. Easily made by coating the material, then evaporating the solvent and exposing the oligomer or polymer to a temperature sufficient to make it higher molecular weight, most preferably a crosslinked polymer with a high glass transition temperature .

The polymer of the present invention is particularly useful as an insulating material having a low dielectric constant in integrated circuit connection structures, such as those processed with gallium arsenide or silicon. Integrated circuits usually have many layers of metal conductors separated by one or more insulating materials. The polymeric material of the present invention can be used as an insulator between separate metal conductors in the same layer and / or between conductors of a connection structure. The polymers of the present invention can be used in composite connection structures with SiO
It can also be used with other materials such as ₂ or Si ₃ N ₄ . For example, the oligomers and polymers of the present invention are disclosed in U.S. Patent Nos. 5,550,405, 5,591,677, Hayashi
Et al. 1996 Symposium on VLSI Technology Digest of T
It can be used in the integrated circuit device manufacturing method taught in Technical Papers, pp. 88-89. The oligomers and polymers of the present invention can be used in place of BCB or other resins.

The oligomer, uncured polymer or cured polymer of the present invention can be used to form an electrical connection structure comprising patterned metal lines at least partially separated by a layer of the composition of the invention and an active group comprising a transistor. It can be used as a dielectric in a method used for processing an integrated circuit including a material.

The polymers of the present invention are also useful for planarizing materials such as silicon wafers used in semiconductors to enable the fabrication of smaller (higher density) circuits. To achieve the desired planarization, an oligomer or polymer coating is applied from solution, for example by spin coating or spray coating, to even out the roughness on the surface of the substrate. This method
Jenekhe, SA., PolymerProcessing to Thin Films for
Microelectronic Applications in Polymers for High Technology, Bowden et al., American Chemical So
ciety 1987, p.261-269.

In the processing of microelectronic devices, relatively thin, typically 0.01-20 microns thin,
Preferably, a defect-free film of 0.1 to 2 microns is coated on a substrate such as silicon, silicon-containing material, silicon dioxide,
Deposits on alumina, copper, silicon nitride, aluminum nitride, aluminum, quartz, and gallium arsenide surfaces. The coating is usually coated with various organic solvents such as xylene,
For example up to 3000 _{Mn in} mesitylene, NMP, gamma-butyrolactone and n-butyl acetate, and 5200 _Mw
It is prepared from a solution of an oligomer having the following molecular weight: The dissolved oligomer or polymer is cast on a substrate by a usual spin and spray coating method. The thickness of this coating can be adjusted by changing the solids content, molecular weight, ie viscosity, of the solution or by changing the spin rate.

The polyphenylene oligomer or polymer in the present invention can be applied by dip coating, spray coating, extrusion coating, or twisting, preferably spin coating. In all cases, the environment around the substrate and coating before curing is controlled with respect to temperature and humidity. In particular,
NMP absorbs moisture from water vapor in the surrounding air. NM
When dissolved in P, protect this solution from moist air,
The film must be cast in a low humidity environment. If NMP is used as the solvent, preferably the relative humidity is controlled to less than 30% and the temperature is controlled to 27 ° C or higher. After application, the coating may be cured by one or more hot plates, ovens, or a combination thereof.

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

The oligomers and polymers of the present invention can be used in "damascene" metalwork or subtractive metal patterning methods for processing integrated circuit interconnects. The processing of damasco lines and biases is well known in the art. For example, U.S. Pat.
See 2,354 and 5,093,279.

The patterning of the material may be carried out using oxygen, argon, helium, carbon dioxide, fluorine containing compounds, or mixtures of these with other gases, with a photoresist "soft mask", such as an epoxy novolak, or an inorganic "hard mask". For example, the etching may be performed by a reactive ion etching method using a photoresist combined with SiO ₂ , Si ₃ N ₄ or a metal.

Oligomers and polymers include Al, Al alloy, Cu, Cu alloy, gold, silver, W, and physical vapor
Other common metallic conductive materials (for conductive lines and plugs) deposited by chemical vapor deposition, evaporation, electrodeposition, and other deposition methods
Can be used with Fill the base metal conductor with other metal layers, such as tantalum, titanium, tungsten, chromium, cobalt, alloys thereof, or nitrides thereof, to enhance adhesion, provide a barrier, or provide metal reflectivity. May be improved.

Depending on the processing method, the dielectric material or metal of the present invention may be removed or planarized using a chemical-mechanical polishing method. Silicon, silicate glass, silicon carbide,
A multi-chip module may be constructed with an inventive polyphenylene polymer as a dielectric material on an active or immobile substrate such as aluminum, aluminum nitride, or FR-4.

Silicon, silicate glass, silicon carbide,
Flat panel displays on active or immobile substrates such as aluminum, aluminum nitride, or FR-4 may be constructed with the polyphenylene polymer of the present invention as a dielectric material.

The oligomers and polymers of the present invention may be used as a protective coating on integrated circuit chips to protect against alpha particles. Semiconductor devices are susceptible to soft errors when alpha particles released from small amounts of radioactive impurities in the package strike the active surface. Usually, the integrated circuit chip is placed on a substrate and fixed with a suitable adhesive. The coating of the polymer of the present invention provides an alpha particle protective layer on the active surface of the chip. If desired, further protection may be provided by encapsulants, for example made of epoxy or silicone.

The polymer of the present invention may be used as a substrate (dielectric material) in a circuit board or a printed wire board.
A circuit board formed from the polymer of the present invention is provided with surface patterns for various conductive circuits. The circuit board may include, in addition to the polymer of the present invention, various reinforcing agents, such as non-conductive woven fibers (eg, glass cloth). This circuit board may be single-sided or double-sided,
Or it may be a multilayer.

The polymers of the present invention are also useful in reinforced composites in which the resin matrix polymer has been reinforced by one or more reinforcing materials such as reinforced transitions or mats. Examples of reinforcing materials are glass fibers, especially glass fiber mats (woven or non-woven), graphite,
Especially graphite mats (woven or non-woven), Kevl
Includes ar ™, Nomex ™, and glass spheres. The composite can be made from a preform, a dipping mat in a monomer or oligomer, and resin transfer molding (the mat is placed in a mold, the monomer or prepolymer is added, and heated to polymerize). .

[0062] The layer of the polymer of the present invention comprises Polymers for E
electronic Applications, Lai, CRCPress (1989) p.42-
47, by wet etching, plasma etching, reactive ion etching (RIE), dry etching, or light laser ablation. The patterning is performed by a multi-level method in which a pattern is formed by a lithographic printing method in a resist layer coated on the polymer dielectric layer, and then the bottom layer is etched. A particularly effective method is to mask portions of the oligomer or polymer that should not be removed, remove the unmasked portions of the oligomer or polymer, and then cure the remaining oligomer or polymer, for example, by heat. Including.

Further, the oligomer of the present invention can be used for producing molded articles, films, fibers and foams. Generally, methods well known in the art for casting oligomers or polymers from solution can be used to make this product.

In the production of polyurethane oligomer or polymer moldings, additives such as fillers, pigments, carbon black, conductive metal particles, abrasives and lubricating polymers may be used. The method of mixing the additive is not a problem, and it is preferable to add the additive to the oligomer or polymer solution before the production of the molded article. Liquid compositions containing oligomers or polymers alone or containing fillers can be applied to many different substrates by the usual methods (doctor, rolling, dipping, brushing, spraying, spin coating, extrusion coating or meniscus coating) Can be. If the polyphenylene oligomer or polymer is produced in solid form, the additives are added to the melt before it is processed into shaped articles.

The oligomers and polymers of the present invention may be used in solution deposition, liquid phase epitaxy, screen printing, melt spinning, dip coating, spinning, brushing (such as varnish), spray coating, powder coating, plasma deposition, dispersion spray, Solution casting, slurry spray, dry powder spray, fluid bed method, weld ring, explosion method (including wire explosion spraying method and explosion bonding), press bonding with heat, plasma polymerization, dispersing in dispersing medium, Removal of dispersing media, pressure bonding, pressurized heat bonding, gas environment vulcanization, extruded melt polymer, hot gas welding, baking, coating and sintering. It can be applied to various substrates by methods. Single and multilayer films can also be applied to substrates at the air-water interface or other interfaces using the Langmueller Blodgett method.

When applying the oligomer or polymer of the present invention from solution, the polymerization conditions and other processing parameters most advantageously employed will depend on a number of factors, particularly the particular oligomer or polymer to be submitted, coating conditions, coating quality. And thickness, as well as the end use, which will select the solvent. Examples of the solvent that can be used are as described above.

The substrate coated with the oligomer or polymer of the present invention may be any material as long as it has sufficient integrity to be coated with the monomer, oligomer or polymer. Examples of substrates include wood, metal, ceramics, glass, other polymers, paper, cardboard, woven, non-woven mats, synthetic fibers, Ke
vlar ™, including carbon fibers, gallium arsenide, silicon and other inorganic substrates and their oxides. The substrate used is selected based on the desired application. An example is
Glass fiber (woven fabric, non-woven fabric or strand), ceramics, metal such as aluminum, magnesium,
Titanium, copper, chromium, gold, silver, tungsten, stainless steel, Hastalloy ™, carbon steel, other metal alloys and oxides thereof, and thermosetting and thermoplastic polymers such as epoxy resins, polyimides, perfluorocyclobutane polymers , Benzocyclobutane polymers, polystyrene, polyamide, polycarbonate, polyarylene ether and polyester.
These substrates may be the polymer of the invention in cured form.

The substrate can be of any shape, the shape depending on the end use. For example, this substrate can be a disc, plate, wire, tube, plate,
It may be in the form of spheres, rods, pipes, cylinders, chunks, fibers, woven or nonwoven fabrics, yarns (including mixed yarns), ordered polymers, and woven or nonwoven mats. In each case, the substrate may be hollow or solid. When hollow, the polymer layer may be provided on one or both of the inside and the outside of the substrate. The substrate may include a porous layer, such as graphite mat or fabric, glass mat or fabric, scrim, and particulate material.

The oligomers or polymers of the present invention can be any of a number of materials, including compatible polymers, polymers with common solvents, metals, especially textured metals, silicon, silicon dioxide, especially etched silicon and silicon dioxide, glass, Adheres directly to silicon nitride, aluminum nitride, alumina, gallium arsenide, quartz, and ceramics. However, if high adhesion is desired, materials to improve the adhesion may be introduced.

Examples of such adhesion promoting materials are silane,
Preferably organosilanes, for example trimethoxy vinyl silane, triethoxy vinyl silane, hexamethyldisilazane _{[(CH 3) 3 -Si-} NH-Si (CH 3) 3], or aminosilane coupling agent, for example, γ- aminopropyltriethoxysilane Silane or chelate, for example, aluminum monoethyl acetoacetate diisopropylate [(iso C ₃ H ₇ O) ₂ Al
(OCOC ₂ H ₅ CHCOCH ₃ )]. In some cases, the adhesion promoter is applied in a 0.01 weight percent to 5 weight percent solution, excess solution is removed, and then polyphenylene is applied. In other cases, for example, a solution of the chelate in toluene is spread over the substrate, and the coated substrate is then baked in oxygen at 350 ° C. for 30 minutes, leaving a very thin (eg, 5 nanometer) aluminum oxide on the surface. By forming the adhesion promoting layer of (1), a chelate of aluminum monoethylacetoacetate diisopropylate can be mixed on the substrate. Other means of depositing aluminum oxide are equally suitable. Also, for example, an adhesion promoter in an amount of 0.05 to 5 weight percent based on the weight of the monomer can be mixed with the monomer prior to polymerization to eliminate the need to form another layer.

Adhesion can be performed by surface treatment, eg, texturing (eg, scratching, etching, plasma treatment or buffing) or cleaning (eg, degreasing or ultrasonic cleaning), or other treatment (eg, plasma, solvent, SO ₃ , plasma glow). Discharge, corona discharge, sodium, wet etching, or ozone treatment), or sanding the surface of the substrate or using an electron beam method, for example, using 6 MeV fluoride ions, electrons having an intensity of 50 to 2000 V, 0.2 to 500 e.
V to 1 MeV hydrogen cation, 200 KeV to 1 MeV helium cation, 0.5 MeV fluorine or chlorine cation, 280 K
eV neon and oxygen are enhanced by rich flame treatment or accelerated argon ion treatment.

3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) and 1,3,5-
For the application of the oligomerization product of the reaction of tris (phenylethynyl) benzene, in a more preferred embodiment of the present invention, from DuPont as VM-652 or The Dow Ch
An adhesion promoter based on silane containing 3-aminopropylsilane dissolved in methanol, available as AP8000 from emical Company, is first applied to the wafer surface, slowly spread over the entire surface, left for 2 seconds, and finally 30
Spin at 00 rpm for 10 seconds to dry. High precision pump /
The filtration system Millipore Gen-2 pours 4 mL of the oligomer solution onto a 200 mm wafer onto the wafer surface while rotating the wafer at 750 rpm. Immediately after pouring, increase the rotation of the wafer to 2000 rpm, and
Hold for 20 seconds. A continuous stream of mesitylene is applied to the backside of the wafer for 5 seconds while pouring the oligomer solution. After spin coating, the film is dried on a hot plate at 70 ° C. for 20 seconds. After the dry baking process, remove the wafer
While rotating at 2000 rpm, 2-5
The beads at the end of mm are removed by directing a continuous stream of mesitylene directly from above or near the end from above. After removing the end beads, the oligomer is further polymerized on a hot plate at 325 ° C. for 90 seconds in a nitrogen blanket.
The film is crosslinked on a hot plate at 450 ° C. for 2 minutes in nitrogen or in a nitrogen purged oven at 450 ° C. for 6 minutes.

The oligomers or polymers of the present invention may be applied with other additives to achieve the desired result.
Examples of such additives are metal-containing compounds, such as magnetic particles (eg barium ferrite, iron oxide (optionally with cobalt) or other metals used in magnetic, optical or other recording media) Particles), conductive particles such as conductive sealants, conductive adhesives, conductive coatings, electromagnetic interference (EMI) / radio frequency interference (RF
I) Metal or carbon for use in shield coatings, electrostatic dissipation, and electrical contact. When these additives are used, the oligomer or polymer of the present invention functions as a binder.

The oligomer or polymer of the present invention comprises
Protection against the environment, such as metals, semiconductors, capacitors, inductors, conductors, solar cells, glass, glass fibers, quartz, and coatings that impart surface immobility to quartz fibers (i.e., in environments including manufacturing, storage and use conditions) As protection against at least one substance).

The following examples illustrate the invention but do not limit its scope. In this example, parts and percentages are by weight unless otherwise indicated.

Example 1 Preparation of Cyclopentadienone Compounds and Acetylene Compounds A number of cyclopentadienone compounds and acetylene compounds were prepared as described below. 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) Was placed in a 1 liter round bottom three neck flask equipped with a reflux condenser and a mechanical stirrer. The reaction mixture was heated to 50 ° C. under nitrogen for 2 hours with charcoal added to escape gas. The thionyl chloride was evaporated and the product, 4-bromophenylacetyl chloride, was placed in an addition funnel with benzene (30 mL).

(B) Preparation of 4-bromodeoxybenzoin Benzene (200 mL) and aluminum chloride (74 g, 0.558 mol
l) into a fresco and the mixture of 4-bromophenylacetyl chloride and benzene in step (a) is added dropwise,
HCl was evolved. The reaction mixture is heated at room temperature for 1 hour.
Stirred for ~ 1.5 hours and poured into ice water. Ethyl acetate (1 L) was added dropwise to precipitate a solid. Separate the layers and add 1M organic layer
Aqueous HCl, saturated NaHCO ₃ , and brine, then dried over Na ₂ SO ₂ . Then the solvent is evaporated,
The title compound was obtained as a yellow solid in 84% yield.

(C) Production of 4-bromobenzyl Perchloric acid (250 mL), water (250 mL), ethylene glycol dimethyl ether (glyme) (500 mL), trihydrated titanium nitrate (I
II) (222.0 g, 0.5 mol) and 4-bromodeoxybenzoin
(68.75 g, 0.25 mol) was placed in a 2 liter round bottom three neck flask equipped with a reflux condenser and a mechanical stirrer. The reaction mixture was heated to reflux under nitrogen for 6 hours. After cooling to ambient temperature, methylene chloride (500 mL) was added. Precipitated Ti
(I) The salt was separated from the resulting two layers. The layers were separated and the organic layer was washed with water, saturated NaHCO _3, and successively washed with brine, and then 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 diethylamine (950 mL)
(PPh ₃ ) ₂ PdCl ₂ (0.121 g, 0.0002 mol) in was stirred at ambient temperature for 72 hours and then concentrated to dryness. The residue was then taken up in methylene chloride. A standard aqueous workup was performed and recrystallized from 2-propanol to give the title compound.

(E) Preparation of Compound A 4- (phenylethylbenzyl (20 g, 0.0644 mol), 1,3-diphenylacetone (14.2 g, 0.0677 mol) and ethanol (1
(50 mL) was 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 was heated to reflux for 30 minutes, then cooled to 40 ° C., and the precipitated product was filtered, washed with cold ethanol and dried. Recrystallization from 2-propanol provided the title compound.

B. 3,3 '-(1,4-phenylene) bis (2,4,5-
Triphenylcyclopentadienone) (compound B) 1,3-diphenylacetone (1.23 g, 0.00584 mol), Ken Se
Commercially available as Bis-PGB from ika Corporation1,
4-bis (phenylglyoxaloyl) benzene (1.000g
, 0.00292 mol) and ethanol (50 mL) were added to a 100 mL 3-neck round bottom flask equipped with a reflux condenser and a nitrogen inlet. The reaction mixture was heated to reflux and KO in water (2.25 mL)
An aqueous solution of H (0.112 g, 0.002 mol) was added. More KOH was added until the solution turned dark. The mixture was refluxed for 45 minutes and analyzed by ¹ H-NMR, ¹³ C-NMR, HPLC and FT-IR. All data were 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) 4-iodophenyl Preparation of Acetate 4-Iodophenol (25.00 g, 0.114 mol) and methylene chloride (100 mL) were placed in a 250 mL round bottom flask equipped with a condenser, nitrogen inlet, thermometer and addition funnel. The slurry was stirred and pyridine (10.11 mL, 0.125 mol) was added via syringe. The reaction mixture was cooled to 10 ° C. using an ice bath and acetyl chloride (8.89 mL, 0.125 mol) was added dropwise. The mixture was stirred at 10 ° C. for 1 hour, then warmed to room temperature,
Stir for 2 hours. The reaction mixture was filtered and the filtrate was washed four times with water. The organic layer was dried over MgSO ₄ and the solvent was removed in vacuo to give 27.3 g of an orange oil. Analysis by NMR was consistent with the structure of the desired product.

(B) Preparation of 4- (phenylethynyl) phenylacetate 4-Iodophenylacetate (50.00 g, 0.191 mol), phenylacetylene (23.40 g, 0.229 mol) and triethylamine (54 mL) were placed in a condenser and nitrogen. A 250 mL round bottom flask equipped with an inlet, thermometer, and stopper was added. Then PdCl ₂ (PPh ₃ ) ₂ (0.200 g, 0.286 mmol) and PPh ₃ (0.150 g
, 5.73 mmol) was added and the mixture was heated to reflux.
Once the reaction mixture reached 40 ° C., CuI (0.054 g, 0.286 mmol)
Was added. After 2 hours, it was cooled. The mixture was diluted with methylene chloride and poured into water (500mL). The aqueous layer was extracted with methylene chloride (100mL). The combined organic layers were washed three times with 300 mL of water, dried (MgSO ₄ ) and filtered. Removal of the solvent in vacuo gave 49 g of a yellow solid. This was recrystallized from hexane to give pale yellow crystals (mp 104.5 ° C to 105.5 ° C)
I got

(C) Production of 4- (phenylethynyl) phenol 4- (phenylethynyl) phenylacetate (60.6 g, 0.1%)
256mol), 20% sodium hydroxide aqueous solution (400m
L) and tetrahydrofuran (400 mL) were added to a 2 liter Erlenmeyer flask and stirred at room temperature for 5 hours. The mixture was acidified with glacial acetic acid (120 mL) until the pH was 7. The aqueous layer was taken out and extracted with tetrahydrofuran.
The organic layers were combined and concentrated to give a tan solid. Heat this solid with hexane (700 mL) on a steam bath,
The hot solution was separated from the solid. This was repeated with hexane (700 mL). Upon cooling, white solid crystals appeared from the hexane solution, which were isolated by filtration and dried in vacuo to give 18 g of a white solid (mp 126-127 ° C. NMR analysis showed the structure and Matched.

(D) Preparation of Compound C Decafluorobiphenyl (5.00 g, 14.96 mol), 4- (phenylethynyl) phenol (5.81 g, 29.93 mmol), potassium carbonate (16.54 g, also 0.1197), and dimethylacetamide ( 150 mL) was added to a 250 mL round bottom flask equipped with a condenser, nitrogen inlet, thermometer, and stopper. The mixture was stirred and heated to 70 ° C. for 16.5 hours. The reaction mixture was filtered to remove the solid. The filtrate was added to water (500 mL) and extracted with methylene chloride. Brine was added to break the emulsion, the organic layer was separated, washed twice with water, and then filtered through silica gel. Removing the solvent in vacuo,
Got the oil. Add methanol to form a white solid,
It was isolated by filtration and dried in vacuo. NMR spectrum was consistent with the structure of the title compound.

D. 4- (4-ethynylphenyl) -2,3,5-triphenylcyclopentadienone (compound D) By using trimethylsilylacetylene instead of phenylacetylene and then removing the trimethylsilyl protecting group using a dilute base, Compound D was produced in the same manner as in Example 1A.

E. 3,4-bis- (4- (phenylethynyl) phenyl) -2,5-diphenylcyclopentadienone (compound E) (a) Preparation of 4,4'-dibromobenzoin 4-bromo in ethanol (125 mL) Benzaldehyde (25.
0 g, 0.135 mol), 3-ethyl-5- (2-hydroxyethyl) -4-
A solution of methyl thiazolium bromide (1.70 g, 0.0068 mol) and triethylamine (4.10 g, 0.0405 mol) was stirred at room temperature for 60 hours. Concentrated to dryness The reaction mixture was then CH ₂ Cl placed in ₂ (150 mL), washed with HCl and saturated NaHCO ₃ of 1M, dried (Na ₂ SO _4), then concentrated, 25.2 g (100 percent ) Was obtained as a viscous yellow oil. It solidified on standing at room temperature. ¹ H NMR (CDCl ₃ ) δ 7.73 (d, J
= 8.5Hz, 2H), δ7.52 (d, J = 8.5Hz, 2H), 7.44 (d, J = 8.2Hz, 2
H), 7.17 (d, J = 8.2 Hz, 2H), ¹³ C NMR (CDCl ₃ ) δ 197.33, ¹³
7.56, 132.33, 132.13, 131.90, 130.43, 129.46, 129.
31, 122.93, 75.68

(B) Preparation of 4,4′-dibromobenzyl 4,4′-dibromobenzoin (20.2 g, 0.055 mol) in 80% aqueous acetic acid (200 mL), ammonium nitrate (4.6 g)
, 0.0575 mol) and a solution of copper (II) acetate (0.100 g, 0.0005 mol) was heated and refluxed for 3 hours. The reaction mixture was cooled to room temperature and the crystallized product was filtered, washed with ethanol, dried and the product as a pale yellow solid (mp 226
C. to 228.degree. C.) in 13.0 g (64 percent). ¹ H NMR (CDC
l ₃ ) δ7.83 (d, J = 8.5Hz, 4H), 7.66 (d, J = 8.5Hz, 4H), ¹³ C
NMR (CDCl ₃ ) 192.25, 132.44, 131.45, 131.22, 130.7

(C) Preparation of 4,4'-bis (phenylethynyl) benzyl 4,4'-dibromobenzyl (1) in diethylamine (150 mL)
5.8 g, 0.0431 mol), phenylacetylene (5.06 g, 0.0495)
mol), (PPh ₃ ) ₂ PdCl ₂ (0.151 g, 0.0002 mol) and CuI (0.82
(0 g, 0.0043 mol) was heated to reflux overnight. The reaction mixture was concentrated and dried, and then CH ₂ Cl placed in ₂ (150 mL), washed with HCl and 10% NaHCO ₃ / H ₂ O, brine 1M, dried (Na ₂ SO _4), then concentrated . 7.92 g (45 percent) of a light tan solid crystallized from 2-propanol
(mp 168 ° -170 ° C.). ¹ HNMR (CDCl ₃ ) δ7.97 (d,
J = 8.2Hz, 4H), 7.64 (d, J = 8.2Hz, 4H), 7.55 (m, 4H), 7.37
(m, 6H), ¹³ C NMR (CDCl ₃ ) δ 193.03, 132.46, 132.03, ¹³
1.82, 130.21, 129.84, 129.06, 128.47, 122.37, 94.2
8, 88.55

(D) Preparation of Compound E A solution of KOH (0.34 g, 0.0061 mol) in ethanol (5 mL) was treated at 75 ° C. with 4,4′-bis (phenylethynyl) benzyl (5.0 g) in ethanol (75 mL). , 0.0122 mol) and 1,3-diphenylacetone (2.69 g, 0.0128 mol). The resulting solution was heated, refluxed for 1 hour, cooled to room temperature, the precipitate was filtered and dried. The product was digested from boiling ethanol to give 5.26 g (74 percent) of a red solid.
mp 222 ° C., ¹ H NMR (CDCl ₃ ) δ 7.5 (bd, J = 3.6 Hz, 4H), 7.
34 (m, 5H), 7.25 (bs, 5H), 6.93 (d, J = 8.0Hz, 4H), ¹³ C NM
R (CDCl ₃ ) δ 199.02, 152.72, 132.31, 131.14, 130.83,
129.93, 129.67, 128.99, 128.04, 127.93, 127.71, 12
7.28, 125.31, 123.12, 122.46, 90.60, 88.71, MS (E
I) 585 (28), 584 (M +, 56), 556 (19), 378 (36), 278 ((1
00)

F. 3,4-bis (3- (phenylethynyl) phenyl) -2,5-diphenylcyclopentadienone (compound F) (a) Preparation of 3,3'-dibromobenzoin In the same manner as in Example 1E (a) In ethanol (125 mL)
3-bromobenzaldehyde (25.0 g, 0.135 mol), 3-ethyl-5- (2-hydroxyethyl) -4-methylthiazolium bromide (1.70, 0.0068 mol), and triethylamine (4.10
g, 0.0405 mol) to give 24.8 g (99 percent) of a viscous yellow oil. _{^{1 H NMR (CDCl 3) δ8.04}} (s, 1H), 7.75 (d, J
= 7.8Hz, 1H), 7.61 (d, J = 8.0Hz, 1H), 7.61 (d, J = 8.0Hz, 1
H), 7.47 (s, 1H), 7.26-7.15 (m, 4H), 5.87 (s, 1H), ^13C
NMR (CDCl ₃₎ δ196.96,140.48,136.86,134.94,131.9
3, 131.86, 130.69, 130.63, 130.26, 127.57, 126.3
3, 123.19, 75.76

(B) Preparation of 3,3'-dibromobenzyl 80% acetic acid aqueous solution was prepared in the same manner as in Example 1E (b).
3,3'-dibromobenzoin (24.8 g, 0.067 m
ol), ammonium nitrate (5.63 g, 0.070 mol)-and copper acetate
From (II) (0.12 g, 0.0007 mol), 17.0 g (69 percent) of a pale yellow solid was obtained. _{^{1 H NMR (CDCl 3) δ8.12}} (s, 2H), 7.88
(d, J = 7.8Hz, 2H), 7.79 (d, J = 7.9Hz, 2H), 7.40 (dd, J = 8.0,
8.0 Hz, 2H), ¹³ C NMR (CDCl ₃ ) δ 191.58, 137.97, 134.2
7, 132.53, 130.60, 128.59, 123.39

(C) Preparation of 3,3′-bis (phenylethynyl) benzyl 3,3′-dibromobenzyl in triethylamine (30 mL)
(5.0 g, 0.0136 mol) and phenylacetylene (3.47 g, 0.1 g).
(0340 mol) was degassed by bubbling nitrogen through for 10 minutes. (PPh ₃ ) ₂ PdCl ₂ (0.067 g, 0.0001 mol) was added and the reaction mixture was heated to reflux overnight. The mixture was concentrated and dried, and then CH ₂ Cl placed in ₂ (100 mL), 1M
HCl, saturated NaHCO ₃ , dried (Na ₂ SO ₄ ), and concentrated to give 3.67 g (66 percent) of a white solid. mp14
4 ° C to 145 ° C. _{^{1 H NMR (CDCl 3) δ8.12}} (s, 2H), 7.96 (d, J
= 7.9Hz, 2H), 7.81 (d, J = 7.7Hz, 2H), 7.52 (m, 6H), 7.36
^{(m, 6H), 13 C} NMR (CDCl 3) δ192.83,137.40,132.82,13
1.52,129.04,128.58,128.25,124.50,122.37,91.1
1, 87.62

(D) Preparation of Compound F A solution of KOH (0.25 g, 0.0045 mol) in ethanol (5 mL) was treated at 75 ° C. with 3,3′-bis (phenylethynyl) benzyl (3.67 g) in ethanol (100 mL). , 0.0089 mol) and 1,3-
It was added dropwise to a solution of diphenylacetone (2.07 g, 0.0098 mol). The resulting solution was heated, refluxed for 1 hour, and cooled to room temperature. The resulting precipitate was filtered and dried. The product was digested from boiling ethanol to give 2.0 g (38 percent) of a red solid. ^{mp208 ℃ (DSC), 1 H} NMR (CDCl 3) δ7.45 (b
m, 6H), 7.31-7.21 (bm, 20H), 6.9 (d, J = 7.9Hz, 2H), ¹³
C NMR (CDCl ₃₎ δ199.38,152.83,132.87,131.48,131.
25, 131.12, 129.80, 129.60, 128.53, 127.99, 127.9
2, 127.84, 127.70, 127.29, 125.03, 122.96, 122.4
7, 90.60, 88.71

G. 1,3,5-Tris (phenylethynyl) benzene (Compound G) Triethylamine (375 g), triphenylphosphine (4.7 g)
865 g), palladium acetate (1.0205 g), and N, N-dimethylformamide (2000 mL) were added to a 5 liter flask equipped with a thermocouple, overhead mechanical stirrer, condenser, addition funnel, and heating mantle with temperature controller. Placed in a three neck round bottom flask. The mixture was stirred for 5 minutes to dissolve the catalyst. Then, diethylhydroxylamine (5 g), 1,3,
5-tribromobenzene (190 g) and phenylacetylene (6
7.67 g) was added. The reactor was purged with nitrogen for 15 minutes and heated to 70 ° C. while maintaining a nitrogen atmosphere. After heating at 70.degree. C. for 30 minutes, phenylacetylene (135.33 g) was added slowly over about 1 hour to raise the temperature to 80.degree. Heating was continued for another 9 hours. It was then cooled to room temperature and water (1 liter) was added to precipitate the crude product. Filtering the product,
Wash three times with 500 mL of water and add 1 mL with 500 mL of cyclohexane.
Washed twice. The catalyst was vacuum dried overnight at 75 ° C. to give a product of 97.25% purity by gas chromatography, 226.40%.
g (99.1% yield) was obtained. The catalyst was dissolved in toluene (1800 mL), filtered through silica gel, the solvent was removed on a rotary evaporator, and 214.20 g of a 99.19% pure product was obtained by gas chromatography (yield 94.2%).
%). The residue was then recrystallized from a mixture of toluene (375 mL) and 2-propanol (696 mL). The white crystals were filtered, and toluene (100 mL) and 2-propanol (400 m
L), dried under vacuum at 75 DEG C. and 1,9,83% pure 1,3,5-tris (phenylethynyl) benzene by gas chromatography (190.0 g, yield 83.91).
%). Further recrystallization from toluene / isopropanol provided material with acceptable levels of organic and ionic impurities.

H. 4,4'-bis (phenylethynyl) diphenyl ether (compound H) thermocouple, overhead mechanical stirrer, cooler,
And a 1-liter three-necked round-bottomed flask equipped with a heating mantle equipped with a temperature controller, triethylamine (111.5 g), triphenylphosphine (1.158 g), palladium acetate (0.2487 g).
g), diethylhydroxylamine (1.24 g), 4,4'-dibromodiphenyl ether (68.6 g), phenylacetylene (67.74 g), N, N-dimethylformamide (136 mL) and 72
mL of water was charged. Purge the reactor with nitrogen for 15 minutes,
Then, it was heated to 90 ° C. for 19 hours while maintaining the nitrogen atmosphere. It was then cooled to room temperature and water (80 mL) was added. The crude product is filtered, the solid is washed once with 120 ml of toluene and four times with 160 ml of water, dried in vacuo overnight and 4,4'-bis (phenyl) 99.64% pure by gas chromatography. 66.3 White needle-like crystals of (ethynyl) diphenyl ether
7 g (85.6% yield) was 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)
Placed in a 1 liter three-necked flask equipped with a mechanical stirrer, a condenser connected to an HBr trap and an addition funnel. The mixture was stirred and the temperature was maintained by a water bath. CHCl ₃ (150m
Br _{2 in} L) (47.5 mL) was added over 2.5 hours. The mixture was stirred at room temperature for another 2 hours. GC has 5 percent monobromo-o-terphenyl, 81 percent dibromo-o-terphenyl and 9 percent tribromo-o-terphenyl.
-Showed terphenyl.

Make ice and 2N NaOH solution basic to the above solution
Added until it was. Discard the upper layer and add CHCl _ThreeMore solution
Washed with water. This CHCl_ThreeAdd sodium sulfate to the solution
And then filtered through a Buchner funnel filled with Celite.
I have. Chloroform was removed. 750 mL for white solid
Of glacial acetic acid and heat the slurry to 95 ° C in a water bath.
Was. Almost half of the solid dissolved. Transfer the hot solution to a 1000 mL
Moved to the car. The residual solids weigh 71 g, which is 1.4
-Cent monobromo-o-terphenyl, 93% 4,
4 "-dibromo-o-terphenyl and 6 percent 4,4 ',
4 "-tribromo-o-terphenyl. Acetic acid
The solution was cooled to room temperature. White crystals were collected. GC is 1
Percent monobromo-o-terphenyl, 83%
4,4 "-dibromo-o-terphenyl, and 13 percent 4,
4 ', 4 "-tribromo-o-terphenyl was shown.
To 4,4 "-bis (phenylethynyl) -o-terphenyl
Used for fabrication.

(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 added to a mechanical stirrer and cooled. vessel was the reaction system purged for 20 minutes with N ₂ inlet, and were placed in a four-necked flask 1000mL equipped with a thermometer. nitrogen.

After dissolution of the solid, 2.784 g of Pd (PPh ₃ ) ₂ C
l ₂ , 2.538 g of CuI and 5.545 g of PPh ₃ were added. Nitrogen was bubbled through the solution with stirring for 30 minutes. Heating was started and the mixture was refluxed. Reflux was continued overnight.
A white solid formed during the reaction.

This solution was placed in a 2 liter beaker containing ice. The flask was washed several times with water and poured into a beaker. The solid formed was filtered on a Buchner funnel and washed several times with water. This solid was dissolved in a 2 liter beaker using toluene. The upper layer was transferred to a one liter flask. The lower layer containing undissolved material was washed with toluene and combined with the upper layer to which the toluene solution was transferred to form a dark brown solution. The dark brown solution was decolorized with charcoal. The solution was heated with stirring in a water bath. Then Na ₂ SO ₄ was added.

The solution was filtered through a calcined glass filter and the solvent was evaporated. The solid was dissolved in 350 mL of hot toluene in a 2 L beaker and 1300 mL of isopropanol was added to crystallize the solid. The 2 liter beaker was placed in the refrigerator overnight and the crystals were collected and washed with isopropanol. After weighing the yellow solid
It was 25 g. The yellow solid was washed with acetone and then crystallized twice in ethyl acetate. The yield of white flakes was 12 g.

J. 4,4′-diethynyl diphenyl 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 triphenylphosphine (1.0 g, 0.0038 mol) were purged with nitrogen for 30 minutes while heating to slow reflux.

2-Methyl-3-butyn-2-ol (7.6 g, 0.090 mol), purged with nitrogen for 30 minutes, was quickly added to the refluxing solution in 5 minutes. The resulting reaction mixture was heated to reflux for 14 hours, cooled to room temperature, concentrated and dried. The residue was taken up in CH ₂ Cl _2, washed with water and brine, then concentrated. The residue was taken up in toluene (200 mL) and sodium hydride (0.10 g, 0.20 mol) was added. The reaction mixture was heated to reflux and about 100 mL of solvent was evaporated. The solution was cooled and then concentrated. The residue is taken up in CH ₂ Cl ₂ and 1N H
Washed with Cl, water, saturated aqueous NaHCO ₃ and brine, then dried (Na ₂ SO ₄ ) and concentrated to give a dark oil. The residue was filtered through silica gel, eluted with CH ₂ Cl ₂ and concentrated to give a viscous oil. It solidified on standing. _{^{1 H NMR (CDCl 3) δ7.45}} (d, J = 8.6Hz, 4H), 6.93 (d, J =
8.7 Hz, 4H), 3.04 (s, 2H), ¹³ C NMR (CDCl ₃ ) δ 157.02, ¹³
3.93, 119.20, 118.94, 117.16, 83.16. The reaction scheme is as follows.

[0106]

Embedded image

K. 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (compound K) (a) Production of 4,4'-diphenylacetyldiphenyl ether methylene dichloride (200 mL) ) In aluminum chloride (97.
To a slurry of 9 g (0.734 mol) was added a solution of diphenyl ether (50.0 g, 0.294 mol) and phenylacetyl chloride (102 g, 0.661 mol) in methylene chloride (50 mL) over 30 minutes. After the addition was complete, the reaction mixture was warmed to ambient temperature and stirred overnight. 1.5k with stirring the reaction mixture
g of ice / water was carefully poured. Methylene chloride (1500 mL) was added to dissolve the solid and the layers were separated. The organic layer was filtered through celite, concentrated and dried. Recrystallize from toluene to give the title compound as a light brown prism.
110 g (92 percent) were obtained.

(B) Preparation of 4,4′-bis (phenylglyoxaloyl) diphenyl ether An aqueous HBr solution (97 mL of a 48 weight percent solution) was added to DMSO (400
4,4'-Diphenylacetyldiphenyl ether in
(50.0 g, 0.123 mol) was added to the slurry and the resulting mixture was heated to 100 ° C. for 2 hours and then cooled to room temperature. The reaction mixture was partitioned between toluene (500mL) and water (750mL). The organic layer was washed with water (3 × 250 mL), then with brine and concentrated to give a viscous yellow oil. It solidified on standing at ambient temperature. Recrystallization from ethanol yielded 35.9 g (67 percent) of a yellow cube.

(C) Preparation of Compound K 195.4 g (0.4498 mol, 1.0 eq) in a 5 liter nitrogen purged flask equipped with a thermocouple, reflux condenser with nitrogen inlet, mechanical stirrer, and addition funnel. 4,4'-bis (phenylglyoxaloyl) diphenyl ether of
193.9 g of diphenylacetone (0.9220 mol, 2.05 eq) and 2.5 L of deoxygenated ethanol were charged. The mixture was heated to reflux where a homogeneous solution was obtained, which was purged with nitrogen for 30 minutes. Add 25.2 g KOH (0.4498) to the addition funnel.
mol, 1.0 eq), 200 mL of ethanol, and 25 mL of water were added. The temperature was brought to 74 ° C. and the KOH solution was added over 5 minutes. An exothermic reaction appeared and was maintained at reflux until 3/4 of the solution was added, after which the temperature began to drop. A dark purple color appeared upon addition of the base and solids were seen before the addition was complete. At the end of the addition, the heterogeneous solution was vigorously refluxed for 15 minutes to form more solid. The mixture was cooled to 25 ° C., 29.7 g of glacial acetic acid (0.4948 mol, 1.1 eq) was added and stirred for 30 minutes. The crude product was isolated by filtration, washed in a funnel with 1 liter of water, 3 liters of ethanol, 2 liters of methanol, dried in vacuo at 60 ° -90 ° C. for 12 hours, and 323 g (92 percent) of crude DPO-CPD was obtained. It was 94% pure by LC. HP
Dissolved in LC grade methylene chloride (10 weight percent), transferred to a 5 liter flask equipped with a bottom flash valve and mechanical stirrer, and washed 2-7 times with an equal volume of low ionic water for 10-90 minutes . The CH ₂ Cl ₂ solution was then applied to a 5 cm column containing 75 g of silica gel in CH ₂ Cl ₂ . The column was washed with 1 liter of CH ₂ Cl _2, at which time the filtrate was essentially clear. The solution was evaporated to dryness, redissolved in THF and evaporated again to remove residual methylene chloride lumps. Add this powder to an addition funnel and Friedrichs
Transferred to a 5 liter flask equipped with a reflux condenser and dissolved in deoxygenated HPLC THF (0.07-0.12 g / mL). Then 1
An additional liter of THF was added and a nitrogen purge tube was inserted into the solution. The solution was purged with nitrogen for 3 hours,
The THF was concentrated at 45-50 ° C and the residual methylene chloride was removed by distillation. A distillation head was attached to remove 700 mL to 1 liter of THF. The solution was then slowly cooled to room temperature over several hours and then cooled to below 10 ° C. in an ice bath where crystallization occurred. The crystals were filtered using a 5 mm PTFE filter. The crystals are then washed with 1 liter of methanol and dried in vacuum at 80-90 ° C. overnight to give 99% LC purity of DPO-CPD with a yield of 70-85.
Gained in percent. mp 270 ° C.

L. 2,4,4'-tris (phenylethynyl)
Diphenyl ether (compound L) (a) Production of 2,4,4'-tribromodiphenyl ether Diphenyl ether (20.0 g,
(0.118 mol) was slowly added with bromine (57.3 g, 0.358 mol). During this addition, the temperature was slowly raised to 60 ° C and held at this temperature for 2 hours. The mixture was then heated to 70 ° C. for 30 minutes and cooled to ambient temperature. This mixture is treated with CH ₂ Cl ₂ (1
00 mL), washed with 10% aqueous Na ₂ CO ₃ , then dried (Na ₂ SO ₄ ), concentrated and 44.8 g (10
0 percent). It solidified on standing at ambient temperature.

(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), a slurry of copper (I) iodide (574 g, 0.00302 mol) and triphenylphosphine (3.95 g, 0.0151 mol) were purged with nitrogen for 30 minutes while slowly heating to reflux.

Phenylacetylene (41.4 g, 0.406 mol), purged with nitrogen for 30 minutes, was quickly added to the refluxing solution over 5 minutes. The resulting reaction mixture was refluxed for 14 hours. The solution was cooled to ambient temperature and concentrated. The residue was taken up in CH ₂ Cl ₂ and washed with 1N HCl, water, saturated aqueous NaHCO ₃ and brine, and concentrated to 100 mL. The solution was filtered through silica gel, eluted with methylene chloride and the resulting filtrate was concentrated. The residue was crystallized from EtOAc / hexane,
39.0 g (73 percent) of a light brown solid was obtained. mp 123-12
6 ° C. _{^{1 H NMR (CDCl 3) δ7.77}} (bs, 1H), 7.53-7.44 (m, 20
H), 6.98 (dd, J = 8.0, 8.0, 2H), ¹³ C NMR (CDCl ₃ ) δ 156.8
1, 156.00, 136.49, 132.93, 132.57, 131.31, 131.2
2, 128.23, 128.10, 128.06, 127.99, 127.87, 123.0
4, 122.74, 122.51, 119.63, 119.09, 118.67, 117.8
4, 116.30, 95.05, 89.47, 88.72, 87.79, 83.87

M. 3,3 '-(1,4-phenylene) bis (2,5-di
-(4-Fluorophenyl) -4-phenylcyclopentadienone) (Compound M) 1,3-bis (4-fluorophenyl) -2-propanone (1.476 g
Bis-PGB from KenSeika Corporation
1,4-bis (phenylglyoxaloyl) benzene (1.026 g, 0.003 mol), available as dimethyltrimethylammonium hydroxide (0.32 g, 40 percent in methanol), was dissolved in 90 mL of 1-propanol. .
The solution immediately turned purple. Reflux was continued for 2 hours.
The mixture was cooled to room temperature and then brought to 0 ° C. The solid was collected and washed with cold methanol. The end was 1.92 g. This solid has a metallic color and is determined by DSC to be 31
Melted at 6 ° C. E.Elce, ASHay, J.Poly.Sci .: Part
A: 1,3-Bis (4-fluorophenyl) -2-propanone was produced by the method described in Polymer Chemistry, 33, 1143-1151.

N. 4,4 ', 4 "-tris (phenylethynyl)-
o-Terphenyl (compound N) (a) Preparation of 4,4 ', 4 "-tribromo-o-terphenyl o-terphenyl (39.6 g), Fe (3.3 g) and CHCl_Three(450mL)
The mechanical stirrer, the cooler connected to the HBr trap and
Placed in a 1 liter three-necked flask equipped with a funnel. This
Was stirred and the temperature was maintained by a water bath. CHCl
_ThreeBr in (100mL) _Two(26.5 mL) was added over 1.5 hours.
The mixture is stirred at room temperature for a further 2 hours, then
Stirred at 65 ° C. for a further 2 hours. GC is 14 percent
Todibromo-o-terphenyl, 85% tribromo
-o- Terphenyl and 0.7 percent tetrabromo-o-
Terphenyl was indicated.

Make ice and 2N NaOH solution basic to the above solution
Added until it was. Discard the upper layer and add CHCl _ThreeMore solution
Washed with water. This CHCl_ThreeAdd sodium sulfate to the solution
And then filtered through a Buchner funnel filled with Celite.
I have. Chloroform was removed. 750 mL of white solid
Mix with glacial acetic acid and heat the slurry to 95 ° C in a water bath.
Was. The yield after removing all acetic acid is 42.5 g,
This is 11 percent 4,4 "-dibromo-o-terphenyl,
88 percent 4,4 ', 4 "-tribromo-o-terphenyl and
Consists of 0.6 percent tetrabromo-o-terphenyl
I was This solid is treated with 4,4 ', 4 "-tris (phenylethyn
Ru) -o-terphenyl. The acetic acid solution is 56
Percent 4,4 "-dibromo-o-terphenyl, 36%
4,4 ', 4 "-tribromo-o-terphenyl and 1.8 parts
It contained St. tetrabromo-o-terphenyl.

(B) Preparation of compound N 4,4 ', 4 "-tribromo-o-terphenyl (24.7 g, 0.053 mol
l), phenylacetylene (22 mL), triethylamine (28
0 mL) and pyridine (180 mL) were added to a mechanical stirrer,
The mixture was placed in a 1000 mL four-necked flask equipped with an N ₂ inlet and a thermometer. The reaction was purged with nitrogen for 20 minutes.

After the solid had dissolved, 1.113 g of Pd (PPh ₃ ) ₂ C
l ₂ , 1.005 g of CuI, and 2.218 g of PPh ₃ were added. Nitrogen was bubbled through the solution with stirring for 30 minutes. Heating was started and the mixture was refluxed. Reflux was continued overnight.
A white solid formed during the reaction.

The solution was placed in a 2 liter beaker containing ice. The flask was washed several times with water and poured into a beaker. The solid formed was filtered on a Buchner funnel and washed several times with water. This solid was dissolved in a 2 liter beaker using toluene. The upper layer was transferred to a one liter flask. The lower layer containing undissolved material was washed with toluene and combined with the upper layer to which the toluene solution was transferred to form a dark brown solution. The dark brown solution was decolorized with charcoal. The solution was heated with stirring in a water bath. Then Na ₂ SO ₄ was added. This solution was filtered through a calcined glass filter and the solvent was evaporated. 600m solid in 2 liter beaker
Dissolved in L hot acetone. Then collect the crystals,
Washed with acetone. Light yellow solid weighed 11
g. This solid was crystallized twice from ethyl acetate. The yield of the white powder was 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 ( 0.557g, 0.794mmo
l), triphenylphosphine (1.11 g, 4.23 mmol), copper (I) iodide (0.503 g, 2.64 mmol), pyridine (73 mL, 0.93 mol)
l) and triethylamine (110 mL, 0.783 mol) were mixed and stirred for 30 minutes under nitrogen. The mixture was then refluxed overnight. The solution was poured into a water / ice bath. The solid formed was collected and washed with water. This solid was dissolved in toluene and the insoluble material was filtered. This toluene solution was decolorized with charcoal. Isopropanol was added, forming yellow crystals.
The crystals were isolated by filtration, weighed and weighed 4.0 g (13.1 mmo
l, 50% yield). Melting point is 109 ° C (DSC)
Met. NMR and mass spectral analyzes were consistent with the proposed structure of 1,3-bis (phenylethynyl) benzene.

P. 1,4-Bis (phenylethynyl) benzene (Compound P) Compound P was produced in the same manner as for Compound O, except that 1,4-dibromobenzene was used instead of 1,3-dibromobenzene.

Q. 1,2,4-Tris (phenylethynyl) benzene (Compound Q) A slurry of 1,2,4-tribromobenzene (20.0 g, 0.0635 mol) in triethylamine (250 mL) was degassed by purging with nitrogen for 30 minutes. did. Triphenylphosphine (2.2 g, 0.00836
mol) and then Pd (OAc) ₂ (0.100 g, 0.000445 mol)
And CuI (0.315 g, 0.00165 mol) were added and the resulting mixture was heated to reflux. Phenylacetylene (20.1 g, 0.197 mol) purged with nitrogen for 30 minutes was added over 10 minutes. The reaction mixture was heated to reflux overnight. The reaction mixture was cooled to ambient temperature, concentrated and dried. The residue was taken in acetone (200 mL) and water (300 mL) was added slowly with stirring. The precipitate was filtered and methyl alcohol (500 mL)
And then with water (200 mL) and dried to give a light brown solid. This was purified by recrystallization from acetone / methanol to give a white solid in 60% yield. NM
R analysis was consistent with the structure of the desired material. The reaction scheme is shown below.

[0122]

Embedded image

Example 2 1,3-bis (phenylethynyl)
Preparation of Polymer from Mixture of Benzene (Compound O) and 1,3,5-Tris (phenylethynyl) benzene (Compound G) and Compound M 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 mmo
l) was refluxed in 1,3-diisopropylbenzene (4 mL) for 42 hours. The dark solution turned red and became viscous. This solution was spin-coated on a wafer and cured at 400 ° C. for 1 hour to form a film. The reaction scheme is shown below.

[0124]

Embedded image

Example 3: Synthesis of 4,4'-bis (phenylethynyl) -o-terphenyl (compound I) and 4,4 ', 4 "-tris (phenylethynyl) -o-terphenyl (compound N) Preparation of Polymer from Mixture and Compound M 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 m
mol) was refluxed in 5 mL of 1,3-diisopropylbenzene for 48 hours. The yellow viscous solution was cooled to room temperature and spin-coated on the wafer. The polymer was cured at 400 ° C. for 1 hour to form a film. The reaction scheme is shown below.

[0126]

Embedded image

Example 4: 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone)
Preparation of polymer from (compound K) and 4,4'-bis (phenylethynyl) diphenyl ether (compound H) 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclo) Pentadienone) (15.0000g, 0.019158mo
l), 4,4'-bis (phenylethynyl) diphenyl ether (7.0974g, 0.019158mol), and N-methylpyrrolidinone
(51.60 g) was added to a 250 mL round bottom flask. The flask was connected to a nitrogen inlet and the mechanically stirred solution was heated to 200 ° C. in an oil bath. After 19.5 hours at 200 ° C., gel permeation chromatography
Mn of 1551 and Mw of 2383 were shown. The solution was cooled and placed in a bottle. Take a part of this solution with a syringe,
Filtered through a 1.0 micron syringe filter onto a 4 "silicon wafer. The wafer was spin coated under a heat lamp at 2000 rpm for 60 seconds. The coated wafer was placed on a hot plate set at 90 ° C for several minutes. The wafer is placed in a nitrogen purged oven, purged at room temperature for 45 minutes, and then
Per minute to 400 ° C., held at 400 ° C. for 1 hour, and then cooled to room temperature. The wafer thus obtained was coated with a polyphenylene polymer. This solution was found to completely fill the submicron gap when applied and cured.

Example 5: 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone)
Preparation of polymer from (Compound K), 4,4'-bis (phenylethynyl) diphenylether (Compound H) and 1,3,5-tris (phenylethynyl) benzene (Compound G) In a 100 mL three-necked round bottom flask 3,3 ′-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (10.0000 g, 0.01277 mole), 4,4′-bis (phenylethynyl) diphenyl ether (2.3660 g, 0.006386mole)
, 1,3,5-tris (phenylethynyl) benzene (2.4170
g, 0.006386 mole), and N-methylpyrrolidinone (34.5m
L) was added. The flask was connected to a nitrogen inlet and the mechanically stirred solution was heated to 200 ° C. in an oil bath. 20
After 11 hours at 0 ° C., the solution was cooled and bottled. A portion of this solution was taken with a syringe and filtered through a 1.0 micron syringe filter onto a 4 inch silicon wafer. The wafer was spin coated at 2000 rpm for 60 seconds. The coated wafer was placed on a hot plate set at 90 ° C. for 2 minutes. The wafer was then placed in a nitrogen purged oven, purged at room temperature for 45 minutes, then heated at 10 ° C./min to 400 ° C., held at 400 ° C. for 1 hour, and then cooled to room temperature. The wafer thus obtained was coated with a polyphenylene polymer. This solution was found to completely fill the submicron gap when applied and cured. The cured polymer was 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 1,3,5-tris (phenylethynyl)
Preparation of Polymer from Benzene (Compound G) In a 25 mL Schlenk tube, 3,3 ′-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (2.0000 g, 0.002554 mole) ), 1,3-bis (phenylethynyl) benzene (0.4740 g, 0.001703 mole), 1,3,5-tris (phenylethynyl) benzene (0.4834 g, 0.001277)
mole) and N-methylpyrrolidinone (6.9 mL) were added.
The tube was connected to a nitrogen inlet and the mechanically stirred solution was heated to 200 ° C. in an oil bath. After 20 hours at 200 DEG C., gel permeation chromatography showed Mn = 1463 and Mw = 2660 relative to polystyrene standards. The solution was cooled to room temperature and placed in a bottle. A portion of this solution was taken with a syringe and filtered through a 1.0 micron syringe filter onto a 4 inch silicon wafer. The wafer was spin coated under a heating lamp at 2000 rpm for 60 seconds. The coated wafer was placed on a hot plate set at 90 ° C. for 2 minutes. The wafer was then placed in a nitrogen purged oven, purged at room temperature for 45 minutes, and then heated at 10 ° C / min to 400 ° C,
Hold for a time and then cool to room temperature. The wafer thus obtained was coated with a polyphenylene polymer.

Example 7: 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone)
Preparation of Oligomeric Solution from (Compound K) and 1,3,5-Tris (phenylethynyl) benzene (Compound G) Low-ion in a 1 liter, three-necked Pyrex round bottom flask of Pyrex washed and dried with deionized water and HPLC grade acetone 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (100.0 g, 0.128 mole),
Low ionic 1,3,5-tris (phenylethynyl) benzene
(48.3 g, 0.128 mole), and electronic grade N-methylpyrrolidinone (346 g). The flask was connected to a nitrogen / vacuum inlet. The mechanically stirred solution was evacuated by evacuating and refilling with nitrogen five times. Nitrogen gas was then flushed from the headspace of the flask and out through an inorganic oil bubbler. The solution was then heated to an internal temperature of 200 ° C. After heating for 8.5 hours, the solution was cooled and transferred to a bottle made of tetrafluoroethylene. Analysis of this final solution by gel permeation chromatography showed M n = 1498 and M w = 2746 relative to polystyrene standards. Analysis of this final solution by reverse phase chromatography revealed residual 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5
-Triphenylcyclopentadienone) level of 1.8% by weight. Analysis of this final solution by neutron activation showed that the sodium level was 52 ppb, the potassium level was 190 ppb, the palladium level was 90 ppb, the bromine level was 2.4 ppb, the iodine level was 0.6 ppb, and the chlorine level was 2.4 ppb. .

Example 8: Coating and curing of the oligomer solution from Example 7 3 mL of a silane-based adhesion promoter, AP8000, available from The Dow Chemical Company, on a 200 mm wafer, applied to the surface of the wafer Then, the entire surface was slowly spread, left for 2 seconds, and finally spun at 3000 rpm for 10 seconds. 3 mL of the polyphenylene oligomer solution prepared in Example 7 was applied to a 200 mm wafer by a precision pump / filtration system. Millipore Gen-2 was spun at 750 rpm on the surface of the wafer coated with the adhesion promoter.
The rotation of the wafer was immediately increased to 2000 rpm, the oligomer solution was applied and held at this spin speed for 20 seconds. While applying the oligomer solution, a continuous stream of mesitylene was applied to the backside of the wafer for 5 seconds. After spin coating the wafer with the oligomer, the film was dried on a hot plate at 70 ° C. for 20 seconds. After drying, 2,000 wafers
A continuous stream of mesitylene was applied from the back or directly from above while spinning at rpm to remove 2 mm to 5 mm of the edge of the coating. After removal of the ends, the oligomer was further polymerized on a hot plate at 325 ° C. for 90 seconds in a nitrogen atmosphere. The film was then crosslinked at 450 ° C. for 2 minutes on a hot plate in a nitrogen atmosphere or at 450 ° C. for 6 minutes in a nitrogen purged oven. This film is measured by dynamic mechanical analysis,
It had a glass transition temperature higher than 450 ° C.

[0132]

[Table 1]

[0133]

[Table 2]

[0134]

[Table 3]

It is known that different reactants require different reaction parameters since the above compounds are prepared using standard chemical methods. Variations in reaction parameters, such as using one of the reactants in excess, using a catalyst, using a temperature higher or lower than room temperature, performing high speed mixing and other conventional methods, are contemplated by the present invention. Is within the range.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Duane Earl. Lomar United States, Michigan 48642, Midland, Lowell Court 4025 (72) Inventor Infunzo United States, Michigan 48640, Midland, Dilloway Drive 1524 (72) Inventor Zenon Rysenko United States, Michigan 48640, Midland, West Meadowbrook Live 214 (72) Inventor Michael E. Mills United States, Michigan 48642, Midland, Avalon Street 1604 (72) Inventor Gary Earl. Basque USA, Michigan 48640, Midland, Sylvan Lane 613 (72) Inventor Paul H. Townsend, The Thurd United States, 48642, Michigan, Willard Street, Midland 1102 (72) Inventor Dennis W. Brussels. Smith, Jr. United States, Texas 77545, Fresno, Pleasant Trail 4607 (72) Inventor Stephen Jay. Martin United States, 48640, Michigan, Scarborough Lane, Midland 3019 (72) Inventor Robert A. Debreeze USA, Michigan 48642, Midland, Greenbrier Terrace 3408 F-term (reference) 4J032 CA04 CA06 CA07 CA35 CA38 CB03 CB04 CE03 CE06 CE07 CE20 CE22 CE24 CG01 CG06

Claims (14)

[Claims] 1. A product of a Diels-Alder reaction between at least one compound having two or more diene functions and at least one compound having two or more dienophile functions, wherein at least one of said compounds Crosslinked or crosslinkable polyphenylene, one having three of said functional groups. 2. The polyphenylene according to claim 1, wherein the dienophile functional group is an acetylene group. 3. An oligomer, an uncured polymer or a cured polymer, wherein the diene functional groups are cyclopentadienone groups and the ratio of cyclopentadienone groups to acetylene groups is from 1: 1 to 1: 3. Claim 2
Polyphenylene as described. 4. The polyphenylene of claim 3, wherein at least 10% of said cyclopentadienone groups are unreacted. 5. A composition comprising the polyphenylene according to claim 1 in a solvent selected from N-methylpyrrolidinone, a mixture of N-methylpyrrolidinone and cyclohexanone, or a mixture of gamma-butyl lactone and mesitylene. 6. A compound having a diene functional group and a compound having a dienophile functional group at a temperature of 150 to 250 ° C.
The method for producing polyphenylene according to any one of claims 1 to 4, comprising heating for 48 hours. 7. The method of claim 6, further comprising coating the substrate with an oligomer or uncured polymer, 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 a 1 μm deep, 0.5 μm wide gap without leaving voids when cured. 9. The method of claim 7, further comprising either or both patterning the coating and / or planarizing the surface of the cured polymer using chemical mechanical polishing. 10. The base material and the base material on the base material.
A product comprising the substance comprising the cured polyphenylene according to any one of the above. 11. The material of claim 8, wherein said substance is a foam.
The product described. 12. The integrated circuit, wherein the substrate is an active substrate including a transistor, and the material at least partially separates patterned metal lines forming an electrical connection structure. The product described. 13. The method of claim 1, wherein said metal line is copper.
0 described products. 14. The article of claim 10, wherein said substance comprises an adhesion promoter or a layer of an adhesion promoter is present between said substance and a substrate.