Polyarylene resins

Abstract

Certain cyclopentadienone monomers having polar moieties are useful in forming polyarylene resins having improved solubility in certain organic solvents and are useful in forming polyarylene resin layers in electronics applications.

Claims

1. A cyclopentadienone compound of formula (1) ##STR00027## wherein each R.sup.1 is independently chosen from H, C.sub.1-20-alkyl, optionally substituted C.sub.5-30-aryl; each R.sup.2 is independently chosen from H, C.sub.1-20-alkyl, optionally substituted C.sub.5-30-aryl, and (PG-L).sub.t-Ar.sup.1; each PG is C(O)OR.sup.5; R.sup.5 is H; each Ar.sup.1 is independently optionally substituted C.sub.5-30-aryl; L is a single chemical bond; and L.sup.1 is chosen from O, C.sub.1-30-ketoalkyl-, C.sub.1-30-ketoalkyl-C.sub.6-30-aryl, C.sub.6H.sub.4, C.sub.10H.sub.6, C.sub.6H.sub.4C.sub.6H.sub.4, C.sub.6H.sub.4OC.sub.6H.sub.4, C.sub.6H.sub.4OC.sub.6H.sub.4OC.sub.6H.sub.4, and groups of formula (1a); a is an integer from 0 to 3; t is an integer from 1 to 4; and w=1; provided that when a=0, L.sup.1 has the formula (1a) ##STR00028## wherein Ar.sup.2 is a C.sub.5-30-aryl; each R.sup.3 is independently chosen from H, C.sub.1-20-alkyl, optionally substituted C.sub.5-30-aryl, and (PG-L).sub.t-Ar.sup.1; each of L.sup.2, L.sup.3 and L.sup.4 is chosen from a single chemical bond, O, C.sub.1-30-alkyl-, C.sub.1-30-ketoalkyl-, C.sub.1-30-ketoalkyl-C.sub.6-30-aryl-, C.sub.6-30-aryl-, C.sub.6-30-aryl-OC.sub.6-30-aryl-, C.sub.6-30-aryl-OC.sub.6-30-aryl-OC.sub.6-30-aryl-, and combinations of the foregoing; t1 is an integer from 1 to 4; b is 0 or 1; and L.sup.2, L.sup.3 and L.sup.4 may be the same or different.

2. The cyclopentadienone compound of claim 1 wherein each Ar.sup.1 and Ar.sup.2 is independently chosen from pyridyl, phenyl, naphthyl, acenaphthyl, fluorenyl, carbazolyl, anthracenyl, phenanthryl, pyrenyl, coronenyl, tetracenyl, pentacenyl, tetraphenyl, benzotetracenyl, triphenylenyl, perylenyl, tolyl, xylyl, dibenzothiophenyl, thioxanthonyl, indolyl, and acridinyl.

3. A polyarylene resin comprising as polymerized units one or more first cyclopentadienone monomers of claim 1, and one or more polyalkynyl-substituted second monomers.

4. The polyarylene resin of claim 3 wherein at least one polyalkynyl-substituted second monomer has the formula (2) ##STR00029## wherein each Ar.sup.3 and Ar.sup.4 is independently a C.sub.5-30 aryl moiety; each R.sup.11 is independently chosen from H, optionally substituted C.sub.5-30-aryl, and (PG-L.sup.5).sub.t2-Ar.sup.5; each R.sup.12 is independently chosen from H, optionally substituted C.sub.5-30 aryl, and -L.sup.5-PG; PG is a polar moiety; each Ar.sup.5 is independently an optionally substituted C.sub.5-30-aryl; each L.sup.5 is a single chemical bond or a divalent linking group; each Y is independently a single chemical bond or a divalent linking group chosen from O, S, S(O), S(O).sub.2, C(O), (C(R.sup.13).sub.2).sub.z, C.sub.6-30-aryl, and (C(R.sup.13).sub.2).sub.z1(C.sub.6-30-aryl)-(C(R.sup.13).sub.2).sub.z2; each R.sup.13 is independently chosen from H, hydroxy, halo, C.sub.1-10-alkyl, C.sub.1-10-haloalkyl, and optionally substituted C.sub.6-30-aryl; t2=1 to 4; b1=1 to 4; each b2=0 to 2; b1+ each b2=2 to 6; c=0 to 4; each c1=3 to 5; d=0 to 2; z=1 to 10; b1+c+d=6; z1=0 to 10; z2=0 to 10; and z1+z2=1 to 10.

5. The polyarylene resin of claim 4 wherein b1=2 or 3 and d=0.

6. The polyarylene resin of claim 4 wherein R.sup.12 is H, or C.sub.6-10-aryl.

7. A polyarylene resin composition comprising the polyarylene resin of claim 3 and one or more organic solvents.

8. A method of manufacturing an electronic device comprising providing a substrate; coating a layer of the polyarylene resin composition of claim 7 on a surface of the substrate; removing any organic solvent; and curing the polyarylene resin to form a dielectric material layer.

9. A method of forming a patterned layer comprising: (a) coating on a substrate a layer of a polyarylene resin composition of claim 7; (b) removing organic solvent to form a polyarylene resin layer; (c) coating a layer of a photoresist on the polyarylene resin layer; (d) exposing the photoresist layer to actinic radiation through a mask; (e) developing the exposed photoresist layer to form a resist pattern; and (f) transferring the pattern to the polyarylene resin layer to expose portions of the substrate.

10. The method of claim 9 wherein at least one polyalkynyl-substituted second monomer has the formula (2) ##STR00030## wherein each Ar.sup.3 and Ar.sup.4 is independently a C.sub.5-30 aryl moiety; each R.sup.11 is independently chosen from H, optionally substituted C.sub.5-30-aryl, and (PG-L.sup.5).sub.t2-Ar.sup.5; each R.sup.2 is independently chosen from H, optionally substituted C.sub.5-30 aryl, and -L.sup.5-PG; PG is a polar moiety; each Ar.sup.5 is independently an optionally substituted C.sub.5-30-aryl; each L.sup.5 is a single chemical bond or a divalent linking group; each Y is independently a single chemical bond or a divalent linking group chosen from O, S, S(O), S(O).sub.2, C(O), (C(R.sup.13).sub.2).sub.z, C.sub.6-30-aryl, and (C(R.sup.13).sub.2).sub.z1(C.sub.6-30-aryl)-(C(R.sup.13).sub.2).sub.z2; each R.sup.13 is independently chosen from H, hydroxy, halo, C.sub.1-10-alkyl, C.sub.1-10-haloalkyl, and optionally substituted C.sub.6-30-aryl; t2=1 to 4; b1=1 to 4; each b2=0 to 2; b1+ each b2=2 to 6; c=0 to 4; each c1=3 to 5; d=0 to 2; z=1 to 10; b1+c+d=6; z1=0 to 10; z2=0 to 10; and z1+z2=1 to 10.

Description

EXAMPLE 1: DIPHENYLACETONE DERIVATIVE SYNTHESIS

(1) To a 250 mL round-bottomed flask, methyl 4-(bromomethyl)benzoate (12.10 g, 52.83 mmol), p-toluenesulfonylmethyl isocyanide (5.00 g, 25.61 mmol), and tetrabutylammonium iodide (473 mg, 1.28 mmol) were combined in 50 mL dichloromethane with magnetic stirring. The mixture was cooled to 0 C. and then a 40% w/w aqueous sodium hydroxide solution (7.16 mL) was added dropwise to the mixture with rapid stirring. The biphasic mixture was then allowed to warm to room temperature and continue to stirring rapidly for 4 hours after which the reaction was complete indicated by consumption of the methyl 4-(bromomethyl)benzoate by TLC (9:1 heptane:ethyl acetate).

(2) Next, a separatory funnel was used to separate the two phases. The organic phase was separated and set aside and the aqueous phase was extracted twice with 20 mL portions of dichloromethane. The combined organic extracts were dried over magnesium sulfate, filtered, and concentrated in vacuo. This crude concentrated residue was dissolved in a mixture of 40 mL dichloromethane and 15 mL tetrahydrofuran. With rapid stirring, 15 mL of 6 M hydrochloric acid was added slowly dropwise and the mixture was allowed to stir at room temperature for 30 minutes. Next the reaction mixture was quenched with saturated sodium bicarbonate. A separatory funnel was used to separate the two phases. The organic phase was separated and set aside and the aqueous phase was extracted twice with 20 mL portions of dichloromethane. The combined organic extracts were dried over magnesium sulfate, filtered, and concentrated in vacuo over 10 g of silica gel. The dried solid was purified via flash column chromatography using ethyl acetate and heptane (1:20) to yield 4.51 g of Compound (8) (54% yield) confirmed by NMR, and the compound stored at or below 0 C. The overall reaction is illustrated in Reaction Scheme 2.

(3) ##STR00025##

EXAMPLE 2: 4,4-OXYDIBENZIL METHYL ESTER DERIVATIVE SYNTHESIS

(4) To a dry, nitrogen-flushed 500 mL three-neck round-bottomed flask fitted with a water-jacketed condenser and thermocouple adapter, bis(4-ethynylphenyl) ether (3.427 g, 15.70 mmol), methyl 4-bromobenzoate (8.104 g, 37.68 mmol), bis(triphenylphosphine)palladium chloride (661 mg, 0.942 mmol), copper(I) iodide (90 mg, 0.471 mmol), and anhydrous toluene (200 mL) were combined with magnetic stirring under dry nitrogen atmosphere. With stirring, triethylamine (13.13 mL, 9.533 g, 94.21 mmol) was added dropwise via syringe. The mixture was next heated to 80 C. and allowed to stir for two hours. The reaction produced a dark-red heterogeneous suspension and stirring was adjusted and increased when necessary to prevent coagulation of the suspension. The reaction was monitored via TLC for the disappearance of bis(4-ethynylphenyl) ether and observed mono-coupled intermediates. Once complete, the suspension was allowed to cool to room temperature and then vacuum filtered to isolate the solid that contained the desired product. The crude solid product was rinsed with ethyl acetate on the vacuum filter funnel to remove the excess of soluble methyl 4-bromobenzoate and until all the solid appear free of deep red coloration. Next, the solid was dried under high vacuum to yield 9.747 g of crude bis-acetylene solid (78.4% purity) before it was used directly in the next step.

(5) To a dry, nitrogen flushed 250 mL three-neck round-bottom flask fitted with a water-jacketed condenser and thermocouple adapter, 3.00 g of the crude bis-acetylene solid from the previous step, molecular iodine (0.123 g, 0.483 mmol, 5 mol % of acetylene content), and anhydrous dimethylsulfoxide (100 mL) were added. The suspension was heated to 140 C. with stirring and maintained at that temperature for 42 hours. Next, the homogenous mixture was cooled to room temperature and then precipitated by slow dropwise addition into room temperature deionized water. The solid was isolated using vacuum filtration. The crude solid was dissolved in dichloromethane and 2.5 g of silica gel was added followed by concentration in vacuo to dryness. The silica supported crude solid was purified using flash column chromatography using a gradient from 1:1 dichloromethane/heptane to 100% dichloromethane over 15 column volumes to purify the desired product. This yielded 600 mg (22.6% yield) of Compound (9) confirmed by NMR. The overall reaction is illustrated in Reaction Scheme 3.

EXAMPLE 3

(6) To a dry 20 mL vial equipped with a magnetic stir bar, diphenylacetone (90% purity, 80.64 mg, 0.345 mmol), Compound (9) from Example 2 (95% purity, 100 mg, 0.173 mmol), and 3 mL anhydrous ethanol were added with stirring. The capped vial containing the stirred mixture was heated to 75 C. to dissolve the starting materials. Next a solution of potassium hydroxide (29 mg) in 1 mL of ethanol was added dropwise and the vial was recapped and maintained at 75 C. for 45 minutes with stirring. Upon addition of the potassium hydroxide, the solution immediately turned dark purple. The dark color persisted through the 45 minute reaction period. After cooling to room temperature, a small amount of purple solid precipitated out of solution onto the interior surface of the vial. TLC (2:1 heptane/ethyl acetate) of the reaction mixture showed no starting reactants and a single spot on the baseline.

(7) Next, in a 20 mL vial, a small aliquot of the reaction mixture (100 L) diluted to 1 mL with ethanol was acidified to pH 1 using 6 M hydrochloric acid and resulted in a dramatic color change from dark purple to light red. The heterogeneous suspension of dark brown solid particles became a light red homogenous solution upon adding a few drops of the acid. This solution was next diluted with 10 mL dichloromethane and washed three times with 5 mL water (each wash), the washed organic phase was dried with magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. Analysis of the solid using NMR showed a mixture of products.

EXAMPLE 4

(8) The mixture of products from Example 3 is dissolved in 1 mL of acetic anhydride and a single drop of concentrated sulfuric acid (98%) is added with stirring at room temperature. The mixture is allowed to stir at room temperature overnight. Next, the reaction mixture is added slowly, dropwise to stirred water cooled to 0 C. A solid precipitate (Compound (1b)) is expected to be isolated via vacuum filtration.

(9) ##STR00026##

EXAMPLE 5: SYNTHESIS OF COMPOUND (1H)

(10) Phthalic anhydride (0.015 mol, 2.27 g, 1.2 eq) was charged to a dry, 250 mL, 3-neck round bottom flask. Methylene chloride (50 mL) was then charged and the solution was stirred with a magnetic stir bar under nitrogen until all of the phthalic anhydride dissolved (10 min). Next, diphenylene oxide bis(triphenylcyclopentadienone) (DPO-CPD) monomer (0.013 mol, 10 g, 1 eq) was charged to the round bottom flask and the solution was stirred under nitrogen until all of the solid DPO-CPD monomer was dissolved (30 min). Finally, aluminum chloride (granular, 0.066 mol, 8.855 g, 5.2 eq) was added in portions over 10 minutes. The dark black solution was then stirred at room temperature for twenty four hours. The reaction was then quenched by pouring the reaction into an HCl solution (5%, 500 mL) and stirring for twelve hours. The dark red precipitate was then filtered, collected and dried (50 C., 24 hours, reduced pressure) to afford 11.2 g (94.18%) of a dark red solid (Compound (1h)) The isolated product was soluble in PGME, and the structure was confirmed by .sup.1H-NMR and gel permeation chromatography.

EXAMPLE 6: SYNTHESIS OF COMPOUND (1I)

(11) Trimellitic anhydride chloride (0.006 mol, 1.345 g, 1 eq) was added to a dry, 250 mL, 3-neck round bottom flask. Methylene chloride (50 mL) was then charged and the solution was stirred with a magnetic stir bar under nitrogen until all of the trimellitic anhydride chloride dissolved (10 min). Next, DPO-CPD monomer (0.006 mol, 5 g, 1 eq) was charged to the round bottom flask and the solution was stirred under nitrogen until all of the solid DPO-CPD monomer was dissolved (30 min). Finally, aluminum chloride (granular, 0.042 mol, 5.535 g, 6.5 eq) was added in portions over 10 minutes. The dark black solution was then stirred at room temperature for forty eight hours. The reaction was then quenched by pouring the reaction into an HCl solution (5%, 500 mL) and stirring for twelve hours. The dark red precipitate was then filtered, collected and dried (50 C., 24 hours, reduced pressure) to afford 5.6 g (89.93%) of a dark red solid (Compound (1i)). The isolated product mixture was soluble in PGME, and the structure was confirmed by .sup.1H-NMR, .sup.13C-NMR, and gel permeation chromatography.

EXAMPLE 7: SYNTHESIS OF COMPOUND (1J)

(12) Trimellitic anhydride chloride (0.029 mol, 6.051 g, 1.5 eq) was added to a dry, 500 mL, 3-necked round bottom flask. Methylene chloride (250 mL) was then charged and the solution was stirred with a magnetic stir bar under nitrogen until all of the trimellitic anhydride chloride dissolved (10 min). Next, DPO-CPD monomer (0.019 mol, 15 g, 1 eq) was charged to the round bottom flask and the solution was stirred under nitrogen until all of the solid DPO-CPD monomer was dissolved (30 min). Finally, aluminum chloride (granular, 0.153 mol, 20.44 g, 8 eq) was added in portions over 10 minutes. The dark black solution was then stirred at room temperature for forty eight hours. The reaction was then quenched by pouring the reaction into an HCl solution (5%, 500 mL) and stirring for twelve hours. The dark red precipitate was then filtered, collected and dried (50 C., 24 hours, reduced pressure) to afford 16.5 g (87.6%) of a dark red solid (Compound (1j)). The isolated product mixture was soluble in PGME, and the structure was confirmed by .sup.1H-NMR, .sup.13C-NMR, and gel permeation chromatography.

EXAMPLE 8

(13) Compound (1h) from Example 5 (0.009 mol, 8.00 g, 1 eq) was first charged to a 250 mL 3-necked round bottom flask followed by the addition of 1,3,5-tris(phenylethynyl)benzene (TRIS, 0.009 mol, 3.577 g, 1.1 eq). GBL (27.01 g) was then added and the reaction heated to 204 C. within thirty minutes. The reaction was kept at 204 C. for 10 hours and allowed to cool to room temperature. The reaction was then poured into 500 mL of DI water and stirred for one hour. The brown solid was filtered and dried (70 C., 48 hours) to afford 10.2 g of solid Polymer 1. The solid was >10% w/w soluble in PGME. Analysis of Polymer 1 by gel permeation chromatography against polystyrene standards indicated a weight average molecular weigh (M.sub.w) of approximately 9000 Da.

EXAMPLE 9

(14) Compound mixture (1j) from Example 7 (0.004 mol, 3.6 g, 1 eq) was first charged to a 100 mL 3-necked round bottom flask, followed by TRIS. (0.005 mol, 2.007 g, 1.43 eq) and GBL (13 g). The reaction was heated to 204 C. within 30 minutes and held at 204 C. for a total of 10 hours. The reaction was then allowed to cool to room temperature and poured into 250 mL of a 1% HCl solution and stirred for 12 hours. The precipitate was then filtered and dried (70 C., 48 hours) to afford 5.4 g of Polymer 2 as a brown solid. Analysis of Polymer 2 by gel permeation chromatography against polystyrene standards indicated a M.sub.w of approximately 6600 Da.

EXAMPLE 10

(15) The solubility of Polymers 1 and 2 from Examples 8 and 9, respectively, was compared to the solubility of a conventional polyarylene resin (Comparative Polymer 1) having no polar moieties on the cyclopentadienone monomer. Comparative Polymer 1 was prepared by reacting DPO-CPD with TRIS in an approximate 1:1 ratio to yield a polymer having a Mw of approximately 8000 Da. The solubility of each polymer in PGMEA and PGME (conventional solvents used in the electronics industry) was evaluated by observing the amount of polymer to be dissolved in an amount of solvent on a w/w basis. The effect of solvent dilution on a formulation of each of the polymers (5% w/w) in PGMEA was also determined by adding each formulation separately to 10 weight equivalent of PGME (1:10 PGME) and a 70:30 w/w mixture of PGME:PGMEA (1:10 PP73) and determining the turbidity of the resultant dilution. Turbidity was determined using an Orbeco-Hellige Digital Direct-Reading Turbidimeter and comparing the sample solution to DI H.sub.2O as the standard 0 reading. Table 1 reports the solubility of each of the polymers in PGME and PGMEA by weight, and the relative turbidity of the diluted formulations.

(16) TABLE-US-00001 TABLE 1 Polymer PGMEA PGME 1:10 PGME 1:10 PP 73 Comparative ca. 5% None >200 <10 Polymer 1 Polymer 1 >20% >10% <1 <1 Polymer 2 >20% >10% <1 <1

(17) The data in Table 1 clearly show that Polymers 1 and 2 show significant solubility in both PGMEA and PGME as compared to Comparative Polymer 1. A turbidity value of <1 indicates the solution is visually clear. As can be seen from the data in Table 1, dilutions of the formulations of Polymers 1 and 2 in both 10PGME and 70:30 w/w mixture of PGME:PGMEA are visually clear, whereas the dilution of Comparative Polymer 1 shows significant turbidity.