POLYARYLENE MATERIALS

Abstract

Polyarylene oligomers formed from an aromatic dialkyne monomer having a solubility enhancing moiety show improved solubility in certain organic solvents and are useful in forming dielectric material layers in electronics applications.

Claims

1. A polyarylene polymer comprising as polymerized units: one or more first monomers of formula (1) ##STR00013## wherein each Ar.sup.1 and Ar.sup.2 is independently a C.sub.6-30 aryl moiety; each R is independently chosen from H, C.sub.6-30 aryl, and substituted C.sub.6-30 aryl; each R.sup.1 is independently chosen from OH, C.sub.1-6 hydroxyalkyl, C(O)OR.sup.3, C(O)N(R.sup.4).sub.2, OC(O)R.sup.5, NR.sup.4C(O)R.sup.6, N(R.sup.4).sub.3.sup.+An.sup., NO.sub.2; S(O).sub.2OR.sup.7, OS(O).sub.2R.sup.8, NR.sup.4S(O).sub.2R.sup.6, and S(O).sub.2N(R.sup.4).sub.2; each R.sup.2 is independently chosen from C.sub.1-10 alkyl, C.sub.1-10 haloalkyl, C.sub.1-10 hydroxyalkyl, C.sub.1-10 alkoxy, CN, N(R.sup.4).sub.2, and halo R.sup.3H, C.sub.1-10 alkyl, C.sub.1-10 hydroxyalkyl, C.sub.1-10 aminoalkyl, C.sub.6-30 aryl, or M; each R.sup.4 is independently H, C.sub.6-30 aryl or C.sub.1-10 alkyl; each R.sup.5 is independently chosen from H, C.sub.1-10 alkyl, C.sub.1-10 hydroxyalkyl, C.sub.6-30 aryl, O(C.sub.1-10 alkyl), O(C.sub.6-10 aryl) and N(R.sup.4).sub.2; R.sup.6H, C.sub.1-10 alkyl, C.sub.1-10 hydroxyalkyl, C.sub.6-30 aryl, O(C.sub.1-10 alkyl), or NH(C.sub.1-10 alkyl); R.sup.7H, C.sub.1-10 alkyl, C.sub.6-30 aryl, or M; R.sup.8C.sub.6-30 aryl, C.sub.1-10 alkyl, and halo C.sub.1-10 alkyl; M=an alkali metal ion, an alkaline earth metal ion, or an ammonium ion; An.sup. is an anion chosen from halide and C.sub.1-20 carboxylate; Y is a chemical bond or a divalent linking group chosen from O, S, S(O), S(O).sub.2, C(O), (C(R.sup.9).sub.2).sub.z, C.sub.6-30 aryl, and (C(R.sup.9).sub.2).sub.z1(C.sub.6-30 aryl)-(C(R.sup.9).sub.2).sub.z2; each R.sup.9 is independently chosen from H, hydroxy, halo, C.sub.1-10 alkyl, C.sub.1-10 haloalkyl, and C.sub.6-30 aryl; a1=0 to 3; a2=0 to 3; b1=1 to 4; b2=0 to 2; c1=0 to 2; c2=0 to 2; a1+a2=1 to 6; b1+b2=2 to 6; c1+c2=1 to 6; d=0 to 2; z=1 to 10; z1=0 to 10; z2=0 to 10; and z1+z2=1 to 10; and one or more second monomers comprising two cyclopentadienone moieties.

2. The polyarylene polymer of claim 1 further comprising as polymerized units one or more third monomers of formula (13) ##STR00014## wherein Ar.sup.5 is a C.sub.6-30 aromatic moiety; each R.sup.15 is independently chosen from C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, C.sub.1-4alkoxy, optionally substituted C.sub.7-14 aralkyl, and optionally substituted C.sub.6-10 aryl; b4=1 or 2; and f=0 to 4.

3. The polyarylene polymer of claim 2 wherein R.sup.15 is phenyl.

4. The polyarylene polymer of claim 1 wherein R.sup.1 is chosen from OH, C(O)OR.sup.3, C(O)N(R.sup.4).sub.2, OC(O)R.sup.5, S(O).sub.2OR.sup.5, and S(O).sub.2N(R.sup.4).sub.2.

5. The polyarylene polymer of claim 4 wherein R.sup.3H, C.sub.1-6 alkyl, C.sub.1-6 hydroxyalkyl, or M; R.sup.4H, or C.sub.1-6 alkyl; R.sup.5H, C.sub.1-6 alkyl, O(C.sub.1-6 alkyl), or NH(C.sub.1-6 alkyl); and R.sup.7H or C.sub.1-6 alkyl.

6. The polyarylene polymer of claim 4 wherein R.sup.1 is chosen from OH and C(O)OR.sup.3.

7. The polyarylene polymer of claim 1 wherein R is H or phenyl.

8. The polyarylene polymer of claim 1 wherein the one or more first monomers have the formula (2): ##STR00015## wherein Ar.sup.1, R, R.sup.1, a1 and b1 are as defined in claim 1.

9. The polyphenylene polymer of claim 1 wherein Ar.sup.1 and Ar.sup.2 are independently chosen from phenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, coronenyl, tetracenyl, pentacenyl, triphenylenyl, and perylenyl.

10. The polyarylene polymer of claim 1 wherein the one or more second monomers are chosen from one or more monomers of formula (9) ##STR00016## wherein each R.sup.10 is independently chosen from H, phenyl, or substituted phenyl; and Ar.sup.3 is an aromatic moiety.

11. A composition comprising one or more polyarylene polymers of claim 1 and one or more organic solvents.

12. The composition of claim 11 wherein the one or more organic solvents are chosen from propylene glycol methyl ether, propylene glycol methyl ether acetate, methyl 3-methoxypropionate, ethyl lactate, n-butyl acetate, anisole, N-methyl pyrrolidone, gamma-butyrolactone, ethoxybenzene, benzyl propionate, benzyl benzoate, propylene carbonate, and mixtures thereof.

13. A method of forming a dielectric material layer comprising: disposing a layer of the composition of claim 11 on a substrate surface; removing the organic solvent; and curing the oligomer to form a dielectric material layer.

Description

EXAMPLE 1

Preparation of Polymer 1

[0035] To a multineck round-bottomed flask containing a stir bar, diphenylene oxide bis(triphenylcyclopentadienone) (DPO-CPD, 15.00 g, 19.16 mmol), 3,5-diethynylbenzoic acid (DEBzOH, 1.793 g, 10.54 mmol) and 1,3,5-tris(phenylethynyebenzene (TRIS, 3.988 g, 10.54 mmol) were added via powder funnel, followed by GBL (48 g) as the reaction solvent. The reaction was stirred gently at room temperature. The flask was next equipped with a reflux condenser and an internal thermocouple probe attached to a self-regulating thermostat control for a heating mantle Next, the dark maroon contents of the flask were warmed to an internal temperature of 203 C. and maintained at this temperature for 60 hours before cooling to 25 C. by removal of the heating element. The resulting maroon solution was precipitated from GBL using 300 mL water heated to 70 C. as an antisolvent. Filtration and drying of the precipitate in a vacuum oven for 3 days yielded Polymer 1 as an off-white powder. Polymer 1 was analyzed by gel permeation chromatography (GPC) to provide a number-average molecular weight (M.sub.n) of 6761 Da, a weight-average molecular weight (M.sub.w) of 41719 Da, and a polydispersity of 6.171. This reaction is shown in Scheme 1.

##STR00010##

EXAMPLE 2

Preparation of Polymers 2-11

[0036] The procedure of Example 1 is repeated except that 3,5-diethynylbenzoic acid is replaced with the monomers shown in Table 1.

TABLE-US-00001 TABLE 1 Polymer Number Monomer 2 3,5-Bis(phenylethynyl)benzoic acid 3 Methyl 3,5-bis(phenylethynyl)benzoate 4 Methyl 3,5-diethynylbenzoate 5 Ethyl 3,5-diethynylbenzoate 6 3,5-Bis(phenylethynyl)benzenesulfonic acid 7 N-Methyl-3,5-bis(phenylethynyl)benzamide 8 3,5-Diethynylbenzenesulfonic acid 9 3,5-Diethynylphenyl acetate 10 N-Methyl-3,5-diethynylbenzamide 11 N-Ethyl-3,5-diethynylbenzamide

EXAMPLE 3

Preparation of Polymers 12-15

[0037] The procedure of Example 1 is repeated except that the 1,3,5-tris(phenylethynyebenzene is replaced with the monomers shown in Table 2.

TABLE-US-00002 TABLE 2 Polymer Number Monomer 12 1,3-Diethynylbenzene 13 1,4-Diethynylbenzene 14 1,3-Diethynylbenzene + 1,3,5- tris(phenylethynyl)benzene (2:3 mole ratio) 15 1,3-Diethynylbenzene + 1,3,5- tris(phenylethynyl)benzene (1:3 mole ratio)

EXAMPLE 4

Preparation of Polymers 16-22

[0038] The general procedure of Example 1 is repeated using the monomers in the molar ratios shown in Table 3.

TABLE-US-00003 TABLE 3 Polymer Number Monomer 16 DPO-CPD:3,5-diethynylbenzoic acid (1:1.1) 17 DPO-CPD:3,5-diethynylbenzoic acid:TRIS:1,3- diethynylbenzene (1:0.5:0.35:0.25) 18 DPO-CPD:3,5-bis(phenylethynyl)benzoic acid (1:1.15) 19 DPO-CPD:Methyl 3,5-bis(phenylethynyl)benzoate (1:1.05) 20 DPO-CPD:N-methyl-3,5-diethynylbenzamide:1,3- diethynylbenzene (1:0.4:0:65) 21 DPO-CPD:3,5-diethynylbenzamide:TRIS (1:0.55:0.6) 22 DPO-CPD:3,5-diethynylbenzenesulfonic acid:1,4- diethynylbenzene (1:0.6:0.5)

EXAMPLE 5

[0039] Polymer 23 was prepared as follows. To a three neck round-bottomed flask containing a stir bar were added DPO-CPD (25 g, 31.9 mmol), DEBzOH (1.09 g, 6.4 mmol) and GBL (88g). The reaction mixture was stirred gently at room temperature. The flask was next equipped with a reflux condenser and an internal thermocouple probe attached to a self-regulating thermostat control for a heating mantle Next, the dark maroon contents of the flask were warmed to an internal temperature of 160 C. and maintained at this temperature for 4 hours before cooling to about 100 C. by removal of the heating element. Next, TRIS (9.66 g, 25.5 mmol) was added slowly to the reaction. The resulting maroon solution was heated to 203 C. and stirred at this temperature for 47 hrs. GPC analysis of the reaction product (Polymer 23) indicated an M.sub.n of 8434 Da, an M.sub.w of 26395 Da, and a polydispersity of 3.13.

EXAMPLE 6

[0040] The procedure of Example 5 was repeated except that the molar ratio of DPO-CPD:TRIS:DEBzOH ratio used is 1:0.9:0.2 and reaction time was 4 hours at 160 C. and 40 hours at 203 C., to provide Polymer 24 having an M.sub.n of 5486 Da.

EXAMPLE 7

Solubility

[0041] A portion (5 g of 30% solids) of Polymer 23 were transferred to a transparent 20 mL vial. Ethoxybenzene (5 g) was added to the vial to make a 15% diluted Polymer 23 solution. This polymer solution was vortex mixed to ensure a uniform dispersion at room temperature. A portion (about 1 g) of this Polymer 23 solution was transferred to an empty transparent 20 mL vial. The vial was placed on a balance and an edge bead remover solvent composition based on a PGME/PGMEA solvent mixture was added dropwise into the vial using a pipette until a precipitate was visible on the vial wall or the solution becomes turbid. At this point, the amount (weight) of the solvent mixture added was noted and the ratio of the solvent mixture to polymer solution determined If precipitation did not occur after adding 10 g of the solvent mixture, the polymer solution was considered to pass this solvent shock test. The Polymer 23 solution passed this test, and this test was repeated using Comparative Polymers 1-3. Comparative Polymer 1 was a commercially available polyarylene polymer (from Dow Electronic Materials) formed from DPO-CPD and TRIS in an approximate molar ratio of 1:1 and having an M.sub.n of approximately 8800 Da. Comparative Polymer 2 was a polyarylene polymer formed from DPO-CPD and TRIS in an approximate molar ratio of 1:1 and having an M.sub.n of approximately 5500 Da. Comparative Polymer 3 was prepared according to the general procedure of Example 1 of copending U.S. patent application Ser. No. 14/472,429 (Gilmore et al.) and formed from DPO-CPD, 1,3-diethynylbenzene and propiolic acid, and had a M.sub.n of approximately 8400 Da. These results are reported in Table 4 below.

EXAMPLE 8

Critical Film Thickness

[0042] Solutions of Polymer 23 as well as Comparative Polymers 1-3 were used to cast films of the respective polyarylene polymers using a slot die coater. These results are reported in Table 4, where films that passed this critical film thickness test received a score of +++, meaning there were no cracks in a film having a thickness of 1 m. As can be seen from the data in Table 4, only polymers of the invention (Polymer 23) passed the solubility test and formed films that met or exceeded the film thickness target without cracking.

TABLE-US-00004 TABLE 4 Polymer Solubility Test Critical Film Thickness Polymer 23 Pass +++ Comparative Polymer 1 Fail +++ Comparative Polymer 2 Pass + Comparative Polymer 3 Fail not tested

EXAMPLE 9

[0043] The procedure of Example 1 was repeated a number of times except that the molar ratio of DEBzOH to TRIS was varied each time. The M.sub.n of each polymer was determined as described above. Each of these polymers was evaluated to determine its critical film thickness according to the procedure of Example 8 as well as its solubility according to the following test. These results are reported in Table 5.

[0044] A portion (1.2 g of) of each polymer was transferred to a transparent 20 mL vial and 8.8 g of MMP/Anisole/gamma-butyrolactone (61.75/33.25/5) solvent mixture was added to make a 12% diluted polymer solution. Each polymer solution was vortex mixed to ensure a uniform dispersion at room temperature. A portion (0.6 g) of each polymer solution was added to an empty transparent 20 mL vial. The vial was placed on a balance and a conventional edge bead remover solvent composition based on a PGME/PGMEA solvent mixture having a majority of PGME was added dropwise into the vial using a pipette until a precipitate was visible on the vial wall or the solution becomes turbid. At this point, the amount (weight) of the solvent mixture added was noted and the ratio of solvent mixture to polymer solution determined. If precipitation did not occur after adding 20 g of solvent mixture, the polymer solution was considered to pass this solvent shock test. The results, reported in Table 5, clearly show the present polyarylene polymers have very good solubility in conventional edge bead remover compositions and are capable of providing films having a thickness of 1.5 m without cracking.

TABLE-US-00005 TABLE 5 Polymer No. DEBzOH:TRIS M.sub.n Solubility Test Critical Thickness 25 10:90 6400 Da 2.3:1 2.5 m 26 20:80 5490 Da 9.4:1 1.7 m 27 20:80 8430 Da 2.8:1 2.5 m 28 30:70 6200 Da 6.5:1 1.8 m 29 50:50 6760 Da 200:1 2.2 m 30 50:50 5800 Da 200:1 2.2 m 31 60:40 6100 Da 100:1 1.8 m 32 60:40 6200 Da 200:1 2.4 m

EXAMPLE 10

Preparation of Polymer 24

[0045] The general procedure of Example 1 was repeated except that the DEBzOH monomer was replaced with methyl 3,5-diethynylbenzoate (DEBzOMe) and the molar ratio of DEBzOMe:TRIS:DPO-CPD was 0.34:0.66:1.

EXAMPLE 11

Preparation of 3,5-Diethynylphenol

[0046] 3,5-Dibromophenyl acetate was prepared as follows. The overall reaction is shown in Scheme 2 below. 3,5-Dibromophenol (100.0 g) was added to 162.1 g of acetic anhydride at room temperature to yield a light yellow solution. The reaction was stirred at 70 C. for 6 hr. The reaction mixture was then slowly added into ice water and a white precipitate was formed. After stirring at room temperature for 0.5 hr., the solid product was collected by filtration and dried under vacuum for 12 hr. to provide 102.0 g of 3,5-dibromophenyl acetate as a light yellow solid in 88% yield.

[0047] 3,5-Dibromophenyl acetate (50.0 g) was added to 133.0 g of 1,4-dioxane at room temperature to yield a yellow solution. Triethylamine (51.6 g) and cuprous iodide (3.23 g) were added to the reaction mixture. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (5.962 g) was added to the reaction mixture. Nest, 41.8 g of (trimethylsilyl)acetylene was slowly added to reaction mixture via an addition funnel. After completion of addition, the reaction was stirred for 24 hr. at 55 C. under nitrogen. After complete conversion, the product was filtered and solvents were evaporated. The residue was dissolved in heptanes and filtered through a silica plug. After filtration, the solvents were removed to yield 3,5-bis(trimethylsilylethynyl)phenyl acetate as a light yellow solid (51.0 g) in 91% yield.

[0048] 3,5-Bis(trimethylsilylethynyl)phenyl acetate (51.0 g) was dissolved in tetrahydrofuran (THF, 186 g) and water (46 g). The mixture was combined with 21.4 g of lithium hydroxide monohydrate at room temperature to yield a dark black reaction mixture. The reaction mixture was stirred for 6 hr. at 55 C. under nitrogen. The reaction mixture was then diluted with ethyl acetate and then treated with hydrochloric acid until the pH of aqueous layer is 4 to 5. The organic phase was separated and aqueous phase was extracted with ethyl acetate (60 mL3). The organic phase was washed with brine (1266 mL) and dried with MgSO.sub.4 (10 g). The mixture was then filtered and evaporated under vacuum to give 3,5-diethynylphenol (DEPOH) as a light yellow solid (19.8 g) in 90.0% yield.

##STR00011##

EXAMPLE 12

Preparation of Polymer 33

[0049] DPO-CPD (9.0 g, 0.0115 mol) and 3,5-diethynylphenol (1.96 g, 0.0138 mol) from Example 11 were dissolved in 97 g of GBL. The reaction was heated at 120 C. for 1 hr. and then 130 C. for 1 hr. and then 150 C. for 1.5 hr. The mixture was cooled to room temperature and then diluted with 10 g of GBL. The reaction mixture was slowly added to warm water. The precipitated polymer (Polymer 33) was collected by filtration and then dried in vacuum oven at 65 to 70 deg C. for 2 days. 10.0 g brown solid was obtained in 97% yield. GPC: Mw=9292, PDI=2.067.

##STR00012##

EXAMPLE 13

Preparation of Polymer 34

[0050] DPO-CPD (9.0 g, 0.0115 mol) and 3,5-diethynylphenol (1.37 g, 0.0096 mol) from Example 11 were dissolved in 97 g of GBL. The reaction was heated at 130 C. for 2 hr and then cooled down to 80 C. 1,3,5-Tris(phenylethynyl)benzene (TRIS, 1.57 g, 0.0041 mol) was then added to reaction mixture at 80 C. The reaction was then heated at 190 C. for 16 hr. The reaction mixture was cooled to room temperature and then diluted with GBL (10 g). The reaction mixture was slowly added to warm water. The precipitated polymer was collected by filtration and then dried in vacuum oven at 65 to 70 C. for 2 days. Polymer 34 was obtained as a brown solid (10.1 g) in 98% yield. GPC: Mw=7061, PDI=3.714.

EXAMPLE 14

[0051] The general procedure of Example 1 is repeated using DPO-CPD as the second monomer having two cyclopentadienone moieties, using the monomers in the mole ratios shown in Table 6 in place of the DEBzOH first monomer and TRIS third monomer. The following abbreviations are used in Table 6: 1,3-DEB=1,3-diethynylbenzene; 1,4-DEB=1,4-diethynylbenzene; DEPyrDOH=4,9-diethynylpyrene-1,6-diol; DEAnD OH=9,10-diethynylanthracene-2,6-diol; DEPerD OH=5,8-diethynylperylene-1,12-diol; DEPyCO2H=4,9-diethynylpyrene-1,6-dicarboxylic acid; DEBINOL=6,6-Diethynyl-[1,1-binaphthalene]-2,2-diol; DEBP=4,4-diethynyl-1,1-biphenyl; and BPEBP=4,4-bis(phenylethynyl)-1,1-biphenyl.

TABLE-US-00006 TABLE 6 Polymer Number Monomer (mole ratio) 35 DPO-CPD:DEBzOH:DEPOH (1:0.5:0.6) 36 DPO-CPD:DEBzOH:DEPOH (1:0.25:0.77) 37 DPO-CPD:DEPOH:1,4-DEB (1:0.75:0.35) 38 DPO-CPD:Methyl 3,5- bis(phenylethynyl)benzoate:DEAnDOH (1:0.35:0.7) 39 DPO-CPD:DEPyDOH:1,3-DEB (1:0.5:0:55) 40 DPO-CPD:DEPyDOH:TRIS (1:0.6:0.55) 41 DPO-CPD:DEPyDOH:1,4-DEB (1:0.65:0.45) 42 DPO-CPD:DEPerDOH:TRIS (1:0.75:0.26) 43 DPO-CPD:DEPerDOH:1,3-DEB (1:0.6:0.45) 44 DPO-CPD:DEPyCO2H:DEPOH:1,3-DEB (1:0.3:0.45:0.27) 45 DPO-CPD:DEBP:TRIS: (1:0.75:0.26) 46 DPO-CPD:DEBOH:TRIS: (1:0.75:0.26) 47 DPO-CPD:DEBINOL:TRIS (1:0.70:0.36) 48 DPO-CPD:DEBINOL:1,3-DEB (1:0.77:0.2) 49 DPO-CPD:DEPOH:BPEBP (1:0.65:0.47) 50 DPO-CPD:DEBzOH:DEBP (1:0.6:0.5)

EXAMPLE 15

Preparation of 6,6-Diethynyl[1,1-binaphthalene]-2,2-diol

[0052] 2,2-Dihydroxy-6,6-dibromo-1,1-binaphthalene (40 g) was added to 55.1 g of acetic anhydride and 42.7 g pyridine in 250 mL dichloromethane to yield a light yellow solution. The reaction mixture was stirred at room temperature for 24 hr. The product was washed with water (3250 mL) and the organic layer was dried over anhydrous MgSO.sub.4. Removal of organic solvents gave 6,6-dibromo-2,2-diacetyl-1,1-binaphthalene as the desired product as light yellow solid 44.0 g in 93% yield.

[0053] 6,6-Dibromo-2,2-diacetyl-1,1-binaphthalene (9.4 g) was added to 26.1 g of 1,4-dioxane at room temperature to yield a yellow solution. Triethylamine (5.6 g) and cuprous iodide (0.35 g) was added to the reaction mixture. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (0.975 g) was added to the reaction mixture. Trimethylsilylacetylene (5.5 g) was then slowly added to reaction mixture by way of an addition funnel. After completion of addition, the reaction was stirred for 24 hr. at 55 C. under nitrogen. After complete conversion, the product was filtered and solvents were evaporated. The residue was dissolved in heptanes and filtered through a silica plug. After filtration, the solvents were removed to yield a light yellow solid which was used in next step.

[0054] The product from previous step was dissolved in 36.4 g of THF and 8.96 g of water. To the mixture was added 4.67 g of lithium hydroxide monohydrate at room temperature to yield a dark black solution. The reaction was stirred for 24 hr. at 55 C. under nitrogen. The reaction mixture was diluted with ethyl acetate and then treated with hydrochloric acid until the pH of aqueous layer was 4 to 5. The organic phase was separated and aqueous phase was extracted with ethyl acetate (30 mL3). The organic phase was then washed with brine and dried with MgSO.sub.4. The mixture was then filtered and evaporated under vacuum to give 6,6-diethynyl-[1,1-binaphthalenel-2,2-diol as a light yellow solid 4.97 g in 83% yield.