Polyarylene materials

Abstract

Certain polyarylene oligomers having improved solubility are useful in forming dielectric material layers in electronics applications.

Claims

1. An oligomer comprising as polymerized units a first monomer comprising two cyclopentadienone moieties, a second monomer having the formula (1), and a third monomer having the formula (2) ##STR00012## wherein a is the number of R groups and is an integer from 0 to 4; b is 1 or 2; each R is independently chosen from C.sub.1-4 alkyl, halo C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 aralkyl, and optionally substituted C.sub.6-10 aryl; each R.sup.1 is independently H or optionally substituted C.sub.6-10 aryl; R.sup.2 is H, optionally substituted C.sub.1-10 alkyl, optionally substituted C.sub.7-12 aralkyl, optionally substituted C.sub.6-10 aryl, or R.sup.3; and R.sup.3 is a polar moiety selected from the group consisting of carboxyl, C.sub.2-12 aliphatic carboxylate, hydroxy C.sub.1-10 alkyl, C.sub.7-20 aryl carboxylic acid, C.sub.8-20 aryl carboxylic acid anhydride, C.sub.7-20 aryl carboxylates, C.sub.7-20 aryl amide, and C.sub.8-20 aryl imide.

2. The oligomer of claim 1 wherein the third monomer is selected from the group consisting of propiolic acid, acetylene dicarboxylic acid, phenyl propiolic acid, ethynyl benzoic acid, ethynyl phthalic acid, propargyl alcohol, 2-methyl-3-butyn-2-ol, xylityl propiolate, ethynyl phthalic anhydride, ethynyl phthalimide, ethynyl benzamide, 2-butyn-1,4-diol diacetate; 3-butyn-2-one; 1-ethynyl-1-cyclohexanol; 1-ethynylcyclohexylamine; 1-ethnylcyclopentanol; ethynylaniline; N-(ethynylphenyl)acetamide; 2-carbamoyl-5-ethynylbenzoic acid; ethynyl-nitrobenzene; propioamaide; N-hydroxyl -propiolamide; 2-aminobut-3-ynoic acid, and mixtures thereof.

3. The oligomer of claim 1 wherein the first monomer and the second monomer are present in a mole ratio of from 1:1.001 to 1:1.95.

4. The oligomer of claim 1 wherein the first monomer has the formula ##STR00013## wherein each R.sup.4 is independently chosen from H, or optionally substituted phenyl; and Ar.sup.1 is an aromatic moiety.

5. The oligomer of claim 1 wherein b=1.

6. The oligomer of claim 5 further comprising another second monomer wherein b=2.

7. A composition comprising the oligomer of claim 1 and an organic solvent.

8. The composition of claim 7 wherein the organic solvent is chosen from propylene glycol methyl ether, propylene glycol methyl ether acetate, methyl 3-methoxypropionate, ethyl lactate, anisole, N-methyl pyrrolidone, gamma-butyrolactone, ethoxybenzene, benzyl propionate, and mixtures thereof.

9. A method of forming a dielectric material layer comprising: disposing a layer of the composition of claim 7 on a substrate surface; removing the organic solvent; and curing the oligomer to form a dielectric material layer.

10. An oligomer comprising as polymerized units a first monomer comprising two cyclopentadienone moieties, a second monomer having the formula (1), and a third monomer having the formula (2) ##STR00014## wherein a is the number of R groups and is an integer from 0 to 4; b is 1 or 2; each R is independently chosen from C.sub.1-4 alkyl, halo C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 aralkyl, and optionally substituted C.sub.6-10 aryl; each R.sup.1 is independently H or optionally substituted C.sub.6-10 aryl; R.sup.2 is H, optionally substituted C.sub.1-10 alkyl, optionally substituted C.sub.7-12 aralkyl, optionally substituted C.sub.6-10 aryl, or R.sup.3; and R.sup.3 is a a hydrocarbyl moiety having from 1 to 20 carbon atoms and one or more functional groups chosen from C(O), NO.sub.2, and NR.sup.9R.sup.10, where R.sup.9 and R.sup.10 are independently chosen from H, C.sub.1-10 alkyl, C.sub.7-16 aralkyl, and C.sub.6-10 aryl.

Description

COMPARATIVE EXAMPLE 1

(1) A conventional polyarylene having end caps free of polar moieties was prepared according to the following reaction scheme and description.

(2) ##STR00009##

(3) To a multi-neck round-bottomed flask containing a stir bar, diphenylene oxide bis(triphenylcyclopentadienone) (DPO-CPD, 10.95 g, 13.98 mmol) was added via powder funnel, followed by the reaction solvent, ethoxybenzene (33 mL, 40% reagent weight by solvent volume). 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, and placed under a nitrogen atmosphere. At this point, 1,3-diethynylbenzene (1,3-DEB, 2.0 mL, 15.38 mmol) was added via syringe. The dark maroon contents of the flask were warmed to an internal temperature of 160 C. over the course of 30 min. and maintained at this temperature for 2 hr. before cooling to room temperature by removal of the heating element. At this point, 33 mL of ethoxybenzene were added to the solution, and the vessel was further cooled to room temperature, providing a clear, pale orange solution. The weight-averaged molecular weight (M.sub.w) of the oligomer (Comparative 1) was 25000 Da, as determined by GPC using polystyrene standards.

COMPARATIVE EXAMPLE 2

(4) The procedure of Comparative Example 1 was repeated except that the 1,3-DEB was replaced with 1,4-diethynylbenzene (1,4-DEB). The M.sub.w of the resulting oligomer (Comparative 2) was 22000 Da, as determined by GPC using polystyrene standards.

EXAMPLE 1

(5) To a multi-neck round-bottomed flask containing a stir bar, DPO-CPD (6.21 g, 7.93 mmol), 1,3-DEB (1.00 g, 7.93 mmol) and propiolic acid (0.056 g, 0.79 mmol) were added via powder funnel, followed by the reaction solvent, ethoxybenzene (40 mL). 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, and placed under a nitrogen atmosphere. Next, the dark maroon contents of the flask were warmed to an internal temperature of 130 C. and maintained at this temperature for 22 hr. before cooling to 25 C. by removal of the heating element. The resulting red-orange solution was bottled and evaluated as a crude mixture. GPC of the resulting oligomer (Oligomer 1) indicated a M.sub.w of 13900 Da as determined using polystyrene standards.

EXAMPLE 4

(6) The procedure of Example 3 was repeated a number of times using DPO-CPD as the first monomer, either 1,3-DEB or 1,4-DEB as the second monomer, and the third monomers listed in Table 1. The weight-averaged molecular weights of the resulting oligomers are also reported in Table 1.

(7) TABLE-US-00001 TABLE 1 Oligomer No. Second Monomer Third Monomer M.sub.w (Da) 2 1,4-DEB Propiolic acid 9500 3 1,3-DEB Acetylenedicarboxylic 14000 acid 4 1,4-DEB Acetylenedicarboxylic 30000 acid 5 1,3-DEB Propargyl alcohol 19000 6 1,4-DEB Propargyl alcohol 13000 7 1,3-DEB 2-Methyl-3-butyn-2-ol 12000 8 1,4-DEB 2-Methyl-3-butyn-2-ol 18000 9 1,3-DEB 3-Ethynylphenol 14000 10 1,4-DEB 3-Ethynylphenol 12000 11 1,3-DEB Xylityl propiolate 18000 12 1,4-DEB Xylityl propiolate 8500 13 1,3-DEB Ethynyl phthalic 14000 anhydride 14 1,4-DEB Ethynyl phthalic 17000 anhydride

EXAMPLE 5

(8) Oligomers were evaluated for their solubility in various organic solvents. Each oligomer was formulated by adding 5 g of a 30% reaction product solution to a vial along with 5 g of ethoxybenzene (EB) to make a 15% diluted polymer solution. To a 20 mL transparent vial was added 1 g of the polymer solution. Solvent, either MMP, PGMEA or a PGME/PGMEA (30:70 v/v) mixture, was dropwise added to the vial until a persistent precipitate was observed or until the solution became turbid or until a maximum of 10 g of solvent were added. The weight ratio of amount of solvent added in grams to 1 g of polymer solution is reported in Table 2.

(9) TABLE-US-00002 TABLE 2 Oligomer MMP: PGMEA: PGME/PGMEA: No. Solution (w/w) Solution (w/w) Solution (w/w) Comparative 1 4:1 .sup.1:1 0.7:1 Comparative 2 >10:1 3.1:1 0.7:1 1 >10:1 3.3:1 0.6:1 2 >10:1 >10:1 .sup.1:1 3 >10:1 .sup.3:1 0.7:1 4 >10:1 >10:1 1.1:1 5 7:1 2.2:1 0.5:1 6 >10:1 8.5:1 0.8:1 7 >10:1 3.1:1 0.6:1 8 >10:1 3.1:1 0.8:1 9 >10:1 .sup.3:1 0.6:1 10 >10:1 >10:1 1.1:1 11 6.1:1 1.8:1 0.8:1 12 6.6:1 0.5:1 0.6:1 13 >10:1 2.8:1 0.5:1 14 >10:1 3.7:1 0.6:1

(10) The higher the ratio in Table 2, the more soluble an oligomer is in the solvent. The above data show that oligomers formed using 1,4-DEB as the second monomer are more soluble in organic solvents than the corresponding oligomer formed from 1,3-DEB. These data further show that the oligomers of the invention having a third monomer end cap having one or more polar moieties have improved solubility in organic solvents as compared to the corresponding oligomer that does not have a third monomer end cap.

EXAMPLE 6

(11) The procedure of Example 4 is repeated, except that the second monomers and third monomers shown in Table 3 are used. Where a mixture of certain monomers are used, the ratio provided is the molar ratio.

(12) TABLE-US-00003 TABLE 3 Oligomer No. Second Monomer Third Monomer 15 4,4-diethynyl-1,1-biphenyl Propiolic acid 16 4,4-diethynyl-1,1-biphenyl Acetylene dicarboxylic acid 17 1,3-diethynyl-5- Acetylene dicarboxylic (phenylethynyl)benzene acid 18 1,3-diethynyl-5- Propiolic acid (phenylethynyl)benzene 19 4,4-diethynyl-1,1-biphenyl Propargyl alcohol 20 1,3-bis(phenylethynyl)benzene Acetylene dicarboxylic acid 21 1,3-bis(phenylethynyl)benzene Propiolic acid 22 1,4-bis(phenylethynyl)benzene Propiolic acid 23 1,4-DEB + Acetylene dicarboxylic 1,3-diethynyl-5- acid (phenylethynyl)benzene (1:1.5) 24 1,4-DEB + Acetylene dicarboxylic 1,3,5-tris(phenylethynyl)- acid benzene (1:1.25) 25 1,4-DEB 4-ethynylbenzamide 26 1,4-DEB Propiolamide 27 1,4-DEB 2-Butyn-1,4-diol diacetate 28 1,3-DEB 2-Butynoic acid 29 1,3-DEB + 2-Butynoic acid 1,3,5-tris(phenylethynyl)- benzene (1:1) 30 1,4-bis(phenylethynyl)benzene Propargylamine 31 1,4-DEB 3-Ethynylphathalic acid 32 1,4-DEB + 2-Aminobut-3-ynoic acid 1,3,5-tris(phenylethynyl)- benzene (1.1:1)

EXAMPLE 7

(13) An oligomer of the invention having one end cap containing 2 polar moieties was prepared according to the following reaction scheme and description.

(14) ##STR00010##

(15) To a multi-neck round-bottomed flask containing a stir bar, DPO-CPD (5.62 g, 7.21 mmol), 1,4-DEB (1.00 g, 7.21 mmol) and acetylenedicarboxylic acid (ADCA, 0.181 g, 1.59 mmol) were added via powder funnel, followed by the reaction solvent, ethoxybenzene (40 mL). 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, and placed under a nitrogen atmosphere. Next, the dark maroon contents of the flask were warmed to an internal temperature of 130 C. and maintained at this temperature for 28 hr. before cooling to 25 C. by removal of the heating element. The resulting maroon solution was bottled and evaluated as a crude mixture. GPC of the resulting oligomer material (Oligomer 33) indicated an M.sub.n of 8500, an M.sub.w of 18000, and a polydispersity of 2.1.

EXAMPLE 8

(16) An oligomer of the invention having two end caps containing 2 polar moieties was prepared according to the following reaction scheme and description.

(17) ##STR00011##

(18) To a multi-neck round-bottomed flask containing a stir bar, DPO-CPD (5.17 g, 6.61 mmol), 1,4-DEB (1.00 g, 7.21 mmol) and ADCA (0.137 g, 1.20 mmol) were added via powder funnel, followed by the reaction solvent, ethoxybenzene (40 mL). 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, and placed under a nitrogen atmosphere. Next, the dark maroon contents of the flask were warmed to an internal temperature of 130 C. and maintained at this temperature for 28 hr. before cooling to 25 C. by removal of the heating element. The resulting maroon solution was bottled and evaluated as a crude mixture. GPC of the resulting oligomer material (Oligomer 24) indicated an M.sub.n of 9570, an M.sub.w of 21000, and a polydispersity of 2.2.

EXAMPLE 9

(19) The procedure of Example 7 was repeated numerous times to provide Oligomer 33 having the various M.sub.w values reported in Table 4. The procedure of Example 8 was repeated numerous times to provide Oligomer 34 having the various M.sub.w values reported in Table 4. The procedure of Example 2 was repeated numerous times to provide Comparative 2 having the various M.sub.w values reported in Table 4. The solubility test of Example 5 was repeated using the different M.sub.w samples of Oligomer 33, Oligomer 34, and Comparative 2. The solubility results are also reported in Table 4.

(20) TABLE-US-00004 TABLE 4 MMP: PGMEA: PGME/PGMEA: Oligomer Solution Solution Solution No. M.sub.w (Da) (w/w) (w/w) (w/w) Comparative 2a 7000 >10:1 >10:1 1.2:1 Comparative 2b 11000 >10:1 >10:1 0.92:1 Comparative 2c 23000 >10:1 3.5:1 0.59:1 Comparative 2d 30000 >10:1 2.9:1 0.48:1 Comparative 2e 51000 >10:1 .sup.2:1 0.39:1 33a 9000 >10:1 >10:1 1.2:1 33b 18000 >10:1 >10:1 0.77:1 33c 43000 >10:1 2.7:1 0.41:1 33d 61000 >10:1 2.1:1 0.33:1 34a 5000 >10:1 >10:1 2.2:1 34b 9000 >10:1 >10:1 1.2:1 34c 12000 >10:1 >10:1 1.0:1 34d 21000 >10:1 8.6:1 0.69:1 34e 28000 >10:1 3.5:1 0.55:1 34f 41000 >10:1 2.9:1 0.48:1

(21) These data show the general trend that relatively smaller molecular weight versions of an oligomer are more soluble in organic solvents than relative higher molecular weight versions of the same oligomer, irrespective of the end group. These data also show that oligomers comprising end caps having polar moieties have improved solubility in organic solvents as compared to the same oligomers that do not have such end caps containing polar moieties. On average, Oligomers 33 and 34 have PGME/PGMEA solubility that is 14.7% higher than Comparative 2 oligomers of comparable molecular weights.