POLYARYLENE RESINS

Abstract

Polyarylene polymers formed from an aromatic dialkyne monomer having a solubility enhancing moiety and having relatively high weight average molecular weights and a relatively low polydispersity show improved solubility in certain organic solvents and are useful in forming relatively thick dielectric material layers in a single coating step.

Claims

1. A polyarylene polymer comprising as polymerized units one or more first monomers comprising two or more cyclopentadienone moieties; and one or more second monomers of formula (1): ##STR00014## wherein each Ar.sup.1 and Ar.sup.2 is independently a C.sub.5-30-aryl moiety; each R is independently chosen from H, and optionally substituted C.sub.5-30-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.sub.+ 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, or C.sub.1-10-haloalkyl; 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; each Y is independently a single covalent chemical bond or a divalent linking group chosen from O, S, S(), S().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 4; c2=0 to 4; a1+a2=1 to 6; b1+b2=2 to 6; c1+c2=0 to 6; d=0 to 2; z=1 to 10; z1=0 to 10; z2=0 to 10; and z1+z2=1 to 10; wherein the polyarylene polymer has a M.sub.n of 10,000 to 50,000, a M.sub.w of 30,000 to 150,000, and a PDI of 1 to <6.

2. The polyarylene polymer of claim 1 having a PDI of 1 to 4.5

3. The polyarylene polymer of claim 2 having a M.sub.w of 50,000 to 150,000 Da.

4. The polyarylene polymer of claim 1 having a PDI of 1 to 4.

5. The polyarylene polymer of claim 1 having a M.sub.w of 50,000 to 150,000 Da.

6. The polyarylene polymer of claim 1 wherein at least one first monomer has the formula (9) ##STR00015## wherein each R.sup.10 is independently chosen from H, C.sub.1-6-alkyl, or substituted or unsubstituted C.sub.5-10-aryl; and Ar.sup.3 is an aromatic moiety having from 5 to 60 carbons.

7. The polyarylene polymer of claim 1 wherein R.sup.1 is OH or C(O)OH.

8. The polyarylene polymer of claim 1 wherein at least one second monomer has the formula (4) ##STR00016## wherein each R is independently H or phenyl; each R.sup.1 is OH or C(O)OH; and a5=1 or 2.

9. The polyarylene resin of claim 8 having a PDI of 1 to 4.5.

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

11. A composition comprising one or more polyarylene polymers of claim 9 and one or more organic solvents.

12. A method of forming a dielectric material layer comprising: disposing a layer of the composition of claim 1 on a substrate surface; removing the organic solvent; and curing the polymer to form a dielectric material layer.

13. A method of preparing a polyarylene polymer comprising: (a) reacting a molar amount of a first monomer comprising two or more cyclopentadienone moieties with a first portion of a molar amount of a second monomer formula (1): ##STR00017## wherein each Ar.sup.1 and Ar.sup.2 is independently a C.sub.5-30-aryl moiety; each R is independently chosen from H, and optionally substituted C.sub.5-30-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.sub.+ 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, or C.sub.1-10-haloalkyl; 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; each Y is independently a single covalent chemical bond or a divalent linking group chosen from O, S, S(), S().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 4; c2=0 to 4; a1+a2=1 to 6; b1+b2=2 to 6; c1+c2=0 to 6; d=0 to 2; z=1 to 10; z1=0 to 10; z2=0 to 10; and z1+z2=1 to 10; then (b) reacting the molar amount of the first monomer with a second portion of the second monomer; and (c) optionally repeating step (b) with one or more additional portions of the second monomer; wherein the first portion of the second monomer is less than 1 equivalent based on the molar amount of the first monomer; wherein the sum of the first portion, the second portion and any optional addition portions of the second monomer is from 0.8 to 1.2 molar equivalents based on the molar amount of the first monomer; and wherein the polyarylene polymer has a M.sub.n of 10,000 to 50,000, a M.sub.w of 30,000 to 150,000, and a PDI of 1 to <6.

Description

EXAMPLE 1

[0035] A 4-L cylindrical reactor was charged with 485.010 g diphenylene oxide bis(triphenylcyclopentadienone) (DPO-CPD, 1.0 equivalents), 27.370 g (0.25 equivalents) of 3,5-diethynylbenzoic acid (DEBzOH), and 2422 g of GBL at room temperature. The top of the flask was then equipped with a dry ice condenser, a thermocouple with a temperature controller, N.sub.2 inlets, and a stir system. The flask was placed into a fitted heating mantle. The system was evacuated and purged three times with N.sub.2 to remove air from the reactor, which was subsequently blanketed with a constant flow of N.sub.2. The reaction was then heated to an internal temperature of 135 C. After 1 hour, the system was allowed to cool to 90 C., followed by adding a second aliquot (27.780 g, 0.25 equivalents) of DEBzOH to the flask, along with an additional 300 g of GBL. The reaction mixture was again heated to 135 C. and kept at this temperature for 1 hour. The system was again allowed to cool to 90 C., followed by adding a third aliquot (27.110 g, 0.25 equivalents) of DEBzOH to the flask, along with an additional 330 g GBL. The reaction mixture was again heated to 135 C. and kept at this temperature for 1 hour, after which time the system was again allowed to cool to 90 C., followed by adding a fourth aliquot (30.763 g, 0.29 equivalents) of DEBzOH to the flask, along with an additional 330 g GBL. The reaction mixture was again heated to 135 C. and kept at this temperature for 6 hours, after which the reaction mixture was then cooled to room temperature. The resulting polymer (Polymer 1) was isolated from the reaction mixture by precipitating it from solution by adding isopropanol at room temperature, filtered, and washed with additional isopropanol before the filtrate was dried at 70 C. for 24 hours.

[0036] Before precipitation of Polymer 1, the reaction mixture was analyzed by GPC using an Agilent HPLC system equipped with a refractive index detector and using uninhibited tetrahydrofuran as eluting solvent at 1.2 mL/min; Temperature: 35 C.; Injection Volume: 150 L; Polystyrene Narrow Standard calibration 483,000 to 162, Lower Mw cutoff=160 Da; with the HPLC column setting as follows: Shodex-KF805, exclusion limit 4,000,000; Shodex-KF804, exclusion limit 400,000; Shodex-KF803, exclusion limit 70,000; and Shodex-KF802, exclusion limit 5,000. The GPC results indicated Polymer 1 had RT (retention time)=23.700 min, a Mn of 23,787 Da, Mw of 81,630 Da, and a PDI of 3.4.

EXAMPLE 2

[0037] The procedure of Example 1 was repeated except that 500.09 g of DPO-CPD was used and DEBzOH was added as follows: 28.053 g (0.25 equivalents) as the first aliquot; 28.023 g ((0.25 equivalents) as the second aliquot; 28.097 g (0.25 equivalents) as the third aliquot; and 32.39 g (0.29 equivalents) as the fourth aliquot. After the addition of the fourth aliquot, the mixture was allowed to react for 8.5 hours to provide Polymer 2. Analysis by GPC indicated Polymer 2 had a RT of 24.083 min, a M.sub.n of 22,650 Da, M.sub.w of 85,600 Da, and a PDI of 3.8.

EXAMPLE 3

[0038] A reaction flask was charged with 20.13 g DPO-CPD, 3.31 g (0.75 equivalents) of DEBzOH, and 58 g of GBL at room temperature. The top of the flask was then equipped with a dry ice condenser, a thermocouple with a temperature controller, N.sub.2 inlets, and a stir system. The flask was placed into a fitted heating mantle The system was evacuated and purged three times with N.sub.2 to remove air from the flask followed by a constant flow of N.sub.2. The reaction was then heated to 135 C. After 4 hours, the system was allowed to cool to 90 C., followed by adding a second aliquot (1.27 g, 0.29 equivalents) of DEBzOH to the flask, along with an additional 10 g of GBL. The reaction mixture was again heated to 135 C. and kept at this temperature for 3 hours to provide Polymer 3. Analysis of the product by GPC indicated Polymer 3 had a RT of 24.233 min, a M.sub.n of 21,300 Da, M.sub.w of 52,400 Da, and a PDI of 2.46.

EXAMPLE 4

[0039] The general procedure of Example 3 was repeated except that 60 g of DPO-CPD was charged to the reaction flask, along with 10.08 g (0.75 equivalents) of DEBzOH and 210 g of GBL and a different temperature profile, in which the mixture was first heated to 90 C. for 2 hours followed by heating at 115 C. for 2 hours then 135 C. for 4 hours. Next, the system was allowed to cool to 90 C., followed by adding a second aliquot (3.92 g, 0.29 equivalents) of DEBzOH to the flask, along with an additional 70 g of GBL. The reaction mixture was again heated to 135 C. and kept at this temperature for 2 hours to provide Polymer 4. Analysis of the product by GPC indicated Polymer 4 had RT of 23.467 min, a M.sub.n of 26,545 Da, M.sub.w of 140,539 Da, and a PDI of 5.29.

EXAMPLE 5

[0040] The general procedure of Example 1 was repeated to provide Polymers 5 to 10, having the M.sub.n, M.sub.w and PDI reported in Table 1.

TABLE-US-00001 TABLE 1 Polymer M.sub.n M.sub.w PDI 5 24,650 84,700 3.4 6 22,650 85,600 3.8 7 24,600 95,100 3.9 8 32,200 103,800 3.2 9 23,800 81,600 3.4 10 23,950 88,100 3.7

EXAMPLE 6

[0041] The thermal stability of each of Polymers 5 and 6 from Example 5 was determined via thermogravimetric analysis on a TA Q5000 instrument using two different metrics. Degradation temperature, the temperature at which weight loss in the films is equal to 1% after an isothermal hold at 150 C., was measured by ramping the temperature of the sample from room temperature to 150 C. at a rate of 10 C./minute. Each sample was held at 150 C. for fifteen minutes, followed by heating once more at 10 C./minute to 600 C. Both Polymers 5 and 6 were found to have a degradation temperature of approximately 325 C. Standard thermal stability, which was also measured by thermogravimetric analysis, is the weight loss during a one hour isothermal hold at a specified temperature, either 400 C. or 450 C. Both Polymers 5 and 6 had good thermal stability, each having a weight loss of 0.5% at 400 C. and 1.5% at 450 C.

EXAMPLE 7

[0042] Films formed from Polymer 5 were evaluated to determine film thickness retention after cure. A solution of Polymer 5 (28 wt %) in a solvent blend of MMP/anisole/GBL (61.75/33.25/5 w/w/w) and containing 1 wt % of nonionic surfactants was spin coated on a silicon wafer at various spin speeds to form films of varying thicknesses. The thickness of each film was measured before and after curing at 400 C. for 60 min, and the change in thickness reported as a percentage of film thickness remaining in Table 2. Similarly, a solution of Polymer 5 (30 wt %) in a solvent blend of MMP/anisole/GBL (61.75/33.25/5 w/w/w) and containing 1 wt % of nonionic surfactants was coated on silicon wafers by bar coating using various spacer bar heights. The thickness of each film was measured before and after curing at 400 C., and the change in thickness reported as a percentage of film thickness remaining in Table 3. Films having a thickness of >100 m were easily coated, however, such thick films required a stepwise curing profile.

TABLE-US-00002 TABLE 2 Pre-Cure Post-Cure Thickness Spin Speed Thickness Thickness Retention (rpm) (m) (m) (%) 300 17.9 16.2 90.5 500 12.1 11.3 93.4 750 9.2 8.4 91.3 1000 7.9 7.2 91.1 1500 6.1 5.6 91.8 2000 5.5 4.8 87.3

TABLE-US-00003 TABLE 3 Spacer Bar Pre-Cure Post-Cure Thickness Height Thickness Thickness Retention (mm) (m) (m) (%) 0.23 30 25 83.3 0.25 35 28 80.0 0.30 40 34 85.0 0.38 43 35 81.4 0.51 102 Requires step-cure 0.64 110 Requires step-cure

EXAMPLE 8

[0043] The procedure of Example 7 was repeated except that Polymer 6 was used in place of Polymer 5. Films formed from Polymer 6 were found to have essentially the same film thickness retention.

EXAMPLE 9

[0044] Thirty micron free-standing slot-die coated films formed from Polymer 6 were cut into strips and tested at The Pennsylvania State University using a flexible testing apparatus that was custom built in their labs. Each film was mounted on a KAPTON polyimide belt and repetitively bent around a mandrel with a 1 mm diameter, corresponding to approximately a 3% strain in the film. Several film strips were tested using the apparatus, and, on average, the films survived approximately 7,000 bending cycles before breaking. Even after breaking, confocal microscopy images of the films showed no cracks or tears induced by the bending.

EXAMPLE 10

[0045] Young's Modulus and elongation of films formed from Polymer 5 were measured on an Instron 33R4464 using 10 m thick free-standing films. The 25.4 mm by 9.9 mm films underwent tensile strain at a rate of 5 mm/minute. The calculated Young's Modulus for Polymer 5 from the stress-strain curve is 1.7 GPa. Such low modulus indicates that films of the present polymers have good flexibility, particularly as compared to conventional inorganic materials used in display applications. Much of the stress-strain curve follows an approximately linear relationship, indicating that elastic deformation occurs over the majority of the strained region, while comparatively less plastic deformation occurs. The curve of applied load versus extension shows that the films of Polymer 5 sustain approximately a 5% elongation before catastrophic mechanical failure occurs.