POLYARYLENE RESIN COMPOSITIONS

Abstract

Polyarylene oligomer compositions capable of curing at lower temperatures than conventional polyarylene oligomers are useful in forming dielectric material layers in electronics applications.

Claims

1. A composition comprising: one or more polyarylene polymers having a backbone comprising as repeating units one or more aryl moieties having one or more epoxy-reactive moieties, the polyarylene polymer comprising as polymerized units one or more polyalkynyl-substituted aryl first monomers and one or more biscyclopentadienone second monomers; and one or more epoxide-containing crosslinkers.

2. The composition of claim 1 wherein the epoxy-reactive moiety has the formula ##STR00020## where LG is a linking group or a single chemical bond; each ERS is an epoxy-reactive substituent; w is an integer from 1 to 6; and * is the point of attachment to an aryl moiety.

3. The composition of claim 2 wherein each epoxy-reactive substituent is independently chosen from C(O)OH, OH, SH, NR.sup.20R.sup.21, and combinations thereof, wherein R.sup.20 and R.sup.21 are independently chosen from H, C.sub.1-10-alkyl, C.sub.6-10-aryl, and C.sub.7-20-aralkyl.

4. The composition of claim 1 wherein the one or more first monomers comprise an aryl moiety substituted with the one or more epoxy-reactive moieties.

5. The composition of claim 4 wherein the one or more second monomers are chosen from compounds of the formula ##STR00021## wherein each r.sup.10 is independently chosen from H, phenyl, or substituted phenyl; and Ar.sup.3 is an aryl moiety.

6. The composition of claim 1 wherein at least one polyarylene polymer has repeating units of the formula ##STR00022## wherein LG is a linking group or a single chemical bond; each ERS is an epoxy-reactive substituent; w is an integer from 1 to 6; Ar is an optionally substituted C.sub.5-30 aryl moiety; Ar.sup.10 and Ar.sup.11 are each independently optionally substituted C.sub.6-10 aryl moieties; Ar.sup.3 is an aryl moiety; and o is the number of repeat units in the oligomer and is an integer from 2 to 1000.

7. The composition of claim 1 further comprising one or more organic solvents.

8. A method comprising: providing a substrate; coating a layer of the composition of claim 7 on a surface of the substrate; and curing the layer of the composition to form a cross-linked polyarylene layer.

9. A composition comprising: (a) one or more polyarylene polymers, at least one polyarylene polymer comprising as polymerized units one or more monomers of the formula ##STR00023## wherein Ar.sup.1 and each Ar.sup.2 are independently a C.sub.5-30-aryl moiety; each IV is independently chosen from H, C.sub.5-30-aryl, and substituted C.sub.5-30 aryl; each R.sup.2 is independently chosen from C.sub.1-10-alkyl, C.sub.1-10-haloalkyl, C.sub.1-10-alkoxy, CN, and halo; each Z is an epoxy-reactive moiety; 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.5).sub.2).sub.z, C.sub.5-30-aryl, and (C(R.sup.5).sub.2).sub.z1(C.sub.5-30-aryl)-(C(R.sup.5).sub.2).sub.z2; each R.sup.5 is independently chosen from H, hydroxy, halo, C.sub.1-10-alkyl, C.sub.1-10-haloalkyl, and C.sub.5-30-aryl; a1=0 to 3; each a2=0 to 3; b1=1 to 4; each b2=0 to 2; c1=0 to 2; each c2=0 to 2; a1+each a2=1 to 6; b1+each b2=2 to 6; c1+each 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; and (b) one or more epoxide-containing crosslinkers.

10. The composition of claim 9 wherein each Z is independently has the formula ##STR00024## where LG is a linking group or a single chemical bond; each ERS is an epoxy-reactive substituent; w is an integer from 1 to 6; and * is the point of attachment to an aryl moiety.

11. The composition of claim 10 wherein the epoxy-reactive substituent is chosen from one or more of C(O)OH, OH, SH, NR.sup.20R.sup.21, and combinations thereof, wherein R.sup.20 and R.sup.21 are independently chosen from H, C.sub.1-10-alkyl, C.sub.6-10-aryl, and C.sub.7-20-aralkyl.

12. The composition of claim 11 wherein the one or more polyarylene polymers further comprise as polymerized units one or more second monomers comprising two cyclopentadienone moieties.

13. The composition of claim 12 wherein the one or more second monomers are chosen from one or more monomers of formula ##STR00025## wherein each R.sup.10 is independently chosen from H, phenyl, or substituted phenyl; and Ar.sup.3 is an aryl moiety.

14. The composition of claim 9 further comprising one or more organic solvents.

15. A method comprising: providing a substrate; coating a layer of the composition of claim 14 on a surface of the substrate; and curing the layer of the composition to form a cross-linked polyarylene layer.

Description

EXAMPLE 1

Preparation of Polymer 1

[0048] 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 (DEB z0H, 1.793 g, 10.54 mmol) and 1,3,5-tris(phenylethynyl)benzene (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 GPC to provide an M.sub.n of 6761 Da, an M.sub.w of 41719 Da, and a polydispersity index (M.sub.w/M.sub.n) of 6.17. This reaction is shown in Scheme 2.

##STR00018##

EXAMPLE 2

Preparation of Polymer 2

[0049] DPO-CPD (9.0 g, 0.0115 mol) and 3,5-diethynylphenol (1.96 g, 0.0138 mol) 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 2) was collected by filtration and then dried in vacuum oven at 65 to 70 C. for 2 days, yielding 10.0 g of a brown solid in 97% yield. Analysis of the polymer by GPC indicated an M.sub.w of 9300, and a polydispersity index (M.sub.w/M.sub.n) of 2.1. This reaction is illustrated in Scheme 3.

##STR00019##

EXAMPLE 3

Preparation of Polymer 3

[0050] DPO-CPD (9.0 g, 0.0115 mol) and 3,5-diethynylphenol (1.37 g, 0.0096 mol) were dissolved in 97 g of GBL. The reaction was heated at 130 C. for 2 hr. and then cooled down to 80 C. 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 3 was obtained as a brown solid (10.1 g) in 98% yield. Analysis by GPC indicated a Mw of 7100 and a polydispersity index of 3.7.

EXAMPLE 4

Preparation of Polymer 4

[0051] The procedure of Example 1 was generally repeated except that no TRIS monomer was used. The resulting polymer, Polymer 4, had an M.sub.n of 20.7 kDa.

EXAMPLE 5

Polymers 5-9

[0052] The procedure of Example 1 is repeated except that 3,5-diethynylbenzoic acid is replaced with the monomers shown in Table 1 with similar results expected.

TABLE-US-00001 TABLE 1 Polymer Number Monomer 5 2-(3,5-Diethynylphenoxy)ethan-1-ol 6 3,5-Diethynylaniline 7 3,5-Bis(phenylethynyl)benzoic acid 8 6,6-Diethynyl-[1,1-binaphthalene]-2,2-diol 9 4,9-Diethynylpyrene-1,6-dicarboxylic acid

[0053] Comparative Polymers. Comparative Polymer 1 was prepared according to the general procedure of Example 1 except that no DEBzOH monomer was used. The resulting polymer, Comparative Polymer 1, was precipitated from water and was found to have an M.sub.n of 9.7 kDa.

[0054] Comparative Polymer 2 was prepared according to the general procedure of Example 4 except that the DEBzOH monomer was replaced with 3,5-diethynylbenzamide. The ratio of 3,5-diethynylbenzamide to DPO-CPD was 1.1:1.

EXAMPLE 6

[0055] Bisphenol A diglycidyl ether (BPA-DGE, 20 mg) was added to 1 g of a 10 wt % solution in PGMEA of a polyarylene oligomer in a 20 mL scintillation vial. The polyarylene oligomers used are shown in Table 2. The Control sample was BPA-DGE alone in PGMEA with no polyarylene oligomer present.

TABLE-US-00002 TABLE 2 Formulation Polyarylene No. Oligomer 1 Polymer 4 Cl Comparative Polymer 1 C2 Comparative Polymer 2 Control None

[0056] Each vial was warmed in a heating block to 100 C. without a cap, allowing for the evaporation of solvent and the formation of a thick film on the bottom of the vial. The temperature of the heating block was raised to 165 C., and the vial was kept at this temperature for 2 hrs. Each resulting film was dissolved in tetrahydrofuran (THF), and diluted for analysis by GPC. GPC analysis of the films formed from each of Formulations C1 and C2 indicated little to no reaction occurred. GPC analysis of the film formed from Formulation 1 showed significant broadening of the molecular weight distribution with a concomitant increase in polydispersity, indicating significant crosslinking occurred. GPC analysis of the control sample showed no change.

EXAMPLE 7

[0057] Formulation 2 was prepared according to the procedure of Example 6 using Polymer 4 and BPA-DGE, except that the amount of BPA-DGE was 50 wt %, based on the weight of Polymer 4. Following the procedure of Example 6, GPC analysis of the THF extract of the film formed from Formulation 2 indicated complete crosslinking.

[0058] EXAMPLE 8

[0059] Various formulations of the invention are expected to be prepared by combining the epoxide-containing crosslinkers and polyarylene oligomers shown in Table 3 in PGMEA. The amount of the crosslinker reported in Table 3 is in wt %, based on the weight of the polyarylene oligomer. The following abbreviations are used in Table 3: BPF-DGE =bisphenol F diglycidyl ether; BPBP-DGE=bisphenol BP diglycidyl ether; TPM-DGE=triphenylolmethane triglycidyl ether; CO-TGE=castor oil triglycidyl ether; PG-TGE=triglycidyl ether of propoxylated glycerol having on average 8 moles of propoxylation; and G-TGE=glycerol triglycidyl ether; BNM-TTGE=bis(naphthyldiol)methane tetraglycidyl ether.

TABLE-US-00003 TABLE 3 Formulation Polyarylene No. Crosslinker Oligomer 3 BPF-DGE (15 wt %) Polymer 1 4 BPBP-DGE (25 wt %) Polymer 4 5 TPM-TGE (15 wt %) Polymer 2 6 PG-TGE (20 wt %) Polymer 2 7 G-TGE (30 wt %) Polymer 9 8 TPM-TGE (25 wt %) Polymer 7 9 CO-TGE (23 wt %) Polymer 6 10 BPA-DGE (35 wt %) Polymer 6 11 BNM-TTGE (30 wt %) Polymer 8 12 BPA-DGE (30 wt %) Polymer 5