Silylated polyarylenes

Patent metadata

Field	Value
Publication number	US-9481810-B2
Application number	US-201414569811-A
Country	US
Kind code	B2
Filing date	Dec 15, 2014
Priority date	Dec 15, 2014
Publication date	Nov 1, 2016
Grant date	Nov 1, 2016

Abstract

Polyarylenes comprising as polymerized units a first monomer having two cyclopentadienone moieties and a second monomer having two or more alkyne moieties, wherein at least one alkyne moiety is directly bonded to a silicon atom are provided. Such polyarylenes are useful as dielectric materials in the manufacture of electronic devices.

First claim

What is claimed is:

1. An arylene oligomer comprising as polymerized units a first monomer having two cyclopentadienone moieties and a second monomer having two or more alkyne moieties, wherein at least one alkyne moiety is directly bonded to a silicon atom, and wherein the second monomer is chosen from formula (5) and formula (6)

wherein a is an integer from 0 to 4; b is 2 or 3; c is 2 or 3; each R 6 is independently chosen from H, Si(R 8 ) 3 , C 1-10 alkyl, C 1-10 alkoxy, C 7-15 aralkyl, C 6-10 aryl, and substituted C 6-10 aryl; each R 7 is independently chosen from H, C 1-10 alkyl, C 1-10 alkoxy, C 7-15 aralkyl, C 6-10 aryl, and substituted C 6-10 aryl, each R 8 is independently chosen from H, halogen, hydroxyl, C 1-10 alkyl, C 1-10 alkoxy, C 7-15 aralkyl, C 7-15 aralkoxy, C 6-10 aryl, C 6-20 aryloxy, and substituted C 6-10 aryl; and Ar 3 is C 6-10 carbocyclic aryl; provided that at least one R 6 is Si(R 8 ) 3 .

2. The arylene oligomer of claim 1 wherein the first monomer has the formula

wherein each R 1 is independently chosen from H, phenyl, or substituted phenyl; and Ar 1 is an aromatic moiety.

3. The arylene oligomer of claim 2 wherein each R 1 is phenyl.

4. The arylene oligomer of claim 1 wherein each R 8 is independently chosen from H, hydroxyl, C 1-6 alkyl, C 1-6 alkoxy, C 7-12 aralkyl, C 7-15 aralkoxy, C 6-10 aryl, C 6-15 aryloxy, and substituted C 6-10 aryl.

5. The arylene oligomer of claim 4 wherein each R 8 is independently chosen from H, hydroxyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, phenyl, benzyl, phenethyl, and phenoxy.

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

7. The composition of claim 6 wherein the organic solvent is chosen from benzyl esters of C 2-6 alkanecarboxylic acids, dibenzyl esters of C 2-6 alkanedicarboxylic acids, tetrahydrofurfuryl esters of C 2-6 alkanecarboxylic acids, ditetrahydrofurfuryl esters of C 2-6 alkanedicarboxylic acids, phenethyl esters of C 2-6 alkanecarboxylic acids, diphenethyl esters of (C 2 -C 6 )alkanedicarboxylic acids, cycloalkanones and aromatic solvents.

8. The composition of claim 7 further comprising a water-miscible solvent.

9. A method of preparing the arylene oligomer of claim 1 comprising reacting a first monomer having two cyclopentadienone moieties with a second monomer having two or more alkyne moieties, wherein at least one alkyne moiety is directly bonded to a silicon atom.

10. An electronic device comprising a polymeric layer formed from the arylene oligomer of claim 1 .

11. A method of manufacturing an electronic device comprising: providing an electronic device substrate; disposing a layer of the composition of claim 6 on the electronic device substrate; curing the composition to form a cured polyarylene film on the electronic device substrate; and subjecting the cured polyarylene film to one or more of lithography, etching, metallization, drilling, ablation, and dielectric film stack build-up.

12. The arylene oligomer of claim 1 wherein the second monomer is chosen from 1,3-bis[(trimethylsilyl)ethynyl]benzene, 1,4-bis[(trimethylsily)ethynyl]benzene, 1,3,5-tris(trimethylsilylethynyl)benzene, 1,3-bis[(trimethoxysilyl)ethynyl]benzene, 1,4-bis[(trimethoxysily)ethynyl]benzene, 1,3-bis[(dimethylmethoxysilyl)ethynyl]benzene, 1,4-bis[(dimethylmethoxysily)ethynyl]benzene, 1,3-phenylenebis(ethyne-2,1-diyl))bis(dimethylsilanol), 1,4-phenylenebis(ethyne-2,1-diyl))bis(dimethylsilanol), bis(phenylethynyl)dimethylsilane, and bis(phenylethynyl)dimethoxysilane.

13. The arylene oligomer of claim 1 wherein Ar 3 is phenyl or naphthyl.

14. The arylene oligomer of claim 2 wherein Ar 1 is an aromatic moiety having the structure shown of formula (2)
Ar 2 x Z—Ar 2 y   (2)

wherein x is an integer chosen from 1, 2 or 3; y is an integer chosen from 0, 1or 2; each Ar 2 is independently chosen from

each R 2 is independently chosen from halogen, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, phenyl, and phenoxy; b is an integer from 0 to 4; each of c and d is an integer from 0 to 3; each Z is independently chosen from O, S, SO, SO 2 , NR 3 , PR 3 , P(═O)R 3 , C(═O), CR 4 R 5 , and SiR 4 R 5 ; R 3 , R 4 , and R 5 are independently chosen from H, (C 1 -C 4 )alkyl, halo(C 1 -C 4 )alkyl, and phenyl.

Assignees

• Rohm & Haas Elect Mat
• Rohm & Haas Elect Materials Korea Ltd

Inventors

• Gilmore Christopher D
• Ding Ping
• Kim Young Seok
• Kim Tae Hwan

Classifications

• C08G61/10 Primary

  only aromatic carbon atoms, e.g. polyphenylenes · CPC title

• C08L65/02

  Polyphenylenes · CPC title

• C08G2261/80

  Functional group cleavage, e.g. removal of side-chains or protective groups · CPC title

• C09D183/16 Primary

  in which all the silicon atoms are connected by linkages other than oxygen atoms · CPC title

• C08G2261/74

  Further polymerisation of the obtained polymers, e.g. living polymerisation to obtain block-copolymers · CPC title