Polymers derived from norbornadiene and maleic anhydride and use thereof

Patent metadata

Field	Value
Publication number	US-9944730-B2
Application number	US-201715782103-A
Country	US
Kind code	B2
Filing date	Oct 12, 2017
Priority date	Dec 31, 2015
Publication date	Apr 17, 2018
Grant date	Apr 17, 2018

Abstract

Embodiments encompassing a series of compositions containing polymers of norbornadiene and maleic anhydride monomers which are useful in forming a variety of photopatternable structures are disclosed and claimed. The compositions are useful as permanent dielectric materials. More specifically, embodiments encompassing compositions containing a series of ter- and tetrapolymers of a variety of norbornadiene, maleic anhydride, maleimide and norbornene-type cycloolefinic monomers in which maleic anhydride is fully or partially hydrolyzed (i.e., ring opened and fully or partially esterified), and a photoactive compound are disclosed, which are useful in forming permanent dielectric materials having utility in a variety of electronic material applications, among various other uses.

First claim

What is claimed is:

1. A polymer comprising one or more distinct first repeating unit represented by formula (IA), each of said first repeating unit is derived from a monomer of formula (I):

wherein:
represents a position at which the bonding takes place with another repeat unit;
each of R 1 , R 2 , R 3 and R 4 is independently selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxy(C 1 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, —CO 2 R, halogen and a group of formula (A):

where
R is (C 1 -C 6 )alkyl or tri(C 1 -C 6 )alkylsilyl,
R a is selected from the group consisting of —(CH 2 ) p —, —(CH 2 ) q —OCH 2 — and —(CH 2 ) q —(OCH 2 CH 2 ) r —OCH 2 —, where p is an integer from 0 to 6, q is an integer from 0 to 4 and r is an integer from 0 to 3;
one or more distinct second repeating unit represented by formula (IIA), said second repeating unit is derived from a monomer of formula (II):

wherein:
each of R 5 and R 6 is independently selected from the group consisting of hydrogen, linear or branched (C 1 -C 9 )alkyl and fluorinated or perfluorinated(C 1 -C 9 )alkyl;
R 7 is selected from the group consisting of hydrogen, linear or branched (C 1 -C 9 )alkyl, fluorinated or perfluorinated(C 1 -C 9 )alkyl,
and —(CH 2 ) a —(O—(CH 2 ) b ) c —O—(C 1 -C 6 )alkyl, where a, b and c are integers from 1 to 4; and

one or more distinct third repeating unit represented by formula (IIIA), said third repeating unit is derived from a monomer of formula (III):

wherein:
each of R 8 and R 9 is independently selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C 3 -C 9 )alkyl;
R 10 is selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, (C 5 -C 9 )cycloalkyl, (C 6 -C 10 )aryl and (C 6 -C 10 )aryl(C 1 -C 4 )alkyl;
and wherein molar amount of repeating unit of formula (IIIA) is at least 3 mole percent.

2. The polymer according to claim 1 , which further comprises one or more distinct fourth repeat unit of formula (IVA) derived from a monomer of formula (IV):

wherein:
represents a position at which the bonding takes place with another repeat unit;
m is an integer 0, 1 or 2;
each of R 11 , R 12 , R 13 and R 14 is independently selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxy(C 1 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, —(CH 2 ) a —(O—(CH 2 ) b ) c —O—(C 1 -C 4 )alkyl, where a, b and c are integers from 1 to 4, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy and halogen.

3. The polymer according to claim 1 , which further comprises a repeat unit of formula (IB) derived from the monomer of formula (I):

wherein R 1 , R 2 , R 3 and R 4 are each as defined in claim 1 .

4. The polymer according to claim 1 , which comprises one or more distinct repeating units of formula (IA) wherein,
each of R 1 , R 2 , R 3 and R 4 is independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 1 -C 12 )alkyl and phenyl(C 1 -C 3 )alkyl.

5. The polymer according to claim 1 , which comprises one or more distinct repeating units of formula (IIA) wherein, R 5 and R 6 are the same or different and independently of each other selected from hydrogen or methyl; and R 7 is selected from hydrogen, methyl, ethyl, n-propyl, iso-propyl or n-butyl.

6. The polymer according to claim 1 , which comprises one or more distinct repeating units of formula (IIIA) wherein, R 8 and R 9 are the same or different and independently of each other selected from hydrogen or methyl; and R 10 is selected from hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl or phenethyl.

7. The polymer according to claim 2 , which comprises one or more distinct repeating units of formula (IVA) wherein:
m is 0;
each of R 11 , R 12 , R 13 and R 14 is independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 1 -C 12 )alkyl, phenyl(C 1 -C 3 )alkyl and —(CH 2 ) a —(O—(CH 2 ) b ) c —O—(C 1 -C 4 )alkyl, where a is 1 or 2, b is 2 to 4 and c is 2 or 3.

8. The polymer according to claim 1 , which is having one or more distinct first repeating unit derived from a respective monomer selected from the group consisting of:
bicyclo[2.2.1]hepta-2,5-diene (norbornadiene);
2-methylbicyclo[2.2.1]hepta-2,5-diene;
2-butylbicyclo[2.2.1]hepta-2,5-diene;
2-hexylbicyclo[2.2.1]hepta-2,5-diene;
2-octylbicyclo[2.2.1]hepta-2,5-diene;
2-phenethylbicyclo[2.2.1]hepta-2,5-diene;
tert-butyl bicyclo[2.2.1]hepta-2,5-diene-2-carboxylate;
trimethylsilyl bicyclo[2.2.1]hepta-2,5-diene-2-carboxylate; and
bicyclo[2.2.1]hepta-2,5-dien-2-ylmethanol.

9. The polymer according to claim 1 , which is having one or more distinct second repeating unit derived from a respective monomer selected from the group consisting of:
maleic anhydride;
2-methyl-maleic anhydride (3-methylfuran-2,5-dione);
2,3-dimethyl-maleic anhydride (3,4-dimethylfuran-2,5-dione);
2-ethyl-maleic anhydride (3-ethylfuran-2,5-dione);
2,3-diethyl-maleic anhydride (3,4-diethylfuran-2,5-dione);
2-trifluoromethyl-maleic anhydride (3-trifluoromethylfuran-2,5-dione);
2,3-bis(trifluoromethyl)-maleic anhydride (3,4-bis(trifluoromethyl)furan-2,5-dione); and
2-methyl-3-trifluoromethyl-maleic anhydride (3-methyl-4-(trifluoromethyl)furan-2,5-dione).

10. The polymer according to claim 1 , which is having one or more distinct third repeating unit derived from a respective monomer selected from the group consisting of:
maleimide;
N-methylmaleimide;
N-butylmaleimide;
3-methylmaleimide (3-methylpyrrolidine-2,5-dione);
N-cyclohexylmaleimide;
N-phenylmaleimide;
N-benzylmaleimide; and
N-phenethylmaleimide.

11. The polymer according to claim 2 , which is having one or more distinct fourth repeating unit derived from a respective monomer selected from the group consisting of:
norbornene;
5-hexylbicyclo[2.2.1]hept-2-ene;
5-octylbicyclo[2.2.1]hept-2-ene;
5-decylbicyclo[2.2.1]hept-2-ene;
5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene (NBTON);
1-(bicyclo[2.2.1]hept-5-en-2-yl)-2,5, 8,11-tetraoxadodecane;
5-benzylbicyclo[2.2.1]hept-2-ene; and
5-phenethylbicyclo[2.2.1]hept-2-ene.

12. The polymer according to claim 1 , which is selected from the group consisting of:
a terpolymer of norbornadiene (

Assignees

• Promerus Llc

Inventors

• Rhodes Larry F
• Kandanarachchi Pramod

Classifications

• C08F32/06

  having two or more carbon-to-carbon double bonds · CPC title

• G03F7/168

  Finishing the coated layer, e.g. drying, baking, soaking · CPC title

• C08L47/00 Primary

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers (C08L45/00 takes precedence; of conjugated diene rubbers C08L9/00 - C08L21/00) · CPC title

• G03F7/162

  Coating on a rotating support, e.g. using a whirler or a spinner · CPC title

• G03F7/2002

  with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image · CPC title