# US 11,306,182 B2 · Oligomer, composition including oligomer, article prepared from the composition, method for preparing article, and display device including the article

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- Number: US 11,306,182 B2
- Document ID: US11306182B2
- Status: Granted
- Kind: B2
- Application number: 16/354,829
- Filed: 2019-03-15
- Published: 2019-09-19
- Granted: 2022-04-19
- Earliest claimed: 2018-03-16
- Assignees: Samsung Electronics Co., Ltd.; Samsung Display Co., Ltd.
- Applicants: Samsung Electronics Co., Ltd.
- Inventors: Fedosya Kalinina; Young Jae Kang; Dmitry Androsov; Hyunseok Choi
- Web page: https://patentgrep.com/patent/US11306182B2

## CPC

- C08G 73/1067: {Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound}
- C08G 73/101: {containing chain terminating or branching agents}
- C08G 73/1039: {comprising halogen-containing substituents}
- C08G 73/1042: {Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds}
- C08G 73/1078: {wholly aromatic in the diamino moiety}
- G02F 1/13363: Birefringent elements, e.g. for optical compensation
- G02F 1/133723: {Polyimide, polyamide-imide}
- Y02E 10/549: Organic PV cells
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

An oligomer including two ends and a main chain located between the two ends, a group represented by Chemical Formula 1 at one end and a structural unit represented by Chemical Formula 2 or Chemical Formula 3 in the main chain: wherein, in Chemical Formulae 1 to 3, R1, Ar1, and Ar2 are the same as defined in the detailed description.

## Claims

### Claim 1

An oligomer comprising:
two ends and a main chain located between the two ends,
a group represented by Chemical Formula 1 at one end, and a structural unit represented by Chemical Formula 2 or Chemical Formula 3 in the main chain:
wherein, in Chemical Formula 1,
R1 is a C4 to C10 tertiary alkoxy group, a R—CH═CH—O— group wherein R is hydrogen or substituted or unsubstituted C1 to C8 alkyl group, a R—CH═CH—CH2—O— group wherein R is hydrogen or substituted or unsubstituted C1 to C7 alkyl group, a substituted phenyloxy group, a substituted or unsubstituted benzyloxy group, or a 9-fluorenylmethyloxy group, and
Ar2 comprises a substituted or unsubstituted C6 to C30 aromatic organic group, wherein the substituted or unsubstituted C6 to C30 aromatic organic group is present as a substituted or unsubstituted single aromatic ring; a fused ring comprising two or more substituted or unsubstituted aromatic rings; or a ring system comprising two or more of the substituted or unsubstituted single aromatic ring and/or the fused ring that are linked by a single bond, a fluorenylene group, a substituted or unsubstituted C1 to C10 cycloalkylene group, a substituted or unsubstituted C6 to C15 arylene group, —O—, —S—, —C(═O)—, —CH(OH)—, —S(═O)2—, —Si(CH3)2—, —(CH2)p— (wherein, 1≤p≤10), —(CF2)q— (wherein, 1≤q≤10), —C(CH3)2—, —C(CF3)2—, —C(═O)NH—, or a combination thereof;
wherein, in Chemical Formula 2 and Chemical Formula 3,
Ar2 is the same as defined in Chemical Formula 1,
Ar1 comprises a combination of a group represented by Chemical Formula 4 and a group represented by Chemical Formula 5:
wherein, in Chemical Formula 4,
R10 is a single bond, —O—, —S—, —C(═O)—, —CH(OH)—, —C(═O)NH—, —S(═O)2—, —Si(CH3)2—, —(CH2)p— (wherein, 1≤p≤10), —(CF2)q— (wherein, 1≤q≤10), —C(CnH2n+1)2—, —C(CnF2n+1)2—, —(CH2)p—C(CnH2n+1)2—(CH2)q—, —(CH2)p—C(CnF2n+1)2—(CH2)q— (wherein 1≤n≤10, 1≤p≤10, and 1≤q≤10), or a combination thereof,
R12 and R13 are independently a halogen, a hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic organic group, a substituted or unsubstituted C6 to C20 aromatic organic group, a —OR201 group (wherein, R201 is a C1 to C10 aliphatic organic group), or a —SiR210R211R212 group (wherein R210, R211, and R212 are independently hydrogen or a C1 to C10 aliphatic organic group), and
n7 and n8 are independently one of integers of 0 to 3;
wherein, in Chemical Formula 5,
R4 and R5 are independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 acyl group, a hydroxy group, a halogen, a nitro group, —NR′R″ (wherein, R′ and R″ are independently hydrogen, a C1 to C30 alkyl group, or a C6 to C30 aryl group), —SiR′R″R′″ (wherein R′, R″, and R′″ are independently hydrogen, a C1 to C30 alkyl group, or a C6 to C30 aryl group), or a combination thereof,
L1 is O or NRb (wherein, Rb is hydrogen or a C1 to C20 alkyl group),
A1 is a substituted or unsubstituted C6 to C30 aromatic organic group, and
Ra is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a hydroxy group, a halogen, a nitro group, —NR′R″ (wherein, R′ and R″ are independently hydrogen, a C1 to C30 alkyl group, a C6 to C30 aryl group, or a C7 to C30 arylalkyl group), —C(═O)—NR′R″ (wherein, R′ and R″ are independently hydrogen, a C1 to C30 alkyl group, a C6 to C30 aryl group, or a C7 to C30 arylalkyl group), —SiR′R″R′″ (wherein R′, R″, and R′″ are independently hydrogen, a C1 to C30 alkyl group, a C6 to C30 aryl group, or a C7 to C30 arylalkyl group), or a group represented by Chemical Formula 6:
*L2-A2qL3-A3)r] Chemical Formula 6
wherein, in Chemical Formula 6,
L2 and L3 are independently, O, C(═O), C(═O)O, C≡C, or C(═O)NRb (wherein, Rb is hydrogen or a C1 to C30 alkyl group),
A2 and A3 are independently substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted C7 to C20 arylalkyl or arylalkylene group,
q and r are independently integers of 0 to 3;
k is one of integers of 1 to 2,
m is one of integers of 0 to 3,
n is one of integers of 0 to 20, and
o and p are independently one of integers of 0 to 3.

### Claim 2 (depends on 1)

The oligomer of claim 1, wherein R1 of Chemical Formula 1 is a t-butoxy group, a 2-methyl-2-butoxy group, a C10 cycloalkoxy group, vinyloxy group, allyloxy group, an n-nitrophenyloxy group, a nitrobenzyloxy group, or a benzyloxy group.

### Claim 3 (depends on 1)

The oligomer of claim 1, wherein R1 of Chemical Formula 1 is a t-butoxy group or a benzyloxy group.

### Claim 4 (depends on 1)

The oligomer of claim 1, wherein Ar2 of Chemical Formula 1 to Chemical Formula 3 is a group where substituted or unsubstituted two aromatic rings are linked by a single bond, a fluorenylene group, a substituted or unsubstituted C1 to C10 cycloalkylene group, a substituted or unsubstituted C6 to C15 arylene group, —O—, —S—, —C(═O)—, —CH(OH)—, —S(═O)2—, —Si(CH3)2—, —(CH2)p— (wherein, 1≤p≤10), —(CF2)q— (wherein, 1≤q≤10), —C(CH3)2—, —C(CF3)2—, —C(═O)NH—, or a combination thereof.

### Claim 5 (depends on 1)

The oligomer of claim 1, wherein Ar2 of Chemical Formula 1 to Chemical Formula 3 is a group where two aromatic rings, each of which is substituted with an electron withdrawing group, are linked by a single bond.

### Claim 6 (depends on 1)

The oligomer of claim 1, wherein R10 of Chemical Formula 4 is a single bond, —O—, —S—, —C(═O)—, —CH(OH)—, —C(═O)NH—, —S(═O)2—, —Si(CH3)2—, —(CH2)p— (wherein, 1≤p≤3), —(CF2)q— (wherein, 1≤q≤3), —C(CnH2n+1)2—, —C(CnF2n+1)2—, —(CH2)p—C(CnH2n+1)2—(CH2)q—, —(CH2)p—C(CnF2n+1)2—(CH2)q— (wherein 1≤n≤10, 1≤p≤3, and 1≤q≤3), or a combination thereof.

### Claim 7 (depends on 1)

The oligomer of claim 1, wherein L1 of Chemical Formula 5 is O, A1 is a substituted or unsubstituted C6 to C20 aromatic organic group, Ra is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a halogen, —NR′R″ (wherein, R′ and R″ are independently hydrogen, a C1 to C30 alkyl group, a C6 to C30 aryl group, or a C7 to C30 arylalkyl group), —C(═O)—NR′R″ (wherein, R′ and R″ are independently hydrogen, a C1 to C30 alkyl group, a C6 to C30 aryl group, or a C7 to C30 arylalkyl group), or the group represented by Chemical Formula 6, k is 1, m is one of integers of 0 to 2, and n is one of integers of 1 to 3.

### Claim 8 (depends on 5)

The oligomer of claim 5, wherein L2 and L3 of Chemical Formula 6 are independently C(═O)O, C≡C, or C(═O)NRb (wherein, Rb is hydrogen or a C1 to C20 alkyl group), A2 and A3 are independently substituted or unsubstituted C6 to C20 aromatic ring, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted C7 to C20 arylalkyl or arylalkylene group, and q and r are independently an integer ranging from 0 to 2, provided that 1≤q+r≤2.

### Claim 9 (depends on 1)

The oligomer of claim 1, wherein R10 of Chemical Formula 4 comprises a single bond, —C(CF3)2—, or a combination thereof,
L1 of Chemical Formula 5 is O, A1 is a C6 aromatic organic group, Ra is hydrogen, C1 to C30 alkyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, —F, —Cl, —NR′R″ (wherein, R′ and R″ are independently hydrogen, a C1 to C30 alkyl group, a C6 to C30 aryl group, or a C7 to C30 arylalkyl group), —C(═O)—NR′R″ (wherein, R′ and R″ are independently hydrogen, a C1 to C30 alkyl group, a C6 to C30 aryl group, or a C7 to C30 arylalkyl group), or the group represented by Chemical Formula 6, k is 1, m is one of integers of 0 to 2, and n is one of integers of 1 to 3.

### Claim 10 (depends on 1)

The oligomer of claim 1, wherein the oligomer comprises one of groups represented by Chemical Formula 7 to Chemical Formula 10 at the other end:
wherein, in Chemical Formula 7 to Chemical Formula 10,
Ar1 is the same as defined in claim 1,
in Chemical Formula 9 and Chemical Formula 10,
R6 is hydrogen, a halogen, a vinyl group, an ethynyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, a C3 to C20 cycloalkyl group, a C6 to C20 aryl group, or a combination thereof, and
s is one of integers of 1 to 30.

### Claim 11 (depends on 1)

The oligomer of claim 1, wherein a weight average molecular weight (Mw) of the oligomer measured by Gel Permeation Chromatography is about 1,000 grams per mole to about 25,000 grams per mole.

### Claim 12 (depends on 1)

A composition for preparing a polymer comprising the oligomer of claim 1 and a solvent.

### Claim 13 (depends on 1, 12)

The composition of claim 12, wherein the oligomer comprises one of groups represented by Chemical Formula 7 to Chemical Formula 10 at the other end:
wherein, in Chemical Formula 7 to Chemical Formula 10,
Ar1 is the same as defined in claim 1,
wherein, in Chemical Formula 9 and Chemical Formula 10,
R6 is hydrogen, a halogen, a vinyl group, an ethynyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, a C3 to C20 cycloalkyl group, a C6 to C20 aryl group, or a combination thereof, and
s is one of integers of 1 to 30.

### Claim 14 (depends on 1, 12)

The composition of claim 12, wherein the composition further comprises a second oligomer comprising a structural unit represented by Chemical Formula 2 or Chemical Formula 3 in the main chain and a group represented by Chemical Formula 7 or Chemical Formula 8 at one end:
wherein, in Chemical Formula 2, Chemical Formula 3, Chemical Formula 7 and Chemical Formula 8,
Ar1 and Ar2 are the same as defined in claim 1.

### Claim 15 (depends on 1, 14)

The composition of claim 14, wherein the second oligomer comprises a group represented by Chemical Formula 9 or Chemical Formula 10 at the other end:
wherein, in Chemical Formula 9 or Chemical Formula 10,
Ar1 is the same as defined in claim 1,
R6 is hydrogen, a halogen, a vinyl group, an ethynyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, a C3 to C20 cycloalkyl group, a C6 to C20 aryl group, or a combination thereof, and
s is one of integers of 1 to 30.

### Claim 16 (depends on 12)

The composition of claim 12, wherein an amount of the oligomer in the composition is about 10 percent by weight to about 50 percent by weight, and viscosity of the composition is less than or equal to about 500 centipoises.

### Claim 17 (depends on 12)

A method for preparing an article, comprising
coating the composition of claim 12 on a substrate,
heating the same to remove a solvent at a temperature greater than or equal to which the end group represented by Chemical Formula 1 of the oligomer in the composition is converted to a group represented by Chemical Formula 16, and
additionally, heating the same for the oligomer to further polymerize to form a polymer
Chemical Formula 1
wherein, in Chemical Formula 1,
R1 is a C4 to C10 tertiary alkoxy group, a C3 to C10 cycloalkoxy group, a R—CH═CH—O— group wherein R is hydrogen or substituted or unsubstituted C1 to C8 alkyl group, a R—CH═CH—CH2—O— group wherein R is hydrogen or substituted or unsubstituted C1 to C7 alkyl group, a substituted phenyloxy group, a substituted or unsubstituted benzyloxy group, or a 9-fluorenylmethyloxy group, and
Ar2 comprises a substituted or unsubstituted C6 to C30 aromatic organic group, wherein the substituted or unsubstituted C6 to C30 aromatic organic group is present as a substituted or unsubstituted single aromatic ring; a fused ring comprising two or more substituted or unsubstituted aromatic rings; or a ring system comprising two or more of the substituted or unsubstituted single aromatic ring and/or the fused ring that are linked by a single bond, a fluorenylene group, a substituted or unsubstituted C1 to C10 cycloalkylene group, a substituted or unsubstituted C6 to C15 arylene group, —O—, —S—, —C(═O)—, —CH(OH)—, —S(═O)2—, —Si(CH3)2—, —(CH2)p— (wherein, 1≤p≤10), —(CF2)q— (wherein, 1≤q≤10), —C(CH3)2—, —C(CF3)2—, —C(═O)NH—, or a combination thereof;
NH2—Ar2—* Chemical Formula 16
wherein, in Chemical Formula 16, Ar2 is the same as defined in Chemical Formula 1.

### Claim 18

An oligomer comprising:
two ends and a main chain located between the two ends,
a group represented by Chemical Formula 1 at one end, and a structural unit represented by Chemical Formula 2 or Chemical Formula 3 in the main chain:
wherein, in Chemical Formula 1,
R1 is a C4 to C10 tertiary alkoxy group, a R—CH═CH—O— group wherein R is hydrogen or substituted or unsubstituted C1 to C8 alkyl group, a R—CH═CH—CH2—O— group wherein R is hydrogen or substituted or unsubstituted C1 to C7 alkyl group, a substituted phenyloxy group, a substituted or unsubstituted benzyloxy group, or a 9-fluorenylmethyloxy group, and
Ar2 comprises a substituted or unsubstituted C6 to C30 aromatic organic group, wherein the substituted or unsubstituted C6 to C30 aromatic organic group is present as a substituted or unsubstituted single aromatic ring; a fused ring comprising two or more substituted or unsubstituted aromatic rings; or a ring system comprising two or more of the substituted or unsubstituted single aromatic ring and/or the fused ring that are linked by a single bond, a fluorenylene group, a substituted or unsubstituted C1 to C10 cycloalkylene group, a substituted or unsubstituted C6 to C15 arylene group, —O—, —S—, —C(═O)—, —CH(OH)—, —S(═O)2—, —Si(CH3)2—, —(CH2)p— (wherein, 1≤p≤10), —(CF2)q— (wherein, 1≤q≤10), —C(CH3)2—, —C(CF3)2—, —C(═O)NH—, or a combination thereof;
wherein, in Chemical Formula 2 and Chemical Formula 3,
Ar2 is the same as defined in Chemical Formula 1,
Ar1 is represented by Chemical Formula 5:
wherein, in Chemical Formula 5,
R4 and R5 are independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 acyl group, a hydroxy group, a halogen, a nitro group, —NR′R″ (wherein, R′ and R″ are independently hydrogen, a C1 to C30 alkyl group, or a C6 to C30 aryl group), —SiR′R″R′″ (wherein R′, R″, and R′″ are independently hydrogen, a C1 to C30 alkyl group, or a C6 to C30 aryl group), or a combination thereof,
L1 is O or NRb (wherein, Rb is hydrogen or a C1 to C20 alkyl group),
A1 is a substituted or unsubstituted C6 to C30 aromatic organic group, and
Ra is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a hydroxy group, a halogen, a nitro group, —NR′R″ (wherein, R′ and R″ are independently hydrogen, a C1 to C30 alkyl group, a C6 to C30 aryl group, or a C7 to C30 arylalkyl group), —C(═O)—NR′R″ (wherein, R′ and R″ are independently hydrogen, a C1 to C30 alkyl group, a C6 to C30 aryl group, or a C7 to C30 arylalkyl group), —SiR′R″R′″ (wherein R′, R″, and R′″ are independently hydrogen, a C1 to C30 alkyl group, a C6 to C30 aryl group, or a C7 to C30 arylalkyl group), or a group represented by Chemical Formula 6:
*L2-A2qL3-A3)r] Chemical Formula 6
wherein, in Chemical Formula 6,
L2 and L3 are independently, O, C(═O), C(═O)O, C≡C, or C(═O)NRb (wherein, Rb is hydrogen or a C1 to C30 alkyl group),
A2 and A3 are independently substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted C7 to C20 arylalkyl or arylalkylene group,
q and r are independently integers of 0 to 3;
k is one of integers of 1 to 2,
m is one of integers of 0 to 3,
n is one of integers of 0 to 20, and
o and p are independently one of integers of 0 to 3.