# US 2021/0277157 A1 · Vinylether-based polymer as dielectric

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- Number: US 2021/0277157 A1
- Document ID: US20210277157A1
- Status: Published application
- Kind: A1
- Application number: 17/255,397
- Filed: 2019-05-22
- Published: 2021-09-09
- Earliest claimed: 2018-06-26
- Assignees: Clap Co., Ltd.
- Applicants: Clap Co., Ltd.
- Inventors: Daniel KAELBLEIN; Fulvio Giacomo BRUNETTI; Georg BECK; Daniel BAHL; Ulrich BERENS; Ingo MUENSTER
- Web page: https://patentgrep.com/patent/US20210277157A1

## CPC

- C08F 16/14: Monomers containing only one unsaturated aliphatic radical
- C08F 116/14: Monomers containing only one unsaturated aliphatic radical
- C08F 212/22: {Oxygen}
- C08F 216/1408: {Monomers containing halogen}
- H10K 85/141: {comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE}
- H10K 85/151: {Copolymers}
- H10K 10/471: {the gate dielectric comprising only organic materials}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES

## Abstract

The present invention provides polymers comprising units of formula (1) as well as compositions comprising the polymers, processes for the preparation of the polymers, electronic devices comprising the polymers, and processes for the preparation of the electronic devices, and the use of the polymers as dielectric materials.

## Claims

### Claim 1

Polymers comprising units of formula (1)
wherein
X1 and X2 are independently O or S,
L1 is a linking group, and
R1, R2, R3, R4 and R5 are independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Ra, O—C1-30-alkyl, O—C1-30-alkyl substituted with one or more substituents Ra, C(O)—C1-30-alkyl, C(O)—C1-30-alkyl substituted with one or more substituents Ra, C5-7-cycloalkyl, C5-7-cycloalkyl substituted with one or more substituents Rb, O—C5-7-cycloalkyl, O—C5-7-cycloalkyl substituted with one or more substituents Rb, C(O)—C5-7-cycloalkyl, C(O)—C5-7-cycloalkyl substituted with one or more substituents Rb, C6-14-aryl, C6-14-aryl substituted with one or more substituents Rb, O—C6-14-aryl, O—C6-14-aryl substituted with one or more substituents Rb, C(O)—C6-14-aryl, C(O)—C6-14-aryl substituted with one or more substituents Rb, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents Rb,
or
R1 and R2 together with the C-atoms to which they are attached form a 5 to 6 membered ring or a 5 to 6 membered ring substituted with one or more substituents Rc, and
R3, R4 and R5 are independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Ra, O—C1-30-alkyl, O—C1-30-alkyl substituted with one or more substituents Ra, C(O)—C1-30-alkyl, C(O)—C1-30-alkyl substituted with one or more substituents Ra, C5-7-cycloalkyl, C5-7-cycloalkyl substituted with one or more substituents Rb, O—C5-7-cycloalkyl, O—C5-7-cycloalkyl substituted with one or more substituents Rb, C(O)—C5-7-cycloalkyl, C(O)—C5-7-cycloalkyl substituted with one or more substituents Rb, C6-14-aryl, C6-14-aryl substituted with one or more substituents Rb, O—C6-14-aryl, O—C6-14-aryl substituted with one or more substituents Rb, C(O)—C6-14-aryl, C(O)—C6-14-aryl substituted with one or more substituents Rb, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents Rb,
or
R2 and R3 together with the C-atoms to which they are attached form a 5 to 6 membered ring or a 5 to 6 membered ring substituted with one or more substituents Rc, and
R1, R4 and R5 are independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Ra, O—C1-30-alkyl, O—C1-30-alkyl substituted with one or more substituents Ra, C(O)—C1-30-alkyl, C(O)—C1-30-alkyl substituted with one or more substituents Ra, C5-7-cycloalkyl, C5-7-cycloalkyl substituted with one or more substituents Rb, O—C5-7-cycloalkyl, O—C5-7-cycloalkyl substituted with one or more substituents Rb, C(O)—C5-7-cycloalkyl, C(O)—C5-7-cycloalkyl substituted with one or more substituents Rb, C6-14-aryl, C6-14-aryl substituted with one or more substituents Rb, O—C6-14-aryl, O—C6-14-aryl substituted with one or more substituents Rb, C(O)—C6-14-aryl, C(O)—C6-14-aryl substituted with one or more substituents Rb, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents Rb,
or
R3 and R4 together with the C-atoms to which they are attached form a 5 to 6 membered ring or a 5 to 6 membered ring substituted with one or more substituents Rc, and
R1, R2 and R5 are independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Ra, O—C1-30-alkyl, O—C1-30-alkyl substituted with one or more substituents Ra, C(O)—C1-30-alkyl, C(O)—C1-30-alkyl substituted with one or more substituents Ra, C5-7-cycloalkyl, C5-7-cycloalkyl substituted with one or more substituents Rb, O—C5-7-cycloalkyl, O—C5-7-cycloalkyl substituted with one or more substituents Rb, C(O)—C5-7-cycloalkyl, C(O)—C5-7-cycloalkyl substituted with one or more substituents Rb, C6-14-aryl, C6-14-aryl substituted with one or more substituents Rb, O—C6-14-aryl, O—C6-14-aryl substituted with one or more substituents Rb, C(O)—C6-14-aryl, C(O)—C6-14-aryl substituted with one or more substituents Rb, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents Rb,
or
R4 and R5 together with the C-atoms to which they are attached form a 5 to 6 membered ring or a 5 to 6 membered ring substituted with one or more substituents Rc, and
R1, R2 and R3 are independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Ra, O—C1-30-alkyl, O—C1-30-alkyl substituted with one or more substituents Ra, C(O)—C1-30-alkyl, C(O)—C1-30-alkyl substituted with one or more substituents Ra, C5-7-cycloalkyl, C5-7-cycloalkyl substituted with one or more substituents Rb, O—C5-7-cycloalkyl, O—C5-7-cycloalkyl substituted with one or more substituents Rb, C(O)—C5-7-cycloalkyl, C(O)—C5-7-cycloalkyl substituted with one or more substituents Rb, C6-14-aryl, C6-14-aryl substituted with one or more substituents Rb, O—C6-14-aryl, O—C6-14-aryl substituted with one or more substituents Rb, C(O)—C6-14-aryl, C(O)—C6-14-aryl substituted with one or more substituents Rb, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents Rb,
wherein
Ra is at each occurrence selected from the group consisting of O—C1-20-alkyl, C(O)—C1-20-alkyl, C5-6-cycloalkyl, O—C5-6-cycloalkyl, C(O)—C5-6-cycloalkyl, phenyl, O-phenyl, C(O)-phenyl and 5 to 9 membered heteroaryl, and
Rb and Rc are independently and at each occurrence selected from the group consisting of C1-20-alkyl, O—C1-20-alkyl, C(O)—C1-20-alkyl, C5-6-cycloalkyl, O—C5-6-cycloalkyl, C(O)—C5-6-cycloalkyl, phenyl, O-phenyl, C(O)-phenyl and 5 to 9 membered heteroaryl.

### Claim 2 (depends on 1)

The polymers of claim 1, wherein X1 and X2 are O.

### Claim 3 (depends on 1)

The polymers of claim 1, wherein L1 is a linking group which is C1-30-alkylene.

### Claim 4 (depends on 1)

The polymers of any of claim 1, wherein R1, R2, R3, R4 and R5 are independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Ra, O—C1-30-alkyl, O—C1-30-alkyl substituted with one or more substituents Ra, C(O)—C1-30-alkyl, and C(O)—C1-30-alkyl substituted with one or more substituents Ra,
or
R1 and R2 together with the C-atoms to which they are attached form a 5 to 6 membered aromatic ring or a 5 to 6 membered aromatic ring substituted with one or more substituents Rc, and
R3, R4 and R5 are independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Ra, O—C1-30-alkyl, O—C1-30-alkyl substituted with one or more substituents Ra, C(O)—C1-30-alkyl, and C(O)—C1-30-alkyl substituted with one or more substituents Ra,
or
R2 and R3 together with the C-atoms to which they are attached form a 5 to 6 membered aromatic ring or a 5 to 6 membered aromatic ring substituted with one or more substituents Rc, and
R1, R4 and R5 are independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Ra, O—C1-30-alkyl, O—C1-30-alkyl substituted with one or more substituents Ra, C(O)—C1-30-alkyl, and C(O)—C1-30-alkyl substituted with one or more substituents Ra,
or
R3 and R4 together with the C-atoms to which they are attached form a 5 to 6 membered aromatic ring or a 5 to 6 membered aromatic ring substituted with one or more substituents Rc, and
R1, R2 and R5 are independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Ra, O—C1-30-alkyl, O—C1-30-alkyl substituted with one or more substituents Ra, C(O)—C1-30-alkyl, C(O)—C1-30-alkyl substituted with one or more substituents Ra,
or
R4 and R5 together with the C-atoms to which they are attached form a 5 to 6 membered aromatic ring or a 5 to 6 membered aromatic ring substituted with one or more substituents Rc, and
R1, R2 and R3 are independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Ra, O—C1-30-alkyl, O—C1-30-alkyl substituted with one or more substituents Ra, C(O)—C1-30-alkyl, C(O)—C1-30-alkyl substituted with one or more substituents Ra,
wherein
Ra is at each occurrence selected from the group consisting of O—C1-20-alkyl, C(O)—C1-20-alkyl, C5-6-cycloalkyl, O—C5-6-cycloalkyl, C(O)—C5-6-cycloalkyl, phenyl, O-phenyl, and C(O)-phenyl, and
Rc is at each occurrence selected from the group consisting of C1-20-alkyl, O—C1-20-alkyl, C(O)—C1-20-alkyl, C5-6-cycloalkyl, O—C5-6-cycloalkyl, C(O)—C5-6-cycloalkyl, phenyl, O-phenyl, and C(O)-phenyl.

### Claim 5 (depends on 4)

The polymers of claim 4, wherein
R1, R2, R3, R4 and R5 are independently selected from the group consisting of H, C1-10-alkyl and O—C1-10-alkyl,
or
R1 and R2 together with the C-atoms to which they are attached form an aromatic 6-membered aromatic ring, which is
wherein the C-atoms marked with * are the C-atoms to which R1 and R2 are attached, and
R3, R4 and R5 are independently selected from the group consisting of H, C1-10-alkyl and O—C1-10-alkyl,
or
R2 and R3 together with the C-atoms to which they are attached form an aromatic 6-membered aromatic ring, which is
wherein the C-atoms marked with * are the C-atoms to which R2 and R3 are attached, and R1, R4 and R5 are independently selected from the group consisting of H, C1-10-alkyl and O—C1-10-alkyl,
or
R3 and R4 together with the C-atoms to which they are attached form an aromatic 6-membered aromatic ring, which is
wherein the C-atoms marked with * are the C-atoms to which R3 and R4 are attached, and
R1, R2 and R5 are independently selected from the group consisting of H, C1-10-alkyl and O—C1-10-alkyl,
or
R4 and R5 together with the C-atoms to which they are attached form an aromatic 6-membered aromatic ring, which is
wherein the C-atoms marked with * are the C-atoms to which R4 and R5 are attached, and R1, R2, and R3 are independently selected from the group consisting of H, C1-10-alkyl and O—C1-10-alkyl.

### Claim 6 (depends on 1)

The polymers of claim 1 also comprising units of formula (2)
wherein
X3 is independently O or S,
L2 is a covalent bond or a linking group,
R6 is independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Rd, C5-7-cycloalkyl, C5-7-cycloalkyl substituted with one or more substituents Re, C6-14-aryl, C6-14-aryl substituted with one or more substituents Re, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents Re,
wherein
Rd is at each occurrence selected from the group consisting of O—C1-20-alkyl, C(O)—C1-20-alkyl, C5-6-cycloalkyl, O—C5-6-cycloalkyl, C(O)—C5-6-cycloalkyl, phenyl, O-phenyl, C(O)-phenyl and 5 to 9 membered heteroaryl, and
Re is at each occurrence selected from the group consisting of C1-20-alkyl, O—C1-20-alkyl, C(O)—C1-20-alkyl, C5-6-cycloalkyl, O—C5-6-cycloalkyl, C(O)—C5-6-cycloalkyl, phenyl, O-phenyl, C(O)-phenyl and 5 to 9 membered heteroaryl.

### Claim 7 (depends on 6)

The polymers of claim 6, wherein X3 is O.

### Claim 8 (depends on 6)

The polymers of claim 6, wherein L2 is a covalent bond or a linking group, which is phenylene.

### Claim 9 (depends on 6)

The polymers of claim 6, wherein
R6 is independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Rd, C5-7-cycloalkyl, and C5-7-cycloalkyl substituted with one or more substituents Re, wherein
Rd is at each occurrence selected from the group consisting of O—C1-20-alkyl, C(O)—C1-20-alkyl, C5-6-cycloalkyl, O—C5-6-cycloalkyl, C(O)—C5-6-cycloalkyl, phenyl, and O-phenyl, C(O)-phenyl, and
Re is at each occurrence selected from the group consisting of C1-20-alkyl, O—C1-20-alkyl, C(O)—C1-20-alkyl, C5-6-cycloalkyl, O—C5-6-cycloalkyl, C(O)—C5-6-cycloalkyl, phenyl, O-phenyl, and C(O)-phenyl.

### Claim 10 (depends on 9)

The polymers of claim 9, wherein
R6 is independently selected from the group consisting of H, C1-10-alkyl and C5-7-cycloalkyl.

### Claim 11 (depends on 6)

The polymer of claim 6 comprising at least 80 mol % units of formula (1) and (2) based on the mols of all repeating units of the polymer.

### Claim 12 (depends on 1)

A process for the preparation of the polymers of claim 1 comprising units of formula (1)
wherein
X1 and X2, L1 and R1, R2, R3, R4 and R5 are as defined in claim 1, which process comprises the step of polymerizing monomers including the compound of formula (3)
wherein
X1, X2, L1, R1, R2, R3, R4 and R5 are as defined for a compound of formula (1),
in order to yield the polymers of claim 1.

### Claim 13 (depends on 12)

A process of claim 12 for the preparation of the polymers comprising units of formula (1) and (2)
wherein
X1, X2, L1, R1, R2, R3, R4 and R5 are as defined in claim 12, and
X3 is independently O or S,
L2 is a covalent bond or a linking group,
R6 is independently selected from the group consisting of H, C1-30-alkyl, C1-30-alkyl substituted with one or more substituents Rd, C5-7-cycloalkyl, C5-7-cycloalkyl substituted with one or more substituents Re, C6-14-aryl, C6-14-aryl substituted with one or more substituents Re, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents Re,
wherein
Rd is at each occurrence selected from the group consisting of O—C1-20-alkyl, C(O)—C1-20-alkyl, C5-6-cycloalkyl, O—C5-6-cycloalkyl, C(O)—C5-6-cycloalkyl, phenyl, O-phenyl, C(O)-phenyl and 5 to 9 membered heteroaryl, and
Re is at each occurrence selected from the group consisting of C1-20-alkyl, O—C1-20-alkyl, C(O)—C1-20-alkyl, C5-6-cycloalkyl, O—C5-6-cycloalkyl, C(O)—C5-6-cycloalkyl, phenyl, O-phenyl, C(O)-phenyl and 5 to 9 membered heteroaryl,
which process comprises the step of polymerizing monomers including a compound of formula (3) and a compound of formula (4)
wherein
X1, X2, L1, R1, R2, R3, R4 and R5 are as defined for a unit of formula (1), and X3, L2 and R6 are as defined for a unit of formula (2),
in order to yield the polymers comprising units of formula (1) and (2).

### Claim 14 (depends on 1)

A composition comprising at least one polymer of claim 1 and a solvent.

### Claim 15 (depends on 14)

The composition of claim 14, also comprising a crosslinking agent.

### Claim 16 (depends on 1)

An electronic device comprising a layer i) comprising the polymers of claim 1, or ii) formed from the composition comprising the above mentioned polymers and a solvent.

### Claim 17 (depends on 16)

The electronic device of claim 16, which is a field effect transistor.

### Claim 18 (depends on 17)

A process for the preparation of the field effect transistor of claim 17, which comprises the steps of applying the composition on a precursor of the field effect transistor, removing the solvent of the composition and forming a dielectric layer.

### Claim 19 (depends on 1)

Use of the polymers of claim 1 as dielectric material.