# US 7,612,122 B2 · Piperazino based photoinitiators

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- Number: US 7,612,122 B2
- Document ID: US7612122B2
- Status: Granted
- Kind: B2
- Application number: 11/718,952
- Filed: 2005-11-09
- Published: 2008-02-21
- Granted: 2009-11-03
- Earliest claimed: 2005-11-09
- Assignees: Sun Chemical Corporation
- Inventors: Shaun Lawrence Herlihy; Brian Rowatt; Robert Stephen Davidson
- Web page: https://patentgrep.com/patent/US7612122B2

## CPC

- C07D 295/135: with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
- C07D 295/112: with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
- C07D 295/15: to an acyclic saturated chain
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

Compounds of formula (I): [where: the substituents R1 are individually selected from C1-C10 alkyl groups and optionally substituted benzyl groups; the substituents R2 are individually selected from alkyl groups or, together with the nitrogen atom to which they are attached, represent a nitrogen-containing heterocyclic group; Z is selected from C6-C10 arylene groups and groups of formula —(CHR3)n—, where R3 is hydrogen, hydroxy or a C1-C4 alkyl group, and n is 0 to 6; Y is carbonyl or —CH2—; Q is a residue of a mono- or poly-hydroxy compound; and x is 1 to 6; and esters thereof] are useful as multi-functional photoinitiators for use in coating compositions to be cured by radiant energy.

## Claims

### Claim 1

A compound of formula (I):
where:
the substituents R1 are individually selected from C1-C10 alkyl groups and optionally substituted benzyl groups;
the substituents R2 are individually selected from alkyl groups or, together with the nitrogen atom to which they are attached, represent a nitrogen-containing heterocyclic group;
Z is selected from C6-C10 arylene groups and groups of formula —(CHR3)n—,
where R3 is a hydrogen atom, a hydroxy group or a C1-C4 alkyl group, and n is a number from 0 to 6;
Y is selected from carbonyl groups and the —CH2— group;
Q is selected from the residues of mono- or poly-hydroxy compounds having from 1 to 6 hydroxy groups; and
x is a number from 1 to 6;
and esters thereof.

### Claim 2 (depends on 1)

A compound according to claim 1, where at least one of the R1 substituents is a C1-C6 alkyl group.

### Claim 3 (depends on 2)

A compound according to claim 2, where at least one of the R1 substituents is a methyl or ethyl group.

### Claim 4 (depends on 2)

A compound according to claim 2, where at least one of the R1 substituents is a benzyl group.

### Claim 5 (depends on 1)

A compound according to claim 1, where the substituents R2 are individually selected from C1-C6 alkyl groups.

### Claim 6 (depends on 5)

A compound according to claim 5, where the R2 substituent represents a methyl or ethyl group.

### Claim 7 (depends on 1)

A compound according to claim 1, where the R2 substituents, together with the nitrogen atom to which they are attached, represent a 5- to 7-membered nitrogen-containing heterocyclic ring.

### Claim 8 (depends on 7)

A compound according to claim 7, where nitrogen-containing said heterocyclic ring is selected from morpholino, piperidino, 1-pyrrolidinyl, 3-alkyl-1-imidazolidinyl, 2-alkyl-1-pyrazolidinyl, 4-alkyl-1-piperazinyl, 1-pyrrolyl, 1-imidazolyl and 1-pyridyl groups.

### Claim 9 (depends on 8)

A compound according to claim 8, where said heterocyclic ring is selected from piperidino, morpholino and 4-methyl-1-piperazinyl groups.

### Claim 10 (depends on 1)

A compound according to claim 1, where Z is a group of formula —(CHR3)n—, and n is 1 or 2.

### Claim 11 (depends on 1)

A compound according to claim 1, where Z is a group of formula —(CHR3)n—, and n is 2.

### Claim 12 (depends on 10)

A compound according to claim 10, where R3 is selected from hydrogen atoms, methyl groups and ethyl groups.

### Claim 13 (depends on 12)

A compound according to claim 12, where R3 is a hydrogen atom.

### Claim 14 (depends on 1)

A compound according to claim 1, where Z is a group of formula —(CHR3)n—, n is a number from 2 to 6 and one R3 represents a hydrogen atom or a C1-C4 alkyl group, and the other or others of R3 represent hydrogen atoms.

### Claim 15 (depends on 1)

A compound according to claim 1, where Z is a phenylene group.

### Claim 16 (depends on 1)

A compound according to claim 1, wherein Q is a group of formula -Ax-Q′, where:
A is selected from groups of formula —[O(CHR4CHR5)a]y—, —[O(CH2)bCO]y— and —[O(CH2)bCO](y-1)—[O(CHR4CHR5)a]—
where:
R4 and R5 are individually selected from hydrogen atoms and C1-C4 alkyl groups;
a is a number from 1 to 2;
b is a number from 4 to 5; and
y is a number from 1 to 10;
x is a number from 1 to 6; and
Q′ is selected from residues of a mono- or poly-hydroxy compounds having from 1 to 6 hydroxy groups.

### Claim 17 (depends on 16)

A compound according to claim 16, where y is a number from 3 to 10.

### Claim 18 (depends on 17)

A compound according to claim 17, where A is a group of formula —[O(CHR4CHR5)a]y— where a is an integer from 1 to 2, and y is a number from 1 to 10.

### Claim 19 (depends on 17)

A compound according to claim 17, where A is selected from groups of formula —[OCH2CH2]y—, —[OCH2CH2CH2CH2]y— and —[OCH(CH3)CH2]y—, where y is a number from 1 to 10.

### Claim 20 (depends on 17)

A compound according to claim 17, where A is a group of formula —[O(CH2)bCO]y—, where b is a number from 4 to 5 and y is a number from 1 to 10.

### Claim 21 (depends on 17)

A compound according to claim 17, where A is a group of formula —[O(CH2)bCO](y-1)—[O(CHR4CHR5)a]—, where a is a number from 1 to 2, b is a number from 4 to 5 and y is a number from 1 to 10.

### Claim 22 (depends on 16)

A compound according to claim 16, where x is 2.

### Claim 23 (depends on 16)

A compound according to claim 16, where y is a number from 1 to 6.

### Claim 24 (depends on 16)

A compound according to claim 16, where the residue -Ax-Q′ has a molecular weight no greater than 2000.

### Claim 25 (depends on 24)

A compound according to claim 24, where the residue -Ax-Q′ has a molecular weight no greater than 1200.

### Claim 26 (depends on 25)

A compound according to claim 25, where the residue -Ax-Q′ has a molecular weight no greater than 1000.

### Claim 27 (depends on 26)

A compound according to claim 26, where the residue -Ax-Q′ has a molecular weight no greater than 800.

### Claim 28 (depends on 16)

A compound according to claim 16, where Q′ is a residue of a poly(C2-C6 alkylene)glycol.

### Claim 29 (depends on 16)

A compound according to claim 16, where Q′ is a residue of ethylene glycol, propylene glycol, butylene glycol, glycerol, 2,2-propanediol, polyethylene glycol, polypropylene glycol, polybutylene glycol, trimethylolpropane, di-trimethylolpropane, pentaerythritol or di-pentaerythritol.

### Claim 30 (depends on 1)

A compound according to claim 1, where x is 1.

### Claim 31 (depends on 30)

A compound according to claim 30, where Q is the residue of a compound of formula R6—OH, where R6 is selected from C1-C10 alkyl groups and optionally substituted benzyl groups.

### Claim 32 (depends on 30)

A compound according to claim 30, where Q is a C1-C6 alkoxy group or a phenoxy group.

### Claim 33 (depends on 31)

A compound according to claim 31, where Z is a phenylene group.

### Claim 34 (depends on 1)

A compound according to claim 1, where Q is a residue of a poly(C2-C6 alkylene)glycol.

### Claim 35 (depends on 34)

A compound according to claim 34, where Q is a residue of ethylene glycol, propylene glycol, butylene glycol, glycerol, 2,2-propanediol, polyethylene glycol, polypropylene glycol, polybutylene glycol, trimethylolpropane, di-trimethylolpropane, pentaerythritol or di-pentaerythritol.

### Claim 36 (depends on 1)

An energy-curable composition comprising: (a) a polymerisable monomer, prepolymer or oligomer; and (b) a compound as claimed in claim 1 as photoinitiator.

### Claim 37 (depends on 36)

A process for preparing an energy cured polymeric composition comprising a step of exposing a composition according to claim 36 to radiant energy.

### Claim 38 (depends on 37)

A process according to claim 37, where the radiant energy is ultraviolet radiation.