Multi(meth)acrylate-functionalized oligomers and methods of preparing and using such oligomers

Patent metadata

Field	Value
Publication number	US-12448476-B2
Application number	US-202017771080-A
Country	US
Kind code	B2
Filing date	Oct 19, 2020
Priority date	Oct 23, 2019
Publication date	Oct 21, 2025
Grant date	Oct 21, 2025

Abstract

A multi(meth)acrylate-functionalized oligomer has a polyurethane backbone, a plurality of (meth)acrylate groups pendant to the polyurethane backbone, and one or more terminal (meth)acrylate groups. The oligomer contains a) at least one multi(meth)acrylate-functionalized segment having at least two pendant (meth)acrylate groups, b) urethane-containing segments, c) at least one end-cap segment having at least one (meth)acrylate group, and, optionally, d) a chain-extending segment (such as a non-polymeric aliphatic segment, polyether-containing segment, polyester-containing segment, polydiene-containing segment, polycarbonate-containing segment or polyorganosiloxane-containing segment). At least one multi(meth)acrylate-functionalized segment is located at a pendant position and at least one (meth)acrylate group is present at one or more terminal positions of the oligomer. The multi(meth)acrylate-functionalized oligomers are useful in compositions which can be cured, including by photocuring, to provide polymeric articles. The oligomer may be a reaction product of a diisocyanate, a diol or triol compound comprising, respectively, two or three (meth)acrylate groups, and an end-capping compound.

First claim

The invention claimed is:

1. A curable composition comprising (i) at least one multi(meth)acrylate-functionalized oligomer having a polyurethane backbone, a plurality of (meth)acrylate functional groups pendant to the polyurethane backbone, and one or more terminal (meth)acrylate functional groups, wherein the oligomer is comprised of a) at least one multi(meth)acrylate-functionalized segment having at least two pendant (meth)acrylate groups, b) urethane-containing segments, c) at least one end-cap segment having at least one (meth)acrylate group, and, optionally, d) at least one chain-extending segment having no (meth)acrylate groups or no more than one (meth)acrylate group, and wherein at least one multi(meth)acrylate-functionalized segment is located at a position along the polyurethane backbone of the multi(meth)acrylate-functionalized oligomer and at least one (meth)acrylate functional group is present at one or more terminal positions of the multi(meth)acrylate-functionalized oligomer; and (ii) at least one of a) a photoinitiator or b) a curable compound, wherein the curable composition contains less than 10% non-reactive solvent based on the total weight of the curable composition, wherein the multi(meth)acrylate-functionalized oligomer has a number average molecular weight of from 500 to 20,000 g/mol, and wherein the oligomer comprises at least one multi(meth)acrylate-functionalized segment corresponding to one of Formula (IIa):
[—CHR 2 —R 3 —CHR 4 —]  (IIa)

wherein R 2 and R 4 are the same or different and correspond to
—CH 2 —O—C(═O)—CR 5 ═CH 2 , wherein R 5 is H or CH 3 , and R 3 is a divalent organo moiety;
or Formula (IIb):

wherein R 2 and R 4 and R 10 are the same or different and correspond to CH 2 —O—C(═O)—CR 5 ═CH 2 , wherein R 5 is H or CH 3 , R 3 is a trivalent organo moiety and the wavy line represents a point of attachment to another segment of the oligomer, in particular to a urethane-containing segment.

2. The curable composition of claim 1 , comprising the at least one chain-extending segment and the at least one chain-extending segment is selected from the group consisting of nonpolymeric aliphatic segments, polyether-containing segments, polyester-containing segments, polydiene-containing segments, polycarbonate-containing segments and polyorganosiloxane-containing segments.

3. The curable composition of claim 1 , wherein the urethane-containing segments correspond to Formula (I):
[—O—C(═O)—NH—R 1 —NH—C(═O)—O—]  (I)

wherein R 1 is a divalent hydrocarbon moiety.

4. The curable composition of claim 1 , wherein the urethane-containing segment comprises a residue of a diisocyanate selected from the group consisting of tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-(isocyanate methyl)cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, halogenated phenyl diisocyanate, methylene diisocyanate, ethylene diisocyanate, butylene diisocyanate, propylene diisocyanate, octadecylene diisocyanate, 1,5-naphthalene diisocyanate, polymethylene polyphenylene diisocyanate, tolylene diisocyanate polymer, diphenylmethane diisocyanate polymer, hexamethylene diisocyanate polymer, 3-phenyl-2-ethylene diisocyanate, cumene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4′-diisocyanate diphenyl ether, 5,6-dimethyl-1,3-phenylene diisocyanate, 4,4′-diisocyanate diphenyl ether, benzidine diisocyanate, 9,10-anthracene diisocyanate, 4,4′-diisocyanate benzyl, 3,3′-dimethyl-4,4′-diisocyanate diphenylmethane, 2,6′-dimethyl-4,4′-diisocyanate diphenyl, 3,3′-dimethoxy-4,4′-diisocyanate diphenyl, 1,4-anthracene diisocyanate, phenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 4,4′-methylene-bis(cyclohexyl isocyanate), and combinations thereof.

5. The curable composition of claim 1 , wherein the oligomer comprises the at least one multi(meth)acrylate-functionalized segment corresponding to Formula (IIa) and R 3 is —R 3′ — or —CH 2 —O—R 3′ —O—CH 2 — and R 3′ is a divalent hydrocarbon moiety.

6. The curable composition of claim 1 , wherein the oligomer comprises the at least one multi(meth)acrylate-functionalized segment corresponding to Formula (IIb) and R 3 is —R 3′ — or R 3 corresponds formula (IIb′)

wherein R 3′ is a trivalent hydrocarbon moiety.

7. The curable composition of claim 1 , wherein the oligomer comprises at least one chain-extending segment which is a polymer-containing segment and the polymer-containing segment corresponds to Formula (III):
[—R 6 —]  (III)

wherein R 6 is a divalent polymeric moiety selected from the group consisting of polyether moieties, polyester moieties, polydiene moieties, polycarbonate moieties and polyorganosiloxane moieties.

8. The curable composition of claim 7 , wherein the divalent polymeric moiety is a divalent polyether moiety selected from the group consisting of divalent polyoxyethylene moieties, divalent polyoxypropylene moieties, divalent polyoxyethylene/oxypropylene moieties, and divalent polyoxytetramethylene moieties.

9. The curable composition of claim 1 , wherein the oligomer comprises at least one chain-extending segment which is a nonpolymeric aliphatic segment and the nonpolymeric aliphatic segment corresponds to Formula (IIIa):
[—R 6a —]  (IIIa)

wherein R 6a is a divalent nonpolymeric aliphatic hydrocarbon moiety optionally additionally comprising one or more heteroatoms.

10. The curable composition of claim 1 , wherein the oligomer comprises at least one end-cap segment having a structure corresponding to Formula (IV):
—O—R 7 —[O—C(═O)—CR 8 ═CH 2 ] n   (IV)

wherein R 7 is an n+1 valent organo moiety, R 8 is H or CH 3 , and n is an integer of 1 to 3.

11. The curable composition of claim 10 , wherein n=1 and R 7 is —CH 2 CH 2 — or —(CH 2 ) 5 C(═O) [O—(CH 2 ) 5 C(═O)] x OCH 2 CH 2 — wherein x is an integer of from 0 to 9.

12. The curable composition of claim 1 , wherein the multi(meth)acrylate-functionalized oligomer comprises at least one chain-extending segment which is a polymer-containing segment and the multi(meth)acrylate-functionalized oligomer has a number average molecular weight of from 3000 to 20,000 g/mol.

13. The curable composition of claim 1 , wherein the oligomer is comprised of one or more units of Formula (A2):
[—O—C(═O)—NH—R 1 —NH—C(═O)—O—CHR 2 —R 3 —CHR 4 —]  (A2)

wherein R 1 is a divalent hydrocarbon moiety, R 2 and R 4 are the same or different and correspond to —CH 2 —O—C(═O)—CR 5 ═CH 2 , wherein R 5 is H or CH 3 and R 3 is a divalent organo moiety.

14. The curable composition of claim 13 , wherein the oligomer is additionally comprised of one or more units of Formula (B):
[O—C(═O)—NH—R 1 —NH—C(═O)—O—R 6 —]  (B)

wherein R 1 is a divalent hydrocarbon moiety and R 6 is a divalent polymeric moiety selected from the group consisting of divalent polyether moieties, divalent polyester moieties, divalent polydiene moieties, divalent polycarbonate moieties and divalent polyorganosiloxane moieties.

Assignees

• Arkema France

Inventors

• Li Ling
• He Yuhong

Classifications

• C08F2/50

  with sensitising agents · CPC title

• C08F290/067 Primary

  Polyurethanes; Polyureas · CPC title

• C08G18/755

  and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate · CPC title

• C08G18/73

  acyclic · CPC title

• C08G18/675 Primary

  Low-molecular-weight compounds · CPC title