Curable composition and cured composition prepared therefrom

Patent metadata

Field	Value
Publication number	US-11919989-B2
Application number	US-202117165228-A
Country	US
Kind code	B2
Filing date	Feb 2, 2021
Priority date	Feb 28, 2020
Publication date	Mar 5, 2024
Grant date	Mar 5, 2024

Abstract

A curable composition includes a functionalized phenylene ether oligomer, a reactive diluent, and a photoinitiator. The curable composition can be cured to provide a cured composition. Articles comprising the cured composition and methods for the manufacture of the cured composition are also described. The curable composition can be particularly useful for providing three-dimensional, additively-manufactured articles.

First claim

What is claimed is:

1. A curable composition comprising:
20 to 40 weight percent of a functionalized phenylene ether oligomer having an intrinsic viscosity of 0.03 to 0.13 deciliter per gram, measured at 25° C. in chloroform using an Ubbelohde viscometer;
60 to 80 weight percent of a reactive diluent, wherein the reactive diluent is a (meth)acrylate-containing monomer; and
a photoinitiator;
wherein weight percent is based on the total weight of the phenylene ether oligomer and the reactive diluent; and
wherein the functionalized phenylene ether oligomer has the structure

wherein
Q 1 and Q 2 each independently comprise halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, and C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
Q 3 and Q 4 each independently comprise hydrogen, halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, and C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
Z is independently at each occurrence a (meth)acrylate group, a vinyl benzene group, an allyl group, or a maleimide group; and
L is of the structure

wherein
R 3 , R 4 , R 5 , and R 6 each independently comprise hydrogen, halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, and C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
z is 0 or 1; and
Y has a structure

wherein
R 7 is independently at each occurrence hydrogen and C 1-12 hydrocarbyl;
R 8 and R 9 are independently at each occurrence hydrogen, C 1-12 hydrocarbyl, and C 1-6 hydrocarbylene wherein R 8 and R 9 collectively form a C 4-12 alkylene group;
R 10 is independently at each occurrence a C 1-6 hydrocarbylene group;
R 11 is independently at each occurrence a hydrogen, C 1-12 hydrocarbyl or C 1-12 halohydrocarbyl; and
n is 5 to 50; and

x and y are independently 0 to 30, provided that the sum of x and y is at least 2.

2. The curable composition of claim 1 , wherein
Q 1 and Q 2 each independently comprise unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl;
Q 3 and Q 4 each independently comprise hydrogen;
Z is a (meth)acrylate group; and
L is of the structure

wherein
R 3 , R 4 , R 5 , and R 6 each independently comprise hydrogen or unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl; and
z is 1.

3. The curable composition of claim 1 , wherein L is

wherein n is 5 to 45.

4. The curable composition of claim 1 , wherein the reactive diluent comprises
a C 1-24 alkyl (meth)acrylate monomer,
a di(meth)acrylate) comprising dipropylene glycol diacrylate, hexanediol diacrylate, tripropylene glycol diacrylate, isobornyl acrylate, isobornyl methacrylate, 4-t-butylcyclohexyl acrylate, or a combination thereof,
or a combination thereof.

5. A curable composition comprising:
5 to 30 weight percent of a functionalized phenylene ether oligomer having an intrinsic viscosity of 0.03 to 0.13 deciliter per gram, measured at 25° C. in chloroform using an Ubbelohde viscometer;
17 to 37 weight percent of a reactive diluent, wherein the reactive diluent is a (meth)acrylate-containing monomer;
57 to 73 weight percent of a photocurable resin; and
a photoinitiator;
wherein weight percent is based on the total weight of the phenylene ether oligomer, the reactive diluent and the photocurable resin; and
wherein the functionalized phenylene ether oligomer has the structure

wherein
Q 1 and Q 2 each independently comprise halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, and C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
Q 3 and Q 4 each independently comprise hydrogen, halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, and C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
Z is independently at each occurrence a (meth)acrylate group, a vinyl benzene group, an allyl group, or a maleimide group; and
L is of the structure

wherein
R 3 , R 4 , R 5 , and R 6 each independently comprise hydrogen, halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, and C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
z is 0 or 1; and
Y has a structure

wherein
R 7 is independently at each occurrence hydrogen and C 1-12 hydrocarbyl;
R 8 and R 9 are independently at each occurrence hydrogen, C 1-12 hydrocarbyl, and C 1-6 hydrocarbylene wherein R 8 and R 9 collectively form a C 4-12 alkylene group;
R 10 is independently at each occurrence a C 1-6 hydrocarbylene group;
R 11 is independently at each occurrence a hydrogen, C 1-12 hydrocarbyl or C 1-12 halohydrocarbyl; and
n is 5 to 50; and

x and y are independently 0 to 30, provided that the sum of x and y is at least 2.

6. The curable composition of claim 1 , wherein the photoinitiator is a free radical photoinitiator.

7. The curable composition of claim 1 , further comprising a thermal initiator.

8. The curable composition of claim 1 , further comprising:
an auxiliary resin comprising an epoxy resin, a cyanate ester resin, a maleimide resin, a benzoxazine resin, a vinylbenzyl ether resin, an arylcyclobutene resin, a perfluorovinyl ether resin, oligomers or polymers with curable vinyl functionality, or a combination thereof; and
a curing promoter comprising aliphatic and cycloaliphatic amines and amine-functional adducts with epoxy resins, Mannich bases, aromatic amines, polyamides, amidoamines, phenalkamines, dicyandiamide, polycarboxylic acid-functional polyesters, carboxylic acid anhydrides, amine-formaldehyde resins, phenol-formaldehyde resins, polysulfides, polymercaptans, or a combination thereof.

9. The curable composition of claim 1 , comprising
1 to 10 parts per hundred of the photoinitiator, based on the total weight of the phenylene ether oligomer and the reactive diluent.

10. The curable composition of claim 5 , comprising
1 to 10 parts per hundred of the photoinitiator, based on the total weight of the phenylene ether oligomer, the reactive diluent and the photocurable resin.

11. A cured composition comprising a cured product of the curable composition of claim 1 , optionally wherein the cured composition has a glass transition temperature of greater th

Assignees

• Shpp Global Tech Bv

Inventors

• Tarkin-Tas Eylem
• Rice Brian Jason

Classifications

• C08F283/08 Primary

  on to polyphenylene oxides · CPC title

• C08F283/06 Primary

  on to polyethers, polyoxymethylenes or polyacetals {(C08F283/004 takes precedence)} · CPC title

• C08G65/485 Primary

  Polyphenylene oxides · CPC title

• C08F2/48

  by ultraviolet or visible light · CPC title

• C08L51/08

  grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds · CPC title