Curable compositions and membranes

Patent metadata

Field	Value
Publication number	US-9556316-B2
Application number	US-201414897358-A
Country	US
Kind code	B2
Filing date	May 30, 2014
Priority date	Jun 11, 2013
Publication date	Jan 31, 2017
Grant date	Jan 31, 2017

Abstract

A composition comprising: a) 5 to 65 wt % of curable compound comprising one ethylenically unsaturated group and at least one anionic group; b) 2.5 to 70 wt % of crosslinking agent comprising at least two acrylic groups; c) a tertiary amine; and d) 0 to 45 wt % of inert solvent; wherein the molar ratio of component c) to a) is at least 0.7. Also described are a process for making composite membranes and the resultant membranes.

First claim

The invention claimed is:

1. A curable composition comprising:
a) 5 to 65 wt % of curable compound comprising one ethylenically unsaturated group and at least one anionic group;
b) 2.5 to 70 wt % of crosslinking agent comprising at least two acrylic groups;
c) a tertiary amine; and
d) 0 to 45 wt % of inert solvent;

wherein the molar ratio of component c) to a) is at least 0.7.

2. The composition according to claim 1 wherein the molar ratio of component c) to a) is at least 0.9.

3. The composition according to claim 1 wherein the crosslinking agent has a melting point below 80° C., when measured at atmospheric pressure.

4. The composition according to claim 1 wherein the anionic group is selected from sulpho, carboxy and phosphato groups.

5. The composition according to claim 1 wherein the anionic group is a sulpho group.

6. The composition according to claim 1 which comprises at least 5 wt % and less than 70 wt % of the said crosslinking agent.

7. The composition according to claim 1 wherein the said crosslinking agent has a solubility in water of less than 0.03 mol/l, when measured at 25° C.

8. The composition according to claim 1 wherein the weight ratio of component b) to component a) is greater than 0.3.

9. The composition according to claim 1 which further comprises 0.05 to 10 wt % of photoinitiator.

10. The composition according to claim 1 wherein the said crosslinking agent comprises at least two groups selected from acrylamide groups.

11. The composition according to claim 1 wherein the said tertiary amine has a melting point below 50° C.

12. The composition according to claim 1 wherein the said tertiary amine is selected from tri(C 1-12 -alkyl)amines and heterocyclic N—(C 1-12 -alkyl) amines.

13. The composition according to claim 1 wherein the said curable compound has a MW of less than 1000 Dalton and/or said crosslinking agent has a MW of less than 1000 Dalton.

14. The composition according to claim 1 wherein the said tertiary amine has a MW of less than 400 Dalton.

15. The composition according to claim 1 which has a viscosity of below 12 Pa.s when measured at 50° C.

16. A process for preparing a membrane comprising the following steps:
a) applying a curable composition to a support; and
b) curing the composition to form a membrane;

wherein the composition is as defined in claim 1 .

17. The process according to claim 16 wherein the curing is performed by a process comprising irradiating the composition for less than 30 seconds.

18. A cation exchange membrane including a cured composition comprising, prior to curing,
a) 5 to 65 wt % of curable compound comprising one ethylenically unsaturated group and at least one anionic group;
b) 2.5 to 70 wt % of crosslinking agent comprising at least two acrylic groups;
c) a tertiary amine; and
d) 0 to 45 wt % of inert solvent;

wherein the molar ratio of component c) to a) is at least 0.7.

19. An electrodialysis or reverse electrodialysis unit, a flow through capacitor device, an electrodeionization module, a continuous electrodeionization module, a fuel cell, a diffusion dialysis apparatus, a membrane distillation module or a membrane electrode assembly comprising one or more membranes including a cured composition comprising, prior to curing,
a) 5 to 65 wt % of curable compound comprising one ethylenically unsaturated group and at least one anionic group;
b) 2.5 to 70 wt % of crosslinking agent comprising at least two acrylic groups;
c) a tertiary amine; and
d) 0 to 45 wt % of inert solvent;

wherein the molar ratio of component c) to a) is at least 0.7.

20. The composition according to claim 1 wherein:
(a) the crosslinking agent has (i) a melting point below 80° C., when measured at atmospheric pressure; and (ii) a solubility in water of less than 0.03 mol/l, when measured at 25° C.;
(b) the composition comprises at least 5 wt % and less than 70 wt % of the said crosslinking agent;
(c) the composition further comprises 0.05 to 10 wt % of photoinitiator;
(d) the weight ratio of component b) to component a) is greater than 0.3; and
(e) the anionic group is a sulpho group.

21. The composition according to claim 1 wherein:
(a) the said tertiary amine has a melting point below 50° C.;
(b) the said tertiary amine is selected from tri(C 1-12 -alkyl)amines and heterocyclic N—(C 1-12 -alkyl) amines; and
(c) the said curable compound has a MW of less than 1000 Dalton;
(d) the said crosslinking agent has a MW of less than 1000 Dalton; and
(e) the said tertiary amine has a MW of less than 400 Dalton.

22. The composition according to claim 1 wherein:
(a) the crosslinking agent has a melting point below 80° C., when measured at atmospheric pressure;
(b) the anionic group is a sulpho group;
(c) the composition comprises at least 5 wt % and less than 70 wt % of the said crosslinking agent;
(d) the said crosslinking agent has a solubility in water of less than 0.03 mol/l, when measured at 25° C., and has a MW of less than 1000 Dalton;
(e) the weight ratio of component b) to component a) is greater than 0.3; and
(f) the composition comprises 0.05 to 10 wt % of photoinitiator;
(g) the said tertiary amine is selected from tri(C 1-12 -alkyl)amines and heterocyclic N—(C 1-12 -alkyl) amines and has a melting point below 50° C. and a MW of less than 400 Dalton; and
(h) the said curable compound has a MW of less than 1000 Dalton.

23. The process according to claim 16 wherein:
(a) the composition comprises a crosslinking agent having a melting point below 80° C., when measured at atmospheric pressure;
(b) the anionic group is a sulpho group;
(c) the composition comprises at least 5 wt % and less than 70 wt % of the said crosslinking agent;
(d) the said crosslinking agent has a solubility in water of less than 0.03 mol/l, when measured at 25° C. and has a MW of less than 1000 Dalton;
(e) the weight ratio of component b) to component a) is greater than 0.3;
(f) the composition comprises 0.05 to 10 wt % of photoinitiator;
(g) the said tertiary amine is selected from tri(C 1-12 -alkyl)amines and heterocyclic N—(C 1-12 -alkyl) amines and has a melting point below 50° C. and a MW of less than 400 Dalton; and
(h) the said curable compound has a MW of less than 1000 Dalton.

24. A cation exchange membrane including a cured composition comprising, prior to curing,
a) 5 to 65 wt % of curable compound comprising one ethylenically unsaturated group and at least one anionic group;
b) 2.5 to 70 wt % of crosslinking agent comprising at least two acrylic groups;
c) a tertiary amine; and
d) 0 to 45 wt % of inert solvent;

wherein the molar ratio of component c) to a) is at least 0.7, wherein
(e) the composition comprises a crosslinking agent having a melting point below 80° C., when measured at atmospheric pressure;
(f) the anionic group is a sulpho group;
(g) the composition comprises at least 5 wt % and less than 70 wt % of the said crosslinking agent;
(h) the said crosslinking agent has a solubility in water of less than 0.03 mol/l, when measured at 25° C. and has a MW of less than 1000 Dalton;
(i) the weight ratio of component b) to component a) is greater than 0.3;
(j) the composition comprises 0.05 to 10 wt % of photoinitiator;
(k) the said tertiary amine is selected from tri(C 1-12 -alkyl)amines and heterocyclic N—(C 1-12 -alkyl) amines and has a melting point below 50° C. and a MW o

Assignees

• Fujifilm Mfg Europe Bv

Inventors

• Antheunis Harro

Classifications

• C08F220/585

  and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS] · CPC title

• B01D69/02

  characterised by their properties · CPC title

• C02F1/4695

  electrodeionisation · CPC title

• C08J2333/24

  Homopolymers or copolymers of amides or imides · CPC title

• C02F1/447

  by membrane distillation (distillation and evaporation without the use of membranes C02F1/04) · CPC title