Process for producing flame-retardant porous materials based on polyurea

Patent metadata

Field	Value
Publication number	US-10125232-B2
Application number	US-201414225969-A
Country	US
Kind code	B2
Filing date	Mar 26, 2014
Priority date	Mar 18, 2011
Publication date	Nov 13, 2018
Grant date	Nov 13, 2018

Abstract

The invention further relates to the porous materials thus obtainable, and also to the use of the porous materials for thermal insulation.

First claim

The invention claimed is:

1. A process for producing a porous xerogel, comprising:
a) reacting at least one polyfunctional isocyanate (a1) and at least one polyfunctional aromatic amine (a2) in an organic solvent in the presence of water (a3) and in the presence of at least one catalyst (a5); and then
b) removing the organic solvent under subcritical conditions to obtain the porous xerogel,
wherein
(1) a) is carried out in the presence of at least one organic flame retardant (a4), and wherein the at least one organic flame retardant (a4) is soluble in the organic solvent,
(2) the at least one polyfunctional isocyanate (a1) consists of at least one member selected from the group consisting of diphenylmethane 4,4′-diisocyanate, diphenylmethane 2,4′-diisocyanate, diphenylmethane 2,2′-diisocyanate, and oligomeric diphenylmethane diisocyanate,
(3) the at least one polyfunctional aromatic amine (a2) comprises at least one polyfunctional aromatic amine of the general formula I:

wherein
R 1 and R 2 can be identical or different and are selected mutually independently from hydrogen and optionally substituted linear or branched alkyl groups having from 1 to 6 carbon atoms, and
Q 1 to Q 5 and Q 1′ to Q 5′ are identical or different and are selected mutually independently from hydrogen, a primary amino group, and an optionally substituted linear or branched alkyl group having from 1 to 12 carbon atoms,
with the proviso that the at least one polyfunctional aromatic amine of the general formula I comprises at least two primary amino groups, wherein at least one of Q 1 , Q 3 , and Q 5 is a primary amino group, and at least one of Q 1′ , Q 3′ , and Q 5′ is a primary amino group,
(4) the organic solvent comprises acetone, and
(5) the at least one organic flame retardant (a4) comprises at least one member selected from the group consisting of polybrominated compounds and organophosphorus compounds,
wherein in said reacting step a)

the amount of the at least one polyfunctional isocyanate (a1) is from 76 to 97.5% by weight,
the amount of the at least one polyfunctional aromatic amine (a2) is from 2 to 12% by weight, and
the amount of the water (a3) is from 0.5 to 12% by weight,
all of said amounts based on the total combined weight of the at least one polyfunctional isocyanate (a1), the at least one polyfunctional aromatic amine (a2) and the water (a3), which is 100% by weight, and
wherein
the amount of the at least one catalyst (a5) is from 0.2 to 2.5 parts by weight based on a total of 100 parts by weight of (a1), (a2), (a3) and (a4).

2. The process according to claim 1 , wherein Q 2 , Q 4 , Q 2′ , and Q 4′ are selected in such a way that the at least one polyfunctional aromatic amine of the general formula I has at least one linear or branched alkyl group which can bear further functional groups and which has from 1 to 12 carbon atoms in α-position with respect to at least one primary amino group bonded to the aromatic ring.

3. The process according to claim 1 , wherein the at least one organic flame retardant (a4) comprises at least one organophosphoric acid derivative.

4. The process according to claim 1 , wherein the at least one organic flame retardant (a4) comprises at least one organophosphonic acid derivative.

5. The process according to claim 1 , wherein the at least one organic flame retardant (a4) comprises at least one organophosphinic acid derivative.

6. The process according to claim 5 , wherein the at least one organic flame retardant (a4) further comprises at least one polybrominated compound.

7. The process according to claim 1 , wherein the at least one organic flame retardant (a4) comprises at least one compound which comprises a functional group reactive toward isocyanates.

8. The process according to claim 7 , wherein the at least one compound which comprises a functional group reactive toward isocyanates comprises at least 2 functional groups reactive toward isocyanates.

9. The process according to claim 1 , wherein the at least one polyfunctional isocyanate (a1) comprises an oligomeric diphenylmethane diisocyanate.

10. The process according to claim 1 , wherein the at least one polyfunctional isocyanate (a1) comprises an oligomeric diphenylmethane diisocyanate having a functionality of at least 2.4.

11. The process according to claim 1 , wherein the at least one polyfunctional aromatic amine (a2) comprises an oligomeric diaminodiphenylmethane having a functionality of at least 2.4.

12. A porous xerogel obtained by the process according to claim 1 .

13. The porous material according to claim 12 , wherein the volume-average pore diameter of the xerogel is at most 5 micrometers.

14. The process according to claim 1 , wherein the organic solvent consists of acetone.

15. A process for producing a porous xerogel, comprising:
a) reacting at least one polyfunctional isocyanate (a1) and at least one polyfunctional aromatic amine (a2) in an organic solvent in the presence of water (a3) and without the presence of catalyst; and then
b) removing the organic solvent under subcritical conditions to obtain the porous xerogel,
wherein
(1) a) is carried out in the presence of at least one organic flame retardant (a4), and wherein the at least one organic flame retardant (a4) is soluble in the organic solvent,
(2) the at least one polyfunctional isocyanate (a1) consists of at least one member selected from the group consisting of diphenylmethane 4,4′-diisocyanate, diphenylmethane 2,4′-diisocyanate, diphenylmethane 2,2′-diisocyanate, and oligomeric diphenylmethane diisocyanate,
(3) the at least one polyfunctional aromatic amine (a2) comprises at least one polyfunctional aromatic amine of the general formula I:

wherein
R 1 and R 2 can be identical or different and are selected mutually independently from hydrogen optionally substituted and linear or branched alkyl groups having from 1 to 6 carbon atoms, and
Q 1 to Q 5 and Q 1′ to R 5′ are identical or different and are selected mutually independently from hydrogen, a primary amino group, and an optionally substituted linear or branched alkyl group having from 1 to 12 carbon atoms,
with the proviso that the at least one polyfunctional aromatic amine of the general formula I comprises at least two primary amino groups, wherein at least one of Q 1 , Q 3 , and Q 5 is a primary amino group, and at least one of Q 1′ , Q 3′ , and Q 5′ is a primary amino group,
(4) the organic solvent comprises acetone, and
(5) the at least one organic flame retardant (a4) comprises at least one member selected from the group consisting of polybrominated compounds and organophosphorus compounds,
wherein in said reacting step a)

the amount of the at least one polyfunctional isocyanate (a1) is from 68 to 90% by weight,
the amount of the at least one polyfunctional aromatic amine (a2) is from 2 to 12% by weight, and
the amount of the water (a3) is from 8 to 20% by weight,
all of said amounts based on the total combined weight of the at least one polyfunctional isocyanate (a1), the at least one polyfunctional aromatic amine (a2) and the water (a3), which is 100% by weight.

16. The process according to claim 15 , wherein Q 2 , Q 4 , Q 2′ , and Q 4′ are

Assignees

• Basf Se

Inventors

• Fricke Marc
• Elbing Mark

Classifications

• C08J2375/02

  Polyureas · CPC title

• C08G18/3819

  having nitrogen · CPC title

• C08G2101/0091

  Chemistry & Metallurgy · mapped topic

• C08J9/28 Primary

  by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum · CPC title

• C08G18/381

  having bromine atoms · CPC title