Organic amine salt foamer

Patent metadata

Field	Value
Publication number	US-11634552-B2
Application number	US-201716753064-A
Country	US
Kind code	B2
Filing date	Dec 5, 2017
Priority date	Oct 19, 2017
Publication date	Apr 25, 2023
Grant date	Apr 25, 2023

Abstract

Disclosed is an organic amine salt foaming agent, that is, a composite polyurethane foaming agent, comprising: 1) hexafluorobutene; and 2) an alkanolamine salt mixture (MAA), the alkanolamine salt mixture (MAA) contains an organic amine salt compound having the following general formula (I): An−[Bm+]p (I); wherein An− is one or two or three selected from the following anions: (b) carbonate: CO32−; (c) formate: HCOO−; (d) bicarbonate: HO—COO−. A polyurethane foaming method using carbon dioxide and an organic amine in combination is also disclosed, in which carbon dioxide is added to a polyurethane composition for foaming. A method for preparing an alkanolamine carbonate salt with low water content from ammonium carbonate and an epoxide is additionally disclosed, in which a liquid alkanolamine salt mixture is used as a dispersion medium or as a solvent for reaction raw material.

First claim

The invention claimed is:

1. A composite foaming agent, comprising:
1) hexafluorobutene; and
2) an alkanolamine salt mixture (MAA),
wherein the alkanolamine salt mixture (MAA) comprises organic alkanolamine salt compounds, and the organic alkanolamine salt compounds is an organic alkanolamine salt compound having following general formula (I):
A n− [B m+ ] p   (I)

in the above formula, A n− is CO 3 2− ; wherein n=2, m=1, and p=2;
B m+ comprises: one or more organic amine (B) cation(s) having one — + NR 3 R 4 H group;
wherein, R 3 and R 4 is independently chosen from: H, or R;
provided that: the compound of the general formula (I) has at least one R group(s) linked to N atom, and the alkanolamine salt mixture (MAA) contain(s) 50-99 wt % of monoalkanolamine salt or dialkanolamine salt, based on total weight of the alkanolamine salt mixture (MAA);
wherein the R group is H[OCH(R 1a )CH(R 2a )]—;
wherein R 1a , R 2a each independently is selected from the following groups: H, C 1 -C 7 aliphatic hydrocarbyl group optionally substituted by hydroxyl or amino or halogen, and C 3 -C 7 cycloaliphatic hydrocarbyl group optionally substituted by hydroxyl or amino or halogen;
wherein water content in the alkanolamine salt mixture (MAA) is from more than 0 wt % to 40 wt %, and said one or more organic amine cation(s) (B) is/are organic amine cation(s) having 2-20 carbon atoms;
wherein the weight ratio of hexafluorobutene to alkanolamine salt mixture (MAA) in the composite foaming agent is 0.4-5:1.

2. The composite foaming agent according to claim 1 , wherein monoalkanolamine is monoethanolamine and/or monopropanolamine; Dialkanolamine is diethanolamine, ethanol propanol amine and/or dipropanolamine.

3. The composite foaming agent according to claim 1 , wherein:
H[OCH(R 1a )CH(R 2a )]— is H(OCH 2 CH 2 )—, H(OCH 2 CH(CH 3 ))—, H(OCH(CH 3 )CH 2 )—, and
the weight ratio of hexafluorobutene to alkanolamine salt mixture (MAA) in the composite foaming agent is 0.5-4:1.

4. The composite foaming agent according to claim 1 , wherein the weight ratio of hexafluorobutene to alkanolamine salt mixture (MAA) in the composite foaming agent is 0.7-3:1.

5. The composite foaming agent according to claim 1 , wherein the weight ratio of hexafluorobutene to alkanolamine salt mixture (MAA) in the composite foaming agent is 0.7-2:1.

6. The composite foaming agent according to claim 1 , wherein the weight ratio of hexafluorobutene to alkanolamine salt mixture (MAA) in the composite foaming agent is 0.7-1.3:1.

7. The composite foaming agent according to claim 1 , wherein the water content in the alkanolamine salt mixture (MAA) is 5-35 wt %, and the alkanolamine salt mixture (MAA) contains 60-98 wt % of monoalkanolamine salt or dialkanolamine salt; and
the pH of the alkanolamine salt mixture (MAA) is 7.5-10.

8. The composite foaming agent according to claim 1 , wherein the water content in the alkanolamine salt mixture (MAA) is 10-30 wt %, and the alkanolamine salt mixture (MAA) contains 70-97 wt % of monoalkanolamine salt or dialkanolamine salt; and
the pH of the alkanolamine salt mixture (MAA) is 7.8-9.5.

9. The composite foaming agent according to claim 1 , wherein the water content in the alkanolamine salt mixture (MAA) is 15-25 wt %, and the alkanolamine salt mixture (MAA) contains 80-96 wt % of monoalkanolamine salt or dialkanolamine salt; and
the pH of the alkanolamine salt mixture (MAA) is 8-9.

10. The composite foaming agent according to claim 1 , wherein: in the alkanolamine salt mixture (MAA), the total content of the compound of the general formula (I) and water is 70-100%, based on the total weight of alkanolamine salt mixture (MAA).

11. The composite foaming agent according to claim 10 , wherein: in the alkanolamine salt mixture (MAA), the total content of the compound of the general formula (I) and water is 80-99.5%, based on the total weight of alkanolamine salt mixture (MAA).

12. The composite foaming agent according to claim 10 , wherein: in the alkanolamine salt mixture (MAA), the total content of the compound of the general formula (I) and water is 85-99.0%, based on the total weight of alkanolamine salt mixture (MAA).

13. The composite foaming agent according to claim 1 , wherein the alkanolamine salt mixture (MAA) is formed by the reaction of a first raw material and a second raw material in the presence of water; wherein the first raw material is one or more selected from the following compounds:
(NH 4 ) 2 CO 3 , or organic amine compound (M) carbonate;
wherein the organic amine compound (M) is an organic amine compound selected from following compounds:
C 1 hydrocarbyl amines;
Di-(C 1 hydrocarbyl) amines;
C 2 -C 14 hydrocarbylene diamines;
C 4 -C 16 polyalkylene polyamines;
C 3 -C 18 organic triamines having three primary amine groups or C 5 -C 18 organic tetramines having four primary amine groups; or
C 2 -C 10 alkanolamines;
the second material is one or more selected from following epoxides:

wherein R 1a , R 2a each independently is selected from the following groups: H, C 1 -C 7 aliphatic hydrocarbyl group optionally substituted by hydroxyl or amino or halogen, or C 3 -C 7 cycloaliphatic hydrocarbyl group optionally substituted by hydroxyl or amino or halogen.

14. The composite foaming agent according to claim 13 , wherein the amount of water is 70-200 wt %, based on the weight of the first raw material.

15. The composite foaming agent according to claim 1 , wherein R 1a , R 2a each independently is selected from the following groups: H, methyl, chloromethyl, bromomethyl, ethyl, or cyclohexyl.

16. The composite foaming agent according to claim 1 , wherein the mass content of alkali metals and alkaline earth metals in the foaming agent is 0-200 ppm.

Assignees

• Univ Shandong Technology

Inventors

• Bi Gehua
• Bi Yusui

Classifications

• C08J9/08 Primary

  developing carbon dioxide · CPC title

• C08J2375/08

  from polyethers · CPC title

• C08J9/10

  developing nitrogen {, the blowing agent being a compound containing a nitrogen-to-nitrogen bond} · CPC title

• C08J2203/06

  CO2, N2 or noble gases · CPC title

• C08J2203/162

  Halogenated unsaturated hydrocarbons, e.g. H2C=CF2 · CPC title