Conjugated diene phosphinate compounds, preparation method and use thereof
This invention relates to conjugated diene phosphinate compounds for making halogen free phosphinate-containing flame retardants, inimer and metal extractants, method for preparing said compounds from unsaturated ketones or aldehydes, and the 5 use thereof. The compounds of the present invention having the following formula (III), wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 represent, independently, hydrogen, alkyl, aryl, alkaryl, aralkyl, cycloalkyl, heterocycloalkyl, or alkenyl groups; R 7 represents hydrogen, alkyl, aryl, alkaryl, aralkyl, cycloalkyl, alkenyl groups, or metals selected from the group consisting of Na, Li, Ca.
1. A conjugated diene phosphinate compound having the formula III:
wherein,
R 1 , R 2 , and R 4 each represent, independently, hydrogen, alkyl, aryl, alkaryl, aralkyl, cycloalkyl, heterocycloalkyl, or alkenyl;
R 3 and R 5 each represent methyl;
R 6 and R 7 each represent hydrogen;
and optionally wherein any two of R 1 , R 2 , R 3 , R 4 , and R 5 form a 3-8 membered cycloalkyl or heterocycloalkyl ring.
2. The conjugated diene phosphinate compound according to claim 1 , wherein the said alkyl and alkenyl each comprise 1˜24 carbon atoms, said aryl comprises 6˜24 carbon atoms, said alkaryl and aralkyl each comprise 7˜24 carbon atoms, and said cycloalkyl or heterocycloalkyl ring comprises 3˜24 carbon atoms.
3. The conjugated diene phosphinate compound according to claim 1 , wherein the said alkyl and alkenyl each comprise 1˜18 carbon atoms, said aryl comprises 6˜18 carbon atoms, said alkaryl and aralkyl each comprise 7˜18 carbon atoms, and said cycloalkyl or heterocycloalkyl ring comprises 3˜18 carbon atoms.
4. The conjugated diene phosphinate compound according to claim 1 , wherein at least one of R 1 and R 2 is hydrogen.
5. The conjugated diene phosphinate compound according to claim 1 , wherein any two of R 1 , R 2 , R 3 , R 4 , and R 5 form a 3-8 membered cycloalkyl or heterocycloalkyl ring.
6. The conjugated diene phosphinate compound according to claim 1 , wherein R 1 , R 2 and R 4 each represent hydrogen.
7. A method for preparing a conjugated diene phosphinate compound from an α,β- or β,γ-unsaturated ketone or aldehyde, which comprises reacting an α,β- or β,γ-unsaturated ketone or aldehyde having the formula I or II,
with a phosphinic acid having the formula,
to obtain a conjugated diene phosphinate compound having the formula III,
wherein,
R 1 , R 2 , and R 4 each represent, independently, hydrogen, alkyl, aryl, alkaryl, aralkyl, cycloalkyl, heterocycloalkyl, or alkenyl;
R 3 and R 5 each represent methyl;
R 6 and R 7 each represent hydrogen;
and optionally wherein any two of R 1 , R 2 , R 3 , R 4 , and R 5 form a 3-8 membered cycloalkyl or heterocycloalkyl ring.
8. The method according to claim 7 , wherein the said alkyl and alkenyl each comprise 1˜24 carbon atoms, said aryl comprises 6˜24 carbon atoms, said alkaryl and aralkyl each comprise 7˜24 carbon atoms, and said cycloalkyl or heterocycloalkyl ring comprises 3˜24 carbon atoms.
9. The method according to claim 7 , wherein the said alkyl and alkenyl each comprise 1˜18 carbon atoms, said aryl comprises 6˜18 carbon atoms, said alkaryl and aralkyl each comprise 7˜18 carbon atoms, and said cycloalkyl or heterocycloalkyl ring comprises 3˜18 carbon atoms.
10. The method according to claim 7 , wherein at least one of R 1 and R 2 is hydrogen.
11. The method according to claim 7 , wherein any two of R 1 , R 2 , R 3 , R 4 , and R 5 form a 3-8 membered cycloalkyl or heterocycloalkyl ring.
12. The method according to claim 7 , wherein R 1 , R 2 , and R 4 each represent hydrogen.
13. The method according to claim 7 , wherein said compound I or II is added in the molar ratio of (0.5˜2):1 relative to said phosphinic acid.
14. The method according to claim 13 , wherein said compound I or II is added in the molar ratio of (1˜1.5):1 relative to said phosphinic acid.
15. The method according to claim 7 , wherein the reaction is carried out in a solvent selected from the group consisting of toluene, cyclohexane, butyl ether, and a combination thereof.
16. The method according to claim 7 , wherein the reaction is carried out under inert gas protection.
17. The method according to claim 16 , wherein said inert gas is selected from the group consisting of nitrogen, argon, carbon dioxide, and a combination thereof.
18. The method according to claim 7 , wherein the reaction temperature is 0° C˜150° C.
19. The method according to claim 18 , wherein the reaction temperature is 85° C˜125° C.
20. The method according to claim 7 , wherein the reaction time is 4˜24 hours.
21. The method according to claim 20 , wherein the reaction time is 4˜8 hours.
22. A polymer or co-polymer of the compound of formula III according to claim 1 .