Process for preparing polymers by means of ring-opening polymerization
View Patent ↗The present invention relates to a process for preparing polymers by means of ring-opening metathetic polymerization, consisting of the following steps: a) providing a reaction mixture consisting of a cycloalkene or a cycloalkene mixture, b) adding a ruthenium compound of the general formula RuX 1 X 2 L 1 a L 2 b (I) where a=0 or 1, b=1 or 2, such that a+b=2; X 1 , X 2 =independently selected anionic ligands; L 1 =uncharged π-binding ligand; L 2 =N-heterocyclic carbene of the formula IIa, IIb or IIc; c) adding a chain transfer agent in a molar ratio in the range from 1:5 to 1:1000 based on the cycloalkene or the sum total of the cycloalkenes in the cycloalkene mixture, d) converting at a temperature within a range from 0° C. to 250° C.
1. Process for preparing polymers by means of ring-opening metathetic polymerization, comprising the following steps:
a. providing a reaction mixture consisting of a cycloalkene or a cycloalkene mixture,
b. adding a ruthenium compound of the general formula RuX 1 X 2 L 1 a L 2 b (I) where
a=0 or 1, b=1 or 2, such that a+b=2;
X 1 , X 2 =independently selected anionic ligands;
L 1 =uncharged π-binding ligand;
L 2 =N-heterocyclic carbene of the formula IIa, IIb or IIc
where
R and R′ are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, phenyl and p-methoxyphenyl; and
R 1 and R 2 are each independently selected from the group consisting of hydrogen, (C 1 -C 18 )-alkyl, (C 3 -C 8 )-cycloalkyl, (C 3 -C 7 )-heterocycloalkyl, (C 6 -C 14 )-aryl, and (C 3 -C 14 )-heteroaryl;
where
R and R′ are each independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, phenyl and p-methoxyphenyl; and
R 1 , R 2 , R 3 , R 4 , R 5 , R 1a , R 2a , R 3a , R 4a , R 5a are each independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and methoxy;
where
R is selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, phenyl and p-methoxyphenyl; and
R′ and R″ are each independently selected from the group consisting of hydrogen, (C 1 -C 18 )-alkyl, (C 3 -C 8 )-cycloalkyl, (C 3 -C 7 )-heterocycloalkyl, (C 6 -C 14 )-aryl, and (C 3 -C 14 )-heteroaryl;
c. adding a chain transfer agent in a molar ratio in the range from 1:5 to 1:1000 based on the cycloalkene or the sum total of the cycloalkenes in the cycloalkene mixture,
d. converting at a temperature within a range from 0° C. to 250° C.
2. Process according to claim 1 , wherein the cycloalkene is selected from the group consisting of compounds of the general formulae (a)-(c)
3. Process according to claim 1 , wherein the chain transfer agent is selected from the group consisting of allyl acetate and compounds of the general formulae (d)-(i)
4. Process according to claim 1 , wherein the molar ratio of ruthenium compound to cycloalkene is in the range from 1:200 to 1:1 000 000.
5. Process according to claim 1 , wherein a=1, b=1 for the ruthenium compound of formula RuX 1 X 2 L 1 a L 2 b (I), such that a compound of the general formula RuX 1 X 2 L 1 L 2 (VIII) is used.
6. Process according to claim 5 , wherein X 1 and X 2 are the same and are each chlorine, and wherein L 1 is selected from the group consisting of benzene, toluene, xylene, p-cymene, trimethylbenzene, tetramethylbenzene, hexamethylbenzene, tetrahydronaphthalene and naphthalene.
7. Process according to claim 6 , wherein L 2 is selected from the group consisting of N-heterocyclic carbenes of the formulae III, IV, VI and VII
8. Process according to claim 5 , wherein the ruthenium compound of the general formula RuX 1 X 2 L 1 L 2 (VIII) is selected from the group consisting of compounds 5, 6, 7 and 8
9. Process according to claim 2 , wherein the chain transfer agent is selected from the group consisting of allyl acetate and compounds of the general formulae (d)-(i)
10. Process according to claim 9 , wherein the molar ratio of ruthenium compound to cycloalkene is in the range from 1:200 to 1:1 000 000.
11. Process according to claim 10 , wherein a=1, b=1 for the ruthenium compound of formula RuX 1 X 2 L 1 a L 2 b (I), such that a compound of the general formula RuX 1 X 2 L 1 L 2 (VIII) is used.
12. Process according to claim 11 , wherein X 1 and X 2 are the same and are each chlorine, and wherein L 1 is selected from the group consisting of benzene, toluene, xylene, p-cymene, trimethylbenzene, tetramethylbenzene, hexamethylbenzene, tetrahydronaphthalene and naphthalene.
13. Process according to claim 12 , wherein L 2 is selected from the group consisting of N-heterocyclic carbenes of the formulae III, IV, VI and VII
14. Process according to claim 11 , wherein the ruthenium compound of the general formula RuX 1 X 2 L 1 L 2 (VIII) is selected from the group consisting of compounds 5, 6, 7 and 8
15. Process according to claim 1 , wherein the following steps are also included after step d.:
e. adding a hydrogenation catalyst,
f. converting at a temperature within a range from 0° C. to 250° C. and at a hydrogen pressure within a range from 1 bar to 100 bar.
16. Process according to claim 15 , wherein the molar ratio of hydrogenation catalyst to cycloalkene used is in the range from 1:100 to 1:1 000 000.
17. Process according to claim 15 , wherein the cycloalkene is selected from the group consisting of compounds of the general formulae (a)-(c)
18. Process according to claim 15 , wherein the chain transfer agent is selected from the group consisting of allyl acetate and compounds of the general formulae (d)-(i)
19. Process according to claim 15 , wherein the molar ratio of ruthenium compound to cycloalkene is in the range from 1:200 to 1:1 000 000.
20. Process according to claim 15 , wherein a=1, b=1 for the ruthenium compound of formula RuX 1 X 2 L 1 a L 2 b (I), such that a compound of the general formula RuX 1 X 2 L 1 L 2 (VIII) is used.
21. Process according to claim 20 , wherein the ruthenium compound of the general formula RuX 1 X 2 L 1 L 2 (VIII) is selected from the group consisting of compounds 5, 6, 7 and 8
22. Process according to claim 16 , wherein the cycloalkene is selected from the group consisting of compounds of the general formulae (a)-(c)
23. Process according to claim 22 , wherein the chain transfer agent is selected from the group consisting of allyl acetate and compounds of the general formulae (d)-(i)
24. Process according to claim 23 , wherein the molar ratio of ruthenium compound to cycloalkene is in the range from 1:200 to 1:1 000 000.
25. Process according to claim 24 , wherein a=1, b=1 for the ruthenium compound of formula RuX 1 X 2 L 1 a L 2 b (I), such that a compound of the general formula RuX 1 X 2 L 1 L 2 (VIII) is used.
26. Process according to claim 25 , wherein X 1 and X 2 are the same and are each chlorine, and wherein L 1 is selected from the group consisting of benzene, toluene, xylene, p-cymene, trimethylbenzene, tetramethylbenzene, hexamethylbenzene, tetrahydronaphthalene and naphthalene.
27. Process according to claim 26 , wherein L 2 is selected from the group consisting of N-heterocyclic carbenes of the formulae III, IV, VI and VII
28. Process according to claim 25 , wherein the ruthenium compound of the general formula RuX 1 X 2 L 1 L 2 (VIII) is selected from the group consisting of compounds 5, 6, 7 and 8