Claims
- 1. A process for the polymerization or copolymerization of heterocyclic monomers through ring opening which comprises polymerizing or copolymerizing at least one heterocyclic monomer structurally capable of anionic polymerization in a non-polar or slightly polar organic solvent medium in the presence of an anionic initiator and of a macro-heterocyclic complexing agent of the general formula I ##STR37## in which: R.sub.1 is a hydrogen atom or a hydrocarbon group or an alkoxycarbonyl group, or the two R.sub.1 together can form a group of the general formula: ##STR38## wherein A is a hydrocarbon group, D is an oxygen or sulfur atom or a hydrocarbon group, with the proviso that at least two of the D groups are oxygen atoms or sulfur atoms and that if R.sub.1 is a hydrogen atom, a hydrocarbon group or an alkoxycarbonyl group, one of the two D groups is oxygen or sulfur and the other is oxygen, and n and p are integers from 1 to 3 and m is 2 or 3.
- 2. A process according to claim 1 wherein the macro-heterocyclic complexing agent has the formula: ##STR39## in which A, m, n and p are as defined in claim 1.
- 3. A process according to claim 2 wherein A is ##STR40## where R is a hydrocarbon radical.
- 4. A process according to claim 1, wherein the macro-heterocyclic complexing agent has the formula: ##STR41## in which the two substituents R.sub.1 ' together represent one of the following chain links forming a third bridge between the two nitrogen atoms of the molecule: ##STR42## where n and p and m are as defined in claim 1.
- 5. A process according to claim 4, wherein the macro-heterocyclic complexing agent has the formula ##STR43## in which n and p and m are as defined in claim 1.
- 6. A process according to claim 5 wherein the macro-heterocyclic complexing agent is
- 1,10-diaza-4,7,13,18-tetraoxa-bicyclo[5,5,8]eicosane,
- 1,10-diaza-4,7,13,16,21-pentaoxa-bicyclo[8,8,5]tricosane,
- 1,10-diaza-4,7,13,16,21,24-hexaoxa-bicyclo[8,8,8] hexacosane, or
- 1,13-diaza-4,7,10,16,19,24,27-heptaoxa-bicyclo[ 8,8,11]nonacosane.
- 7. A process according to claim 4, wherein the complexing agent is 1,10-diaza-13,16,21,24-tetraoxa-bicyclo[ 8,8,8]hexacosane.
- 8. A process according to claim 4 wherein the complexing agent is 1,10-diaza-4,7,13,16,21,26-hexaoxa-bicyclo[ 8,8,0]heptacosane.
- 9. A process according to claim 4, wherein the complexing agent is 1,10-diaza,4,7,13,16,21,24-hexaoxa-5,5-benzo-bicyclo[8,8,8]hexacosane.
- 10. A process according to claim 4, wherein the complexing agent is 1,10-diaza-4,7,13,16-tetraoxa-21,24-dithia-bicyclo[8,8,8]hexacosane.
- 11. A carbazyl-potassium according to claim 4, wherein the complexing agent is 1,7,16,22-tetraaza-4,10,13,19,25,28,33,36,41,44-decaoxa-tricyclo[20,8.sup.1,22 .8.sup.7,16 ]hexatetra-contane.
- 12. A process according to claim 1, wherein the anionic initiator is:
- a metal of group I or II,
- a hydroxide of a metal of group I
- an alcoholate of a metal of group I or II
- an amide of a metal of group I or II of the type ##STR44## wherein R.sub.1 and R.sub.2 are hydrogen or an alkyl, cycloalkyl or aryl radical and M is a metal of group I or II, n being the valency of the metal, a compound MX.sub.n wherein
- M is a metal of group I or II or of the corresponding subgroup,
- n is the valency of the metal, and
- X is a thiocyanate or acetate group
- a monofunctional or difunctional organo-metallic derivative RM wherein M is a metal of group I or II, and R is an alkyl, cycloalkyl or aryl radical, or
- an aromatic complex of a metal of group I or II, or
- a living monofunctional or difunctional oligomer or polymer.
- 13. A process according to claim 12, wherein the anionic initiator is
- metallic lithium sodium, potassium caesium,
- potassium hydroxide,
- an alkali metal t-butylate, t-amylate or n-amylate,
- potassium thiocyanate, potassium bromide and potassium acetate,
- n-butyl-lithium, t-butyl-lithium, carbaxylpotassium and carbazyl-sodium,
- naphthalene-sodium, naphthalene-lithium and naphthalene-potassium, or
- .alpha.-methylstyrene-sodium or .alpha.-methylstyrene-potassium, 1,1-diphenylethylene-sodium or potassium, poly propylene sulfide) sodium and polystyrene-lithium.
- 14. A process according to claim 1, wherein the non-polar or slightly polar organic solvent is an organic solvent having a dielectric constant not exceeding 10 under normal temperature and pressure conditions.
- 15. A process according to claim 14, wherein the organic solvent is
- a linear or cyclic saturated hydrocarbon,
- an aromatic hydrocarbon, or
- a linear or cyclic ether.
- 16. A process according to claim 15, wherein the organic solvent is hexane, heptane, cyclohexane, benzene, toluene, dioxan, diethylether, dimethoxyethane, dimethoxymethane, tetrahydrofuran or tetrahydropyran.
- 17. A process according to claim 1, wherein the complexing agent is present in at least equimolecular amount, relative to the anionic initiator.
- 18. A process according to claim 1, wherein the initiator is in a solution which is prepared by reacting the anionic initiator with the complexing agent in a non-polar or slightly polar solvent medium, and then the monomer to be polymerised is added thereto.
- 19. A process according to claim 18, wherein the initiator solution is prepared by adding the complexing agent to a metal of group I, in the form of a film or in finely divided form, in a non-polar or slightly polar organic solvent, so as to form a solution of the metal, at ambient temperature or below.
- 20. A process according to claim 18, wherein the solution of initiator is prepared by adding the complexing agent to an alkali metal in a non-polar or slightly polar organic solvent medium so as to form a solution of the said metal, and then adding thereto an aromatic hydrocarbon, to form an aromatic hydrocarbon-alkali metal complex.
- 21. A process according to claim 20, wherein the aromatic hydrocarbon is biphenyl, naphthalene, phenanthrene, pyrene or anthracene.
- 22. A process according to claim 19, wherein the metal is sodium, potassium or cesium, the complexing agent is 1,10-diaza-4,7,13,16,21-pentaoxa-bicyclo[8,8,5]tricosane or 1,10-diaza-4,71,13,16,21,24-hexaoxa-bicyclo[8,8,8]hexacosane and the organic solvent is benzene or toluene.
- 23. A process according to claim 18, wherein the metal is sodium, potassium or lithium, the complexing agent is 1,10-diaza-4,7,13,16,21,24-hexaoxa-bicyclo[8,8,8]hexacosane, the aromatic hydrocarbon is naphthalene and the organic solvent is benzene or toluene.
- 24. A process according to claim 18, wherein the initiator is potassium hydroxide, the complexing agent is 1,10-diaza-4,7,13,16,21,24-hexaoxa-bicyclo[8,8,8]hexacosane and the organic solvent is tetrahydrofuran or benzene.
- 25. A process according to claim 18, wherein the initiator is potassium thiocyanate, the complexing agent is 1,10-diaza-4,7,13,16,21,24-hexaoxa-bicyclo[8,8,8]hexacosane and the solvent is tetrahydrofuran.
- 26. A process according to claim 18, wherein the initiator is potassium acetate, the complexing agent is 1,10-diaza-4,7,13,16,21,24-hexaoxa-5,6-benzo-bicyclo[8,8,8]hexacosane and the organic solvent is tetrahydrofuran.
- 27. A process according to claim 18, wherein the anionic initiator is .alpha.-methylstyrene tetramer-potassium, the complexing agent is 1,10-diaza-4,7,13,16,21,24-hexaoxa-bicyclo[8,8,8]hexacosane and the organic solvent is tetra-hydrofuran or benzene.
- 28. The process according to claim 1, wherein the heterocyclic monomer is (a) a compound of the general formula ##STR45## wherein X is oxygen or sulphur, R being hydrogen, a cycloalkyl or aryl, (b) a cyclohexene sulfide ##STR46## (c) a four-member ring of the general formula ##STR47## wherein R is alkyl or aryl, (d) a lactone of general formula ##STR48## n being an integer from 1 to 4, each of R.sub.1,R.sub.2,R.sub.3 and R.sub.4 being H, alkyl, cycloakyl or aryl or
- (e) a siloxane.
Priority Claims (2)
Number |
Date |
Country |
Kind |
45482/72 |
Oct 1972 |
GBX |
|
36257/73 |
Jul 1973 |
GBX |
|
Parent Case Info
This is a division, of application Ser. No. 401,119 filed Sept. 26, 1973, now U.S. Pat. No. 3,890,278, issued June 17, 1975.
US Referenced Citations (6)
Non-Patent Literature Citations (3)
Entry |
Bywater, "Anionic Polymerization", at pp. 27-30, 47-53, & 64-69, vol. 4, Progress in Polymer Science, Edited by A.D. Jenkins, Pergamon, Oxford & New York, 1974. |
Furukawa et al., "Polymerization of Aldehydes and Oxides", Interscience, 1963, pp. 155.161 & 167-169. |
Miki et al., "Polyalkylene Oxide", Chemical Abstracts 73, 15498z (1970). |
Divisions (1)
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Number |
Date |
Country |
Parent |
401119 |
Sep 1973 |
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