US4116887A
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Antionic polymerization
Assignee: Societe Nationale des Poudres et Explosifs
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Filing: 1975-01-09
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Granted: 1978-09-26
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Expires: 1995-01-09
Abstract
Abstract A novel process for polymerization or copolymerization of monomers is described, according to which the reaction is carried out in the presence of an anionic initiator and a macroheterocyclic complexing agent of formula <IMAGE> (I) in which:
Inventors
- 👤 Jean-Marie Lehn
- 👤 Francois Schue
- 👤 Sylvia Boileau
- 👤 Bernd Kaempf
- 👤 Alain Andre Cau
- 👤 Jean Robert Moinard
- 👤 Serge Fernand Raynal
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 14:35
CPC Classifications
C; C08; C08G; C08G65/00; C08G65/02; C08G65/26; C08G65/2603; C08F; C08F4/00; C08G61/00; C08G61/02; C08G61/10; C08G63/00; C08G63/78; C08G63/82; C08G63/823; C08G63/87; C08G65/2618; C08G65/2621; C08G65/263; C08G65/2642; C08G65/2645; C08G65/2648; C08G65/2651; C08G75/00; C08G75/02; C08G75/06; C08G77/00; C08G77/04; C08G77/06; C08G77/08; C08G85/00
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
168 words
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 1 is a hydrogen atom or a hydrocarbon group or an alkoxycarbonyl group, or the two R 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 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.
Claim 2
Dependent Claim
168 words
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 1 is a hydrogen atom or a hydrocarbon group or an alkoxycarbonyl group, or the two R 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 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.
Claim 3
Dependent Claim
28 words
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.
Claim 4
Dependent Claim
16 words
A process according to claim 2 wherein A is ##STR40## where R is a hydrocarbon radical.
Claim 5
Dependent Claim
56 words
A process according to claim 1, wherein the macro-heterocyclic complexing agent has the formula: ##STR41## in which the two substituents R 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.
Claim 6
Dependent Claim
28 words
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.
Claim 7
Dependent Claim
19 words
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.
Claim 8
Dependent Claim
13 words
A process according to claim 4, wherein the complexing agent is 1,10-diaza-13,16,21,24-tetraoxa-bicyclo[ 8,8,8]hexacosane.
Claim 9
Dependent Claim
13 words
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.
Claim 10
Dependent Claim
12 words
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.
Claim 11
Dependent Claim
12 words
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.
Claim 12
Dependent Claim
16 words
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 7 ,16 ]hexatetra-contane.
Claim 13
Dependent Claim
163 words
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 1 and R 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 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.
Claim 14
Dependent Claim
54 words
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 α-methylstyrene-sodium or α-methylstyrene-potassium, 1,1-diphenylethylene-sodium or potassium, poly propylene sulfide) sodium and polystyrene-lithium.
Claim 15
Dependent Claim
31 words
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.
Claim 16
Dependent Claim
26 words
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.
Claim 17
Dependent Claim
23 words
A process according to claim 15, wherein the organic solvent is hexane, heptane, cyclohexane, benzene, toluene, dioxan, diethylether, dimethoxyethane, dimethoxymethane, tetrahydrofuran or tetrahydropyran.
Claim 18
Dependent Claim
22 words
A process according to claim 1, wherein the complexing agent is present in at least equimolecular amount, relative to the anionic initiator.
Claim 19
Dependent Claim
43 words
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.
Claim 20
Dependent Claim
56 words
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.
Claim 21
Dependent Claim
55 words
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.
Claim 22
Dependent Claim
17 words
A process according to claim 20, wherein the aromatic hydrocarbon is biphenyl, naphthalene, phenanthrene, pyrene or anthracene.
Claim 23
Dependent Claim
29 words
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.
Claim 24
Dependent Claim
32 words
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.
Claim 25
Dependent Claim
25 words
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.
Claim 26
Dependent Claim
22 words
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.
Claim 27
Dependent Claim
23 words
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.
Claim 28
Dependent Claim
26 words
A process according to claim 18, wherein the anionic initiator is α-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.
Claim 29
Dependent Claim
88 words
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 1 ,R 2 ,R 3 and R 4 being H, alkyl, cycloakyl or aryl or (e) a siloxane.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-09-25 | 1982-03-27 | 1982-09-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-09-25 | 1986-03-27 | 1986-09-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-09-25 | 1990-03-27 | 1990-09-26 | $7700.00 | Window Closed / Lapsed |