US4224429A
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Process for the anionic polymerization in the presence of cryptants
Assignee: Societe Nationale des Poudres et Explosifs
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Filing: 1977-08-11
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Granted: 1980-09-23
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Expires: 1997-08-11
Abstract
Abstract A process for the anionic polymerization or copolymerization of olefinic monomers, dienic monomers, vinyl monomers and heterocyclic monomers is described which comprises reacting at least one monomer which is an olefinic monomer, a vinyl monomer or an heterocyclic monomer with a catalyst capable of inducing anionic polymerization and an aprotic macroheterocyclic cryptant, said at least one monomer being the only medium for the reaction. The macroheterocyclic complexing agent has general formula <IMAGE> in which: R1 is hydrogen, a hydrocarbon radical or alkoxycarbonyl, or the two R1 together can form a group of the general formula: <IMAGE> <IMAGE> in which A is a hydrocarbon radical, D is oxygen, sulfur, or a hydrocarbon radical, with the proviso that at leat two of the D groups are oxygen or sulfur and that if R1 is hydrogen, a hydrocarbon radical or alkoxycarbonyl, one of these 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.
Inventors
- 👤 Jean-Marie Lehn
- 👤 Francois Schue
- 👤 Sylvie Boileau
- 👤 Alain A. Cau
- 👤 Bernd Kaempf
- 👤 Jean R. Moinard
- 👤 Serge F. Raynal
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 14:08
CPC Classifications
C; C08; C08G; C08G77/00; C08G77/04; C08G77/06; C08G77/08; C08F; C08F36/00; C08F36/02; C08F36/04; C08F4/00; C08G61/00; C08G61/02; C08G61/10; C08G65/00; C08G65/02; C08G65/26; C08G65/2603; C08G65/2642; C08G65/2645; C08G65/2651
Claims Analysis
Total Claims: 20
Claim 1
Independent Claim
96 words
A process for the anionic polymerization or copolymerization of monomers containing ethylenic unsaturation and heterocyclic monomers which comprises reacting at least one monomer which is a vinyl monomer or an heterocyclic monomer with a catalyst capable of inducing anionic polymerization and an aprotic macroheterocyclic cryptant, said at least one monomer being the only medium for the reaction, said macroheterocyclic cryptant being heterobicyclic, heterotricyclic or heterotetracyclic and containing as heteroatoms: (1) N; (2) N and O; (3) N, S and O; (4) N and S, said cryptant being able of forming a cryptate after entrapping a cation.
Claim 2
Dependent Claim
96 words
A process for the anionic polymerization or copolymerization of monomers containing ethylenic unsaturation and heterocyclic monomers which comprises reacting at least one monomer which is a vinyl monomer or an heterocyclic monomer with a catalyst capable of inducing anionic polymerization and an aprotic macroheterocyclic cryptant, said at least one monomer being the only medium for the reaction, said macroheterocyclic cryptant being heterobicyclic, heterotricyclic or heterotetracyclic and containing as heteroatoms: (1) N; (2) N and O; (3) N, S and O; (4) N and S, said cryptant being able of forming a cryptate after entrapping a cation.
Claim 3
Dependent Claim
113 words
The process according to claim 1 wherein said macroheterocyclic cryptant has general formula ##STR31## in which: R 1 is hydrogen, a hydrocarbon radical or alkoxycarbonyl, or the two R 1 together can form a group of the general formula: ##STR32## in which A is a hydrocarbon radical, D is oxygen, sulfur, or a hydrocarbon radical, with the proviso that at least two of the D groups are oxygen or sulfur and that if R 1 is hydrogen, a hydrocarbon radical or alkoxycarbonyl, one of these 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 4
Dependent Claim
27 words
A process according to claim 2 wherein the macroheterocyclic cryptant has the formula: ##STR33## in which A, m, n and p are as defined in claim 2.
Claim 5
Dependent Claim
16 words
A process according to claim 3 wherein A is ##STR34## where R is a hydrocarbon radical.
Claim 6
Dependent Claim
55 words
A process according to claim 2, wherein the macroheterocyclic cryptant has the formula: ##STR35## 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: ##STR36## wherein n and p and m are as defined in claim 2.
Claim 7
Dependent Claim
27 words
A process according to claim 5, wherein the macroheterocyclic cryptant has the formula ##STR37## in which n and p and m are as defined in claim 2.
Claim 8
Dependent Claim
17 words
A process according to claim 6 wherein the macroheterocyclic cryptant 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 ##STR38##
Claim 9
Dependent Claim
3 words
or 1. 10-diaza-13,16,21,24-tetraoxa-bicyclo[8,8,8]hexacosane.
Claim 10
Dependent Claim
3 words
or 1. 10-diaza-13,16,21,24-tetraoxa-bicyclo[8,8,8]hexacosane.
Claim 11
Dependent Claim
11 words
A process according to claim 5, wherein the cryptant is 1,10-diaza-4,7,13,16,21,26-hexaoxa-bicyclo[8,8,9]heptacosane.
Claim 12
Dependent Claim
11 words
A process according to claim 5, wherein the cryptant is 1,10-diaza-4,7,13,16,21,24-hexaoxa-5,5-benzo-bicyclo[8,8,8]hexacosane.
Claim 13
Dependent Claim
11 words
A process according to claim 5, wherein the cryptant is 1,10-diaza-4,7,13,16-tetraaxa-21,24-dithia-bicyclo[8,8,8]hexacosane.
Claim 14
Dependent Claim
16 words
A process according to claim 5, wherein the cryptant is 1,7,16,22-tetraaza-4,10,13,19,25,28,33,36,41,44-decaoxa-tricyclo[20.8.sup.1,22.8 1 ,22.8 7 ,16 ]hexatetra-contane.
Claim 15
Dependent Claim
180 words
A process according to claim 2, wherein the catalyst is a member selected from the group consisting of: (1) a metal of group Ia or IIa; (2) a hydroxide of a metal of group Ia; (3) an alcoholate of a metal of group Ia or IIa; (4) an amide of a metal of group Ia or IIa of the type ##STR39## wherein R 1 and R 2 are hydrogen or an alkyl, cycloalkyl or aryl and M is a metal of group Ia or IIa, n being the valence of the metal; (5) a compound MX n wherein M is a metal of group Ia or IIa or of the corresponding sub-group, in which n is the valence of the metal, and X is thiocyanate, carbonate, chloride or acetate; (6) a monofunctional or difunctional organo-metallic derivative of formula RM wherein M is a metal of group Ia or IIa, and R is an alkyl, cycloalkyl or aryl radical, (7) an aromatic complex of a metal of group Ia or IIa, and (8) a living monofunctional or difunctional oligomer or polymer.
Claim 16
Dependent Claim
67 words
A process according to claim 12, wherein the catalyst is a member selected from the group consisting of: (1) metallic lithium, sodium, potassium caesium, (2) potassium hydroxide, (3) an alkali metal t-butylate, t-amylate or n-amylate, (4) potassium thiocyanate, potassium bromide and potassium acetate, (5) n-butyl-lithium, t-butyl-lithium, carbazyl-potassium and carbazyl-sodium, (6) naphthalene-sodium, naphthalene-lithium and naphthalene-potassium, and (7) α-methylstyrene-sodium, or α-methylstyrene-potassium, 1,1-diphenylethylene-sodium or potassium, poly(propylene sulfide) sodium and polystyrene-lithium.
Claim 17
Dependent Claim
20 words
A process according to claim 1, wherein the cryptant is present in at least equimolecular amount, relative to the catalyst.
Claim 18
Dependent Claim
36 words
A process according to claim 1 wherein the catalyst is first prepared in solution in a non-polar or slightly polar solvent medium, the solvent is evaporated, then the monomer and the macroheterocyclic agent are added thereto.
Claim 19
Dependent Claim
47 words
The process according to claim 1 wherein the monomer is styrene, α-methyl styrene, 2-vinyl pyridine, methyl methacrylate, isoprene, acrylonitrile, methacrylonitrile, butadiene, β-propiolactone, ethylene oxide, propylene sulfide, octamethyl cyclotetrasiloxane, the cyclic carbonate of neopentyl glycol, trimethylene carbonate, the cyclic carbonate of 2-methyl-2-propyl 1,3-propanediol, 2-ethyl 2-propyl 1,3-propanediol, 2-phenyl-2-methyl 1,3-propanediol.
Claim 20
Dependent Claim
26 words
A process according to claim 1 wherein the macroheterocyclic cryptant is a member selected from the group of the compounds having the formula hereinbelow: ##STR40## ##STR41##
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1983-09-23 | 1984-03-24 | 1984-09-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-09-23 | 1988-03-24 | 1988-09-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-09-23 | 1992-03-24 | 1992-09-23 | $7700.00 | Window Closed / Lapsed |