US5734010A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Process for the preparation of copolymers of carbon monoxide and at least one compound containing an alkenyl unsaturation
Assignee: Enichem SpA
•
Filing: 1997-03-26
•
Granted: 1998-03-31
•
Expires: 2017-03-26
Abstract
Abstract Linear alternating copolymers of carbon monoxide and at least one compound containing an alkenyl unsaturation are obtained by reaction between carbon monoxide and at least one compound containing an alkenyl unsaturation, in a solvent which is liquid under the operating conditions, in the presence of a preformed bischelated catalyst having general formula (I) active without cocatalysts: Pd(chel)(chel')!.sup.++ A.sup.- !.sub.2 (I) wherein: chel and chel', the same or different, represent a nitrogenated or phosphorated bidentate chelating agent, and A - represents an essentially non-co-ordinating, non-esterifiable and non-labile anion selected from (3,5-(CF 3 ) 2 -C 6 H 3 ) 4 B - , tetra(perfluorophenyl)borate B(C 6 F 5 ) 4 - and Al(C 6 F 5 ) 4 - .
Inventors
- 👤 Anna Sommazzi
- 👤 Fabio Garbassi
- 👤 Giovanni Mestroni
- 👤 Barbara Milani
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 08:18
CPC Classifications
C; C08; C08G; C08G67/00; C08G67/02
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
128 words
A process for the preparation of linear alternating copolymers of carbon monoxide and at least one compound containing an unsaturation of the alkenyl type which comprises reacting, in a solvent which is liquid under the operating conditions, the carbon monoxide and one or more compounds containing an unsaturation of the alkenyl type in the presence of a catalyst active without cocatalysts having general formula (I) Pd(chel)(chel')!.sup.++ A.sup.- !.sub.2 (I) wherein: chel and chel', the same or different, represent a nitrogenated or phosphorated bidentate chelating agent, and A - is an essentially non-co-ordinating, non esterifiable and non-labile anion selected from (3,5-(CF 3 ) 2 -C 6 H 3 ) 4 B - , B(C 6 F 5 ) 4 - and Al(C 6 F 5 ) 4 - .
Claim 2
Dependent Claim
128 words
A process for the preparation of linear alternating copolymers of carbon monoxide and at least one compound containing an unsaturation of the alkenyl type which comprises reacting, in a solvent which is liquid under the operating conditions, the carbon monoxide and one or more compounds containing an unsaturation of the alkenyl type in the presence of a catalyst active without cocatalysts having general formula (I) Pd(chel)(chel')!.sup.++ A.sup.- !.sub.2 (I) wherein: chel and chel', the same or different, represent a nitrogenated or phosphorated bidentate chelating agent, and A - is an essentially non-co-ordinating, non esterifiable and non-labile anion selected from (3,5-(CF 3 ) 2 -C 6 H 3 ) 4 B - , B(C 6 F 5 ) 4 - and Al(C 6 F 5 ) 4 - .
Claim 3
Dependent Claim
52 words
The process according to claim 1, characterized in that the nitrogenated bidentate chelating agents are selected from those having general formula (II) ##STR3## wherein: X and Y, the same or different, represent bridged organic groups each having at least three atoms in the bridge, of which at least two are carbon atoms.
Claim 4
Dependent Claim
29 words
The process according to claim 2, wherein when, in addition to the carbon atoms, the X and Y groups contain other atoms these are selected from oxygen and nitrogen.
Claim 5
Dependent Claim
37 words
The process according to claim 3, characterized in that the nitrogenated bidentate chelating agents have the same bridging groups X and Y and contain from 3 to 10 atoms of which at least two are carbon atoms.
Claim 6
Dependent Claim
32 words
The process according to claim 2, characterized in that the nitrogenated bidentate chelating agents are selected from 2,2'-bipyridyl; 4,4'-dimethyl-2,2'bipyridyl; 4,4'-diphenyl-2,2'-bipyridyl; 5,5'-dimethyl-2,2'-bipyridyl; 5-methyl-2,2'-bipyridyl; 1,10-phenanthroline; 4-methyl-1,10-phenanthroline; 5-methyl-1,10-phenanthroline; 4,7-dimethyl-1,10-phenanthroline; 3,8-dimethyl-1,10-phenanthroline; 4,7-diphenyl-1,10-phenanthroline; 4,7-dichloro-1,10-phenanthroline; 3,4,7,8-tetramethyl-1,10-phenanthroline; 4,4'-dimethyl-5,5'-bioxazole; 2,2'-bipyrimidine.
Claim 7
Dependent Claim
92 words
The process according to claim 1, characterized in that the phosphorated bidentate chelating agents are selected from those having general formula (III): ##STR4## wherein: R represents an alkyl radical with from 2 to 4 carbon atoms, a cycloalkylidene radical with from 2 to 10 carbon atoms or an orthophenylene radical; R 1 -R 4 the same or different, each represent a C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl radical or a C 6 -C 12 aromatic radical possibly subsituted with a C 1 -C 4 alkyl or alkoxyl radical.
Claim 8
Dependent Claim
22 words
The process according to claim 6, characterized in that the phosphorated bidentate chelating agents are selected from 1,3-bis(diphenylphosphine)propane; 1,3-bis(di-4-methoxy-phenylphosphine)propane; 1,4-bis(dicyclohexylphosphine)butane and 1,2-bis(diphenylphosphine)cyclohexane.
Claim 9
Dependent Claim
20 words
The process according to claim 1, characterized in that A - is (B(C 6 F 5 ) 4 - ).
Claim 10
Dependent Claim
25 words
The process according to claim 1, characterized in that it additionally contains an organic oxidant selected from quinones, aliphatic nitriles, nitroaromatic derivatives and organic peroxides.
Claim 11
Dependent Claim
14 words
The process according to claim 9, characterized in that the organic oxidant is 1,4-benzoquinone.
Claim 12
Dependent Claim
50 words
The process according to claim 1, characterized in that the compound containing the alkenyl unsaturation is selected from olefins such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene, 1-dodecene or a cyclic compound such as cyclopentene or an aromatic such as styrene, p-methyl-styrene, m-methyl-styrene, p-ethyl-styrene, m-isopropyl-styrene, norbornene or their mixtures.
Claim 13
Dependent Claim
21 words
The process according to claim 1, characterized in that the solvent is selected from methanol, ethanol and 2,2,2-trifluoro-ethanol or their mixtures.
Claim 14
Dependent Claim
28 words
The process according to claim 1, characterized in that the molar ratio between the compound containing the alkenyl unsaturation and the carbon monoxide is between 1:10 and 1:5.
Claim 15
Dependent Claim
17 words
The process according to claim 13, characterized in that the molar ratio is between 1:1 and 1:2.
Claim 16
Dependent Claim
44 words
The process according to claim 1, characterized in that the quantity of catalyst (I) is such as to give a concentration of gram-atoms of palladium per mole of compound containing an unsaturation of the alkenyl type of between 10 -6 and 10 -1 .
Claim 17
Dependent Claim
24 words
The process according to claim 9, characterized in that the quantity of organic oxidant is between 10 and 400 moles per gram-atoms of palladium.
Claim 18
Dependent Claim
34 words
The process according to claim 1, characterized in that the polymerization reaction is carried out at a temperature of between 20° and 150° C. and at a pressure of between 1 and 200 bars.
Claim 19
Dependent Claim
26 words
The process according to claim 20, characterized in that the temperature is between 30° and 100° C. and the pressure is not higher than 100 bars.
Claim 20
Dependent Claim
101 words
A preformed bischelated catalyst active without cocatalyst having general formula (I) Pd(chel)(chel')!.sup.++ A.sup.- !.sub.2 (I) wherein: chel and chel', the same or different, represent a nitrogenated or phosphorated bidentate chelating agent, and A - is an essentially non-co-ordinating, non esterifiable and non-labile anion selected from (3,5-(CF 3 ) 2 -C 6 H 3 ) 4 B - , B(C 6 F 5 ) 4 - and Al(C 6 F 5 ) 4 - , which can be used in a process for the preparation of alternating linear copolymers based on carbon monoxide and at least one compound containing an alkenyl unsaturation.
Claim 21
Dependent Claim
101 words
A preformed bischelated catalyst active without cocatalyst having general formula (I) Pd(chel)(chel')!.sup.++ A.sup.- !.sub.2 (I) wherein: chel and chel', the same or different, represent a nitrogenated or phosphorated bidentate chelating agent, and A - is an essentially non-co-ordinating, non esterifiable and non-labile anion selected from (3,5-(CF 3 ) 2 -C 6 H 3 ) 4 B - , B(C 6 F 5 ) 4 - and Al(C 6 F 5 ) 4 - , which can be used in a process for the preparation of alternating linear copolymers based on carbon monoxide and at least one compound containing an alkenyl unsaturation.
Claim 22
Dependent Claim
52 words
The catalyst according to claim 19, characterized in that the nitrogenated bidentage chelating agent is selected from those having general formula (II) ##STR5## wherein: X and Y, the same or different, represent bridged organic groups each having at least three atoms in the bridge, of which at least two are carbon atoms.
Claim 23
Dependent Claim
29 words
The catalyst according to claim 20, wherein when, in addition to the carbon atoms, the X and Y groups contain other atoms these are selected from oxygen and nitrogen.
Claim 24
Dependent Claim
37 words
The catalyst according to claim 21, characterized in that the nitrogenated bidentate chelating agents have the same bridging groups X and Y and contain from 3 to 10 atoms of which at least two are carbon atoms.
Claim 25
Dependent Claim
32 words
The catalyst according to claim 19, characterized in that the nitrogenated bidentate chelating agents are selected from 2,2'-bipyridyl; 4,4'-dimethyl-2,2'bipyridyl; 4,4'-diphenyl-2,2'-bipyridyl; 5,5'-dimethyl-2,2'-bipyridyl; 5-methyl-2,2'-bipyridyl; 1,10-phenanthroline; 4-methyl-1,10-phenanthroline; 5-methyl-1,10-phenanthroline; 4,7-dimethyl-1,10-phenanthroline; 3,8-dimethyl-1,10-phenanthroline; 4,7-diphenyl-1,10-phenanthroline; 4,7-dichloro-1,10-phenanthroline; 3,4,7,8-tetramethyl-1,10-phenanthroline; 4,4'-dimethyl-5,5'-bioxazole; 2,2'-bipyrimidine.
Claim 26
Dependent Claim
92 words
The catalyst according to claim 19, characterized in that the phosphorated bidentate chelating agents are selected from those having general formula (III): ##STR6## wherein: R represents an alkyl radical with from 2 to 4 carbon atoms, a cycloalkylidene radical with from 2 to 10 carbon atoms or an orthophenylene radical; R 1 -R 4 the same or different, each represent a C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl radical or a C 6 -C 12 aromatic radical possibly subsituted with a C 1 -C 4 alkyl or alkoxyl radical.
Claim 27
Dependent Claim
22 words
The process according to claim 24, characterized in that the phosphorated bidentate chelating agents are selected from 1,3-bis(diphenylphosphine)propane; 1,3-bis(di-4-methoxy-phenylphosphine)propane; 1,4-bis(dicyclohexylphosphine)butane and 1,2-bis(diphenylphosphine)cyclohexane.
Claim 28
Dependent Claim
20 words
The catalyst according to claim 19, characterized in that A - is B(C 6 F 5 ) 4 - .
References Cited (Backward Citations)
US5218085A
Cited
US5420236A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 2001-03-30 | 2001-09-29 | 2002-03-31 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2005-03-30 | 2005-09-29 | 2006-03-31 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2009-03-30 | 2009-09-29 | 2010-03-31 | $7700.00 | Window Closed / Lapsed |