US4400499A
Expired / Lapsed
US
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Integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers from aryl polyhalide monomers
Assignee: BP Corp North America Inc
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Filing: 1981-12-29
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Granted: 1983-08-23
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Expires: 2001-12-29
Abstract
Abstract Described herein is an integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers derived from aryl polyhalide monomers. Aryl polyhalide monomers are first prepared by the reaction of an alkali metal salt of a phenol compound, e.g., dipotassium salt of bisphenol A, with a dihalobenzenoid compound, e.g., 4,4'-dichlorophenylsulfone, in a liquid phase of an aprotic solvent and an azeotrope former, e.g., toluene. Water is removed from the reaction mass as an azeotrope until substantially anhydrous conditions are attained. The aryl polyhalide monomers are then coupled by contacting the monomers with a catalyst mixture of a nickel compound and a ligand in the presence of a reducing metal, e.g., zinc, and an aprotic solvent under substantially anhydrous conditions to form substantially linear high molecular weight thermoplastic polymers.
Inventors
- 👤 Ismael Colon
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 12:27
CPC Classifications
C; C08; C08G; C08G61/00; C08G61/12; C08G61/121; C08G65/00; C08G65/34; C08G65/38; C08G65/40; C08G65/4093; Y; Y02; Y02P; Y02P20/00; Y02P20/10
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
376 words
An integrated process for preparing a substantially linear thermoplastic polymer derived from an aryl polyhalide monomer which comprises: (i) contacting a phenol compound with about stoichiometric amounts of an alkali metal carbonate or hydroxide sufficient to form an alkali metal salt of the phenol compound in a liquid phase of an aprotic solvent and an azeotrope former and for a time and at a temperature sufficient to form the alkali metal salt of the phenol compound; (ii) contacting the alkali metal salt of the phenol compound with a dihalobenzenoid compound sufficient to form an aryl polyhalide monomer in a liquid phase of an aprotic solvent and an azeotrope former for a time and at a temperature sufficient to form the aryl polyhalide monomer, wherein the dihalobenzenoid compound has an inert electron withdrawing group in one or more of the positions ortho and para to the halogen atoms thereby activating the halogen atoms to a level sufficient to react with said alkali metal salt of the phenol compound; (iii) removing water from the reaction mass of (i) and (ii) as an azeotrope with said azeotrope former until substantially anhydrous conditions are attained and excess azeotrope former is substantially removed; and (iv) coupling aryl polyhalide monomers by contacting said monomers with a catalyst mixture in the presence of a reducing metal selected from the group consisting of zinc, magnesium and manganese or mixtures thereof and in a liquid phase of an aprotic solvent under substantially anhydrous conditions for a time and at a temperature sufficient to form a substantially linear thermoplastic polymer, wherein the catalyst mixture comprises an anhydrous nickel compound and at least one ligand selected from the group consisting of a triarylphosphine having from about 6 to about 14 carbon atoms in each aryl moiety and an aromatic bidentate compound containing at least one ring nitrogen atom and from about 5 to about 30 carbon atoms and wherein the ratio of gram atoms of nickel per mole of aryl polyhalide monomer is from about 0.001 to about 0.1, the amount of ligand is from about 1 to about 50 moles per gram atom of nickel and the amount of reducing metal is at least about 1 mole of reducing metal per mole of aryl polyhalide monomer.
Claim 2
Dependent Claim
376 words
An integrated process for preparing a substantially linear thermoplastic polymer derived from an aryl polyhalide monomer which comprises: (i) contacting a phenol compound with about stoichiometric amounts of an alkali metal carbonate or hydroxide sufficient to form an alkali metal salt of the phenol compound in a liquid phase of an aprotic solvent and an azeotrope former and for a time and at a temperature sufficient to form the alkali metal salt of the phenol compound; (ii) contacting the alkali metal salt of the phenol compound with a dihalobenzenoid compound sufficient to form an aryl polyhalide monomer in a liquid phase of an aprotic solvent and an azeotrope former for a time and at a temperature sufficient to form the aryl polyhalide monomer, wherein the dihalobenzenoid compound has an inert electron withdrawing group in one or more of the positions ortho and para to the halogen atoms thereby activating the halogen atoms to a level sufficient to react with said alkali metal salt of the phenol compound; (iii) removing water from the reaction mass of (i) and (ii) as an azeotrope with said azeotrope former until substantially anhydrous conditions are attained and excess azeotrope former is substantially removed; and (iv) coupling aryl polyhalide monomers by contacting said monomers with a catalyst mixture in the presence of a reducing metal selected from the group consisting of zinc, magnesium and manganese or mixtures thereof and in a liquid phase of an aprotic solvent under substantially anhydrous conditions for a time and at a temperature sufficient to form a substantially linear thermoplastic polymer, wherein the catalyst mixture comprises an anhydrous nickel compound and at least one ligand selected from the group consisting of a triarylphosphine having from about 6 to about 14 carbon atoms in each aryl moiety and an aromatic bidentate compound containing at least one ring nitrogen atom and from about 5 to about 30 carbon atoms and wherein the ratio of gram atoms of nickel per mole of aryl polyhalide monomer is from about 0.001 to about 0.1, the amount of ligand is from about 1 to about 50 moles per gram atom of nickel and the amount of reducing metal is at least about 1 mole of reducing metal per mole of aryl polyhalide monomer.
Claim 3
Dependent Claim
39 words
An integrated process as defined in claim 1 wherein the phenol compound is selected from the group consisting of bisphenol A, hydroquinone, bisphenol S and p-chlorophenol and the alkali metal carbonate or hydroxide is potassium carbonate or potassium hydroxide.
Claim 4
Dependent Claim
24 words
An integrated process as defined in claim 2 wherein the alkali metal salt of the phenol compound is the dipotassium salt of bisphenol A.
Claim 5
Dependent Claim
23 words
An integrated process as defined in claim 2 wherein the alkali metal salt of the phenol compound is the dipotassium salt of hydroquinone.
Claim 6
Dependent Claim
23 words
An integrated process as defined in claim 2 wherein the alkali metal salt of the phenol compound is the potassium salt of p-chlorophenol.
Claim 7
Dependent Claim
40 words
An integrated process as defined in claim 2 wherein the aprotic solvent is selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, dimethlsulfoxide and sulfolane and the azeotrope former is selected from the group consisting of toluene, benzene, heptane and xylene.
Claim 8
Dependent Claim
28 words
An integrated process as defined in claim 6 wherein the dihalobenzenoid compound is selected from the group consisting of 4,4'-dichlorophenylsulfone, 4,4'-difluorophenylsulfone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 1,4-bis-(p-chloro-N-methyl-benzenesulfonamido)butane, 4,4'-dichloroazobenzene and piperazine bis-p-chlorobenzenesulfonamide.
Claim 9
Dependent Claim
36 words
An integrated process as defined in claim 7 wherein the reaction of (ii) is conducted at a temperature above 100° C. and below the decomposition temperature of the reactants, the solvent and the aryl polyhalide monomer.
Claim 10
Dependent Claim
45 words
An integrated process as defined in claim 8 wherein the aryl polyhalide monomer is selected from the group consisting of: X--E'--O--E--O--E'--X; X--E--O--E'--O--E--X; and X--E--O--E'--X, wherein X is halogen, E is the residuum of the phenol compound and E' is the residuum of the dihalobenzenoid compound.
Claim 11
Dependent Claim
38 words
An integrated process as defined in claim 9 wherein the aryl polyhalide monomer has the formula: ##STR15## wherein R represents a member of the group consisting of hydrogen, lower alkyl, lower aryl and the halogen substituted groups thereof.
Claim 12
Dependent Claim
17 words
An integrated process as defined in claim 9 wherein the aryl polyhalide monomer has the formula: ##STR16##
Claim 13
Dependent Claim
17 words
An integrated process as defined in claim 9 wherein the aryl polyhalide monomer has the formula: ##STR17##
Claim 14
Dependent Claim
17 words
An integrated process as defined in claim 9 wherein the aryl polyhalide monomer has the formula: ##STR18##
Claim 15
Dependent Claim
17 words
An integrated process as defined in claim 9 wherein the aryl polyhalide monomer has the formula: ##STR19##
Claim 16
Dependent Claim
33 words
An integrated process as defined in claim 9 wherein the aryl polyhalide monomer is a mixture comprising at least two aryl polyhalide monomers selected from the group consisting of: X--E'--O--E--O--E'--X; X--E--O--E'--O--E--X; and X--E--O--E'--X.
Claim 17
Dependent Claim
43 words
An integrated process as defined in claim 15 wherein the water content of the reaction mixture of (i) and (ii) is maintained less than about 0.5 percent by weight and is reduced to about 0.01 weight percent before the polymerization reaction of (iv).
Claim 18
Dependent Claim
55 words
An integrated process as defined in claim 16 wherein the catalyst mixture comprises an anhydrous nickel compound selected from the group consisting of nickel chlorides, bromides and iodides, a triarylphosphine selected from the group consisting of triphenylphosphine and trinaphthylphosphine, and an aromatic bidentate compound selected from the group consisting of 2,2'-bipyridine, 1,10-phenanthroline, 1,8-naphthylpyridine and 2-methylaminopyridine.
Claim 19
Dependent Claim
18 words
An integrated process as defined in claim 16 wherein the catalyst mixture comprises nickel chloride, triphenylphosphine and 2,2'-bipyridine.
Claim 20
Dependent Claim
32 words
An integrated process as defined in claim 17 wherein the reducing metal is a finely divided powder having a mesh size of 20 or finer when measured in the U.S. sieve scale.
Claim 21
Dependent Claim
14 words
An integrated process as defined in claim 17 wherein the reducing metal is zinc.
Claim 22
Dependent Claim
51 words
An integrated process as defined in claim 19 wherein an inorganic salt selected from the group consisting of alkali, alkaline earth, zinc, magnesium, manganese and aluminum halides or mixtures thereof is added as a promoter in an amount of from about 0.1 to about 1000 moles per gram atom of nickel.
Claim 23
Dependent Claim
32 words
An integrated process as defined in claim 21 wherein the inorganic salt is selected from the group consisting of an alkali metal chloride, an alkali metal iodide and an alkali metal bromide.
Claim 24
Dependent Claim
26 words
An integrated process as defined in claim 21 wherein the water content of the reaction mixture of (iv) is maintained at about 0.01 percent by weight.
Claim 25
Dependent Claim
28 words
An integrated process as defined in claim 23 wherein the coupling reaction of (iv) is conducted at a temperature of from about 0° C. to about 250° C.
Claim 26
Dependent Claim
85 words
An integrated process as defined in claim 24 wherein the substantially linear thermoplastic polymer is selected from the group consisting of recurring units of: --E'--O--E--O--E'-- --E--O--E'--O--E--; and --E--O--E'--, where E is the residuum of the phenol compound and E' is the residuum of the dihalobenzenoid compound and wherein the E residuum and the E' residuum may be valently bonded to ether oxygens through aromatic carbon atoms or valently bonded to each of an aromatic carbon atom and an ether oxygen through an aromatic carbon atom.
Claim 27
Dependent Claim
42 words
An integrated process as defined in claim 25 wherein the substantially linear thermoplastic polymer has recurring units of the formula: ##STR20## wherein R represents a member of the group consisting of hydrogen, lower alkyl, lower aryl and the halogen substituted groups thereof.
Claim 28
Dependent Claim
21 words
An integrated process as defined in claim 25 wherein the substantially linear thermoplastic polymer has recurring units of the formula: ##STR21##
Claim 29
Dependent Claim
21 words
An integrated process as defined in claim 25 wherein the substantially linear thermoplastic polymer has recurring units of the formula: ##STR22##
Claim 30
Dependent Claim
21 words
An integrated process as defined in claim 25 wherein the substantially linear thermoplastic polymer has recurring units of the formula: ##STR23##
Claim 31
Dependent Claim
21 words
An integrated process as defined in claim 25 wherein the substantially linear thermoplastic polymer has recurring units of the formula: ##STR24##
Claim 32
Dependent Claim
34 words
An integrated process as defined in claim 1 wherein the substantially linear thermoplastic polymer is selected from the group consisting of a polyester, a polycarbonate, a polysulfone, a polyether, a polyimide and a polyketone.
Claim 33
Dependent Claim
14 words
An integrated process as defined in claim 25 wherein the aprotic solvent is N,N-dimethylacetamide.
Claim 34
Dependent Claim
35 words
An integrated process as defined in claim 25 wherein the catalyst mixture is added directly to the reaction mass of (ii) such that the catalyst is formed in situ in the aryl polyhalide monomer solution.
Claim 35
Dependent Claim
48 words
An integrated process as defined in claim 25 wherein the phenol compound and the alkali metal carbonate or hydroxide are added directly to the reaction mass of (ii) such that the alkali metal salt of the phenol compound is formed in situ in the aryl polyhalide monomer solution.
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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) | 1986-08-22 | 1987-02-21 | 1987-08-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-08-22 | 1991-02-21 | 1991-08-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-08-22 | 1995-02-21 | 1995-08-23 | $7700.00 | Window Closed / Lapsed |