Title of Invention

"A PROCESS FOR THE PREPARATION OF POLY BIS (NAPHTHALIMIDO) SULPHIDES"

Abstract

This invention describes a process for the preparation of poly bis(naphthalimido) sulphides. The process is for the preparation of polymers based on bis(naphthalimido) sulphide compounds. The polymers prepared by the process of the present invention are obtained by nucleophilic halo displacement polymerization reaction. One example would be polythioarylene copolymers, poly (4-thiophenylene) being an important member in the family of polythioarylenes. Another advantage is the presence of imide ring, which would help, in easy displacement of halo group to result in high molecular weight polythioary lene copolymer. The rigid naphthalene ring would lead to polymers with good thermal and mechanical stability. The methyl substitution, ether linkage, highly phenylated diamines in place aromatic diamines help in enhanced solubility.

Full Text

This invention describes a process for the preparation of poly bis(naphthalimido) sulphides. The invention particularly relates to a process for the preparation of polymers based on bis(naphthalimido)sulphide compounds. More particularly, it relates to a process for the preparation of poly bis(naphthalimido) sulphides having general formula given in the drawing accompanying this specification wherein R - -(CH2)n- and n = 2 to 12 or R = 1,4-phenylene, 1,3-phenylene, 4-methyl-l,3-phenylene, 4,4'-thio-diphenylene, 4,4'-methylenediphenylene, 4,4'-oxydiphenylene, 2,5-bis(phenyl) 3,4-diphenyl thiophene, 2,5-bis(phenyl) furan, 3,4 bis( phenyl) 2,5-furan, 3,4-bis(phenyl) 2,5-diphenyl pyrrole, 4,4'-(hexafluoro-isopropylidene) diphenylene, 4,4'-(9-fluorenylidene)-diphenylene, 4,4'-diphenylene sulfone, 1,5'-naphamalene, 2,6'-napthlene, l,4'-cyclohexane, 4,4'-benzophenone, 3,3'-benzophenone, 2,6'-pyridine, 4,4'-(isopropylidene) diphenylene, 4,4'-biphenyl, 4,4'-bis(phenyl ether), 3,3'-bis(phenyl ether), 1,3,3-trimethyl cyclohexane methyl group. Poly bis(naphthaleneimido) sulphide compounds prepared by the process of the present invention can be used to prepare high performance engineering polymers with good chemical and thermal stability. The synthesis of polymers with various specific properties such as high glass transition temperature, improved processability, and long term thermal stability is still major driving force for development of new monomers and polymers therefrom. Bis(naphthalimido) based polymers will have high chemical and thermal stability, and high solubility as compared to those prepared with bis(phthalimido) polymers. In our copending application no. 3323/D/98 we have described and claimed a process for the preparation of bis(4-halo-l,8-napthalimido)alkylenes. The polymers prepared by the process of the present invention are obtained by nucleophilic halo displacement polymerisation reaction. One example would be polythioarylene copolymers, poly(4-thiophenylene) being an important member in the family of polythioarylenes. In the conventional synthetic route to the synthesis of polythioarylenes, the polymer precipitates out of the system as soon as a critical molecular weight is achieved leading to a restriction in the molecular weight. If the compounds prepared by the process of the present invention are used as monomers, since the polymer is soluble, precipitation during the course of the polymerization docs not occur and high molecular weight polymers can be obtained. Another advantage is the presence of imide ring, which would help, in easy displacement of halo group to result in high molecular weight polythioarylene copolymer. The rigid naphthalene ring would lead to polymers with good thermal and mechanical stability. The methyl substitution, ether linkage, highly phcnylated diamincs in place aromatic diamincs helps in enhanced solubility. The compounds prepared by the process of this invention namely poly bis( napthalimido) sulphides are reportedly synthesized first time by the inventors of the present invention and hence there are no earlier methods known fro the preparation of these compounds. The main object of the present invention is therefore to provide a process for the preparation of poly bis (naphthalimido) sulphides, which are soluble in common organic solvents. Accordingly, the present invention provides a process for the preparation of poly bis(naphthalimido) sulphides of formula 1 wherein R = -(CH2)n- and n = 2 to 12 or R= 1 ,4-phenylene, 1,3-phenylene, 4-methyl-l-3-phenylene, 4,4'-thio-diphenylene, 4,4'-methylenediphenylene, 4,4'-oxydiphenylene, 2,5-bis(phenyl) 3,4-diphenyl) thiophene, 2,5-bis(phenyl) furan, 3,4 bis(phenyl) 2,5-furan, 3,4-bis(phenyl) 2,5-diphenyl pyrrole, 4,4'-(hexafluoro-isopropylidene) diphenylene, 4,4'-(9-fluorenylidene)-diphenylene, 4,4 '-diphenylene sulfone, l,5'-naphathalene, 2,6'-napthlene, l,4'-cyclohexane, 4,4'-benzophenone, 3,3'-benzophenone, 2,6'-pyridine, 4,4'-(isopropylidene) diphenylene, 4,4'-biphenyl, 4,4'-bis(phenyl ether), 3,3'- bis(phenyl ether), 1,3,3-trimethyl cyclohexane methyl group which comprises, M .L* reacting a solution of bis(4-halo-l,8-naphthloimido) alkanes / alkylenes or arylenesdn a polar aprotic solvent and alkali metal sulphide such as herein described in an inert atmosphere at temperatures in the range of 1 10 to 250°C for a period ranging between 6 to 1 5 hours, cooling the reaction mixture to room temperature, pouring the reactants into an alkanol such as herein described and separating the product by conventional methods, washing the product with alkanol as defined above to remove the unreacted material and the by product formed during reaction, drying at a temperature ranging between 50 to 100°C to obtain the polybis(naphthalimido) sulphides. In one of the embodiments of the invention, bis(4-halo-l,8-naphthlimido) alkylenes or arylenes used may be such as bis (4-halo-l,8-naphthlimido)ethylene, bis (4-halo-l ,8-naphthlimido) propylcne, bis(4-halo-l,8-naphlhlimido)hcxane, bis(4-halo-l,8-naphthlimido)dodecane, bis(4-halo-l,8-naphthlimido)decane, bis (4-halo-1,8-naphthlimido)pentane, bis(4-halo-l,8-naphthlimido)butane, bis(4-halo-l,8-naphthlimido)l,4-phenyl, bis(4-halo-l,8-naphthlimido) 1,3-phenyl, bis(4-halo-l,8- f naphthlimido) 1,3-phenyl 4-methyl, bis(4-halo-l,8-naphthlimido)methyl, bis(4-halo- l,8-naphthlimido)sulfide diphenyl, bis(4-halo-l,8-naphthlimido)oxy diphenyl, bis(4- halo-l,8-naphthlimido)butane, bis(4-halo-l,8-naphthlimido)-hexafluro- isopropy 1 idene, bis(4-halo-1,8-naphthlimido)-fluorenyledene, bis(4-halo-1,8-naphthlimido)biphenyl, bis(4-halo-l,8-naphthlimido)ether diphenyl, bis(4-halo-l,8-naphthlimido)cyclohexane, bis(4-halo-l,8-naphthlimido) naphthlene, bis(4-halo-l,8-naphthlimido) pyridene, bis(4-halo-l,8-naphthlimido)thiophene, bis(4-halo-l,8-naphthlimido)furan, bis(4-halo-l,8-naphthlimido) benzophenone. In another embodiment the inert gas used may be nitrogen, or argon. In still another embodiment of the present invention, the aprotic solvent used may be such as n-methyl pyrrolidone, n-cyclohexyl pyrrolidone, triphenyl phosphoramide. In yet another embodiment of the invention, the alkali metal sulphide used may be such as sodium sulphide, lithium sulphide, and potassium sulphide. In yet another embodiment of the invention, the alkanol used may be methanol, ethanol. The process of the present invention is described with reference to following examples, which are illustrative only and should not be construed to limit the scope of this invention in any manner. EXAMPLE- 1 5.12 g of 4-chlorobis(naphthlimido)ethylene 0.45 g of lithium sulphide were taken in a glass ampoule and 20 ml n-methyl pyrrolidone was added to it. Nitrogen gas was bubbled through ampoule then sealed and heated in a temperature controlled silicone oil bath at 110 °C for the period of 15 hours, then the ampoule was cooled to room temperature broken to precipitated the product and washed with hot methanol dried and characterised. The yield obtained was 5.45 g. The mp of the product is 320 °C. EXAMPLE -2 6.82 g of 4-bromobis(naphthlimido)hexamethylene 0.78 g of sodium sulphide were taken in a glass ampoule and 20 ml n-cyclohexyl pyrrolidone was added to it. Argon gas was bubbled through ampoule then sealed and heated in a temperature controlled silicone oil bath at 150 °C for the period of 10 hours, then the ampoule was cooled to room temperature broken to precipitated the product and washed with hot ethanol dried and characterised. The yields obtained were 7.00 g. The mp of the product is 282 °C. EXAMPLE -3 6.89 g of 4-chlorobis(naphthlimido)dodecane 1.10 g of potassium sulphide were taken in a glass ampoule and 20 ml n-methyl pyrrolidone was added to it. Nitrogen gas was bubbled through ampoule then sealed and heated in a temperature controlled silicone oil bath at 170 °C for the period of 9 hours, then the ampoule was cooled to room temperature broken to precipitated the product and washed with hot methanol dried and characterised. The yields obtained were 7.40 g. The mp of the product is 220 °C. EXAMPLE- 4 6.12 g of 4-halobis(naphthlimido)phenyl 0.45 g of lithium sulphide were taken in a glass ampoule and 20 ml n-methyl pyrrolidone was added to it. Argon gas was bubbled through ampoule then sealed and heated in a temperature controlled silicone oil bath at 200 °C for the period of 8 hours, then the ampoule was cooled to room temperature broken to precipitated the product and washed with hot ethanol dried and characterised. The yields obtained were 6.50 g. The mp of the product is 368 °C EXAMPLE- 5 6.84 g of 4-bromobis(naphthlimido)4-methylphenyl 0.78 g of sodium sulphide were taken in a glass ampoule and 20 ml n-methyl pyrrolidone was added to it. Nitrogen gas was bubbled through ampoule then sealed and heated in a temperature controlled silicone oil bath at 210 °C for the period of 6 hours, then the ampoule was cooled to room temperature broken to precipitated the product and washed with hot methanol dried and characterised. The yields obtained were 7.60 g. The mp of the product is 343 °C EXAMPLE- 6 7.05 g of 4-chlorobis(naphthlimido)phenylsulfide 1.10 g of potassium sulphide were taken in a glass ampoule and 20 ml n-methyl pyrrolidone was added to it. Argon gas was bubbled through ampoule then sealed and heated in a temperature controlled silicone oil bath at 120 °C for the period of 14 hours, then the ampoule was cooled to room temperature broken to precipitated the product and washed with hot methanol dried and characterised. The yields obtained were 7.58 g. The mp of the product is 353 °C EXAMPLE- 7 6.89 g of 4-chlorobis(naphthlimido)oxyphenyl 0.45 g of lithium sulphide were taken in a glass ampoule and 20 ml n-methyl, pyrrolidone was added to it. Nitrogen gas was bubbled through ampoule then sealed and heated in a temperature controlled silicone oil bath at 130 °C for the period of 13 hours, then the ampoule was cooled to room temperature broken to precipitated the product and washed with hot methanol dried and characterised. The yields obtained were 7.00 g. The mp of the product is 325 °C EXAMPLE- 8 7.10 g of 4-bromobis(naphthlimido)methyl phenyl 0.78g of sodium sulphide were taken in a glass ampoule and 20 ml n-methyl pyrrolidone was added to it. Argon gas was bubbled through ampoule then sealed and heated in a temperature controlled silicone oil bath at 160 °C for the period of 11 hours, then the ampoule was cooled to room temperature broken to precipitated the product and washed with hot methanol dried and characterised. The yields obtained were 7.56 g. The mp of the product is 278 °C. EXAMPLE- 9 8.04 g of 4-chlorobis(naphthlimido)2,5-bis(phenyl) furan, 1.10 g of potassium sulphide were taken in a glass ampoule and 20 ml n-methyl pyrrolidone was added to it. Nitrogen gas was bubbled through ampoule then sealed and heated in a temperature controlled silicone oil bath at 220 °C for the period of 8 hours, then the ampoule was cooled to room temperature broken to precipitated the product and washed with hot methanol dried and characterised. The yields obtained were 7.32 g. The mp of the product is 315 °C EXAMPLE-10 8.83 g of 4-bromobis(naphthlimido)hexafluro-isopropylidene, 0.45 g of lithium sulphide were taken in a glass ampoule and 20 ml n-methyl pyrrolidone was added to it. Argon gas was bubbled through ampoule then sealed and heated in a temperature controlled silicone oil bath at 230 °C for the period of 7 hours, then the ampoule was cooled to room temperature broken to precipitated the product and washed with hot methanol dried and characterised. The yields obtained were 8.60 g. The mp of the product is 338 °C EXAMPLE-11 8.12 g of 4-chlorobis(naphthlimido)fluorenyledene, 0.78g of sodium sulphide were taken in a glass ampoule and 20 ml n-methyl pyrrolidone was added to it. Nitrogen gas was bubbled through ampoule then sealed and heated in a temperature controlled silicone oil bath at 140 °C for the period of 12 hours, then the ampoule was cooled to room temperature broken to precipitated the product and washed with hot methanol dried and characterised. The yields obtained were 8.70 g. The mp of the product is 293 °C Advantages of the present invention: 1. The polymers synthesised by this process of this invention are soluble in common organic solvents are thermally stable. 2. Reasonably high yields are obtained. 3. The process of this invention is amenable for scale up operation. 4. High viscosity polymers are formed. We Claim: 1. A process for the preparation of poly bis(naphthalimido) sulphides of formula 1 wherein R = -(CH2)n- and n = 2 to 12 or R= 1,4-phenylene, 1,3-phenylene, 4- methyl-l-3-phenylene, 4,4'-thio-diphenylene, 4,4'-methylenediphenylene, 4,4'- oxydipenylene, 2,5-bis(phenyl) 3,4-diphenyl) thiophene, 2,5-bis(phenyl) furan, 3,4 bis(phenyl) 2,5-furan, 3,4-bis(phenyl) 2,5-diphenyl pyrrole, 4,4'-(hexafluoro- isopropylidene) diphenylene, 4,4'-(9-fluorenylidene)-diphenylene, 4,4'- diphenylene sulfone, l,5'-naphathalene, 2,6'-napthlene, l,4'-cyclohexane, 4,4'- benzophenone, 3,3'-benzophenone, 2,6'-pyridine, 4,4'-(isopropylidene) diphenylene, 4,4'-biphenyl, 4,4'-bis(phenyl ether), 3,3'-bis(phenyl ether), 1,3,3- trimethyl cyclohexane methyl group which comprises, reacting a solution of bis(4-halo-l,8-naphthloimido) alkanes /alkylenes or arylenes,as herein description in a polar aprotic solvent and alkali metal sulphide such as herein described in an inert atmosphere at temperatures in the range of 110 to 250°C for a period ranging between 6 to 15 hours, cooling the reaction mixture to room temperature, pouring the reactants into an alkanol such as herein described and separating the product by conventional methods, washing the product with alkanol as defined above to remove the unreacted material and the by product formed during reaction, drying at a temperature ranging between 50 to 100°C to obtain the polybis(naphthalimido) sulphides. 2. A process as claimed in claim 1, wherein the bis (4-halo-l,8-naphthlimido) alkanes / alkylenes or arylenes is selected from bis (4-halo-l,8-naphthlimido) ethylene, bis (4-halo-l,8-naphthlimido) propylene, bis(4-halo-l,8-naphthlimido) hexane, bis (4-halo-l,8-naphthlimido) dodecane, bis(4-halo-l,8- naphthlimidoMecane. bis (4-halo-l,8-naphthlimido) pentane, bis (4-halo-l,8-naphthlimido) butane, bis (4-halo-l,8-naphthlimido) 1,4-phenyl, bis (4-halo-l,8-naphthlimido) 1,3-phenyl, bis (4-halo-l,8-naphthlimido)l,3-phenyl 4-methyl, bis(4-halo-l,8-naphthlimido) methyl, bis(4-halo-l,8-naphthlimido) sulfide diphenyl, bis(4-halo-l,8-naphthlimido)oxy diphenyl, bis(4-halo-l,8-naphthlimido)butane, bis (4-halo-l,8-naphthlimido)-hexafluro-isopropylidene, bis (4-halo-1,8-naphthlimido)-fluorenyledene, bis(4-halo-1,8-naphthlimido)biphenyl, bis (4-halo-l,8-naphthlimido)ether diphenyl, bis (4-halo-l,8-naphthlimido) cyclohexane, bis (4-halo-l,8-naphthlimido) naphthlene, bis (4-halo-l,8-naphthlimido) pyridene, bis(4-halo-l,8-naphthlimido) thiophene, bis(4-halo-l,8-naphthlimido) furan, bis (4-halo-l,8-naphthlimido) benzophenone. 3. A process as claimed in claims 1 and 2 wherein the inert gas used is selected from nitrogen or argon. 4. A process as claimed in claims 1 to 3 wherein, the polar aprotic solvent used is selected from n-methyl pyrrolidone, n-cyclohexyl pyrrolidone, triphenyl phoshoramide. 5. A process as claimed in claims 1 to 4 wherein, the alkali metal sulphide used is selected from sodium sulphide, lithium sulphide, and potassium sulphide. 6. A process as claimed in claims 1 to 5 wherein the alkanol used is selected from methanol, ethanol. 7. A process for the preparation of poly bis(naphthalimido) sulphides of general formula given in the drawing accompanying the specification as substantially described with reference to the examples.

Documents:

805-del-1999-abstract.pdf

805-del-1999-claims.pdf

805-del-1999-correspondence-others.pdf

805-del-1999-correspondence-po.pdf

805-del-1999-description (complete).pdf

805-del-1999-drawings.pdf

805-del-1999-form-1.pdf

805-del-1999-form-19.pdf

805-del-1999-form-2.pdf

805-del-1999-form-3.pdf