Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines

Definitions

• This invention relates to a method for the manufacture of poly(etherimide)s. More particularly, it relates to a method for the manufacture of poly(etherimide)s which eliminates the need for an intermediate nitration step.
• Polyetherimides are high heat engineering plastics having a variety of uses. As disclosed in U.S. Patent Nos. 4,417,044; 4,599,429; 4,902,809; and 4,921,970, the present commercial process for the synthesis of polyetherimides requires nitration of N-methylphthalimide to yield 4-nitro-N-methylphthalimide. Nitration often results in the formation of byproducts, which must be separated. In the next step of the process, 4-nitro-N-methylphthalimide is treated with the disodium salt of a dihydroxy compound, usually a bis(phenol) such as bisphenol A, to yield a bisimide (I) having the following general structure:
• a new method for the synthesis of poly(etherimide)s which eliminates the nitration step comprises synthesis and reaction of a substituted N-alkylphthalimide (III)
• Transimidation is effected in the presence of a substituted phthalic anhydride, which yields a substituted ⁇ -alkylphthalimide that corresponds to the substituted phthalic anhydride as a by-product.
• By-product substituted ⁇ -alkylphthalimide may then be recycled for use in the formation bisimide (IN).
• transimidation is effected in the presence of 4-substituted tetrahydrophthalic anhydride, which yields a 4-substituted ⁇ - alkyltetrahydrophthalimide as a by-product.
• the by-product 4-substituted ⁇ - alkyltetrahydrophthalimide may be converted by aromatization to a 4-substituted ⁇ - alkylphthalimide, which may be used in the formation of bis(imide) (IN).
• a convenient route for the manufacture of poly(etherimide)s comprises synthesis and reaction of a substituted N-alkylphthalimide (III):
• alkyl group is a branched or straight chain alkyl group having from one to about 18 carbons.
• the alkyl group is a methyl group.
• the substituent (X) is a nitro, chloro, bromo, or fluoro in the 3- or 4- position.
• Substituted N- alkylphthalimides may be obtained by the treatment of the corresponding substituted phthalic anhydride with a primary amine having the formula H 2 N-alkyl via a melt reaction, for example by contact of a gaseous primary amine such as methylamine with molten 4-halophthalic anhydride.
• Halophthalic anliydrides may be obtained by aromatization of the corresponding halotetrahydrophthalic anhydrides as disclosed in U.S. Patent Nos. 5,233,054, 5,003,088, 5,059,697 and 4,978,760, which are incorporate by reference herein.
• Halophthalic anhydrides may also be obtained by the aromatization of the corresponding halotetrahydophthalic anhydrides in the presence of a catalyst such as a transition metal oxide.
• Nitro substituted phthalic anhydrides may be obtained by the nitration of phthalic anhydrides as taught in U.S. Patent No. 5,155,234.
• Displacement of the substituent of the substituted N-alkylphthalimide (III) may be effected by treatment with the disodium salt of a dihydroxy compound having the formula (VII)
• S is a divalent radical, for example a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms; a cycloalkylene group having from about 3 to about 20 carbon atoms; or an arylene group having from 6 to about 20 carbon atoms, and halogenated derivatives thereof.
• the alkylene, cycloalkylene, and arylene groups may be further substituted with alkyl, halogenated alkyl, fiuoro, alkoxy, nitro, phenyl, phenoxy, aryl or other groups, provided that such substitutions do not interfere with synthesis or reaction.
• the displacement reaction between the dihydroxy compound and the substituted ⁇ -alkylphthalimide may be conducted in an inert solvent such as toluene, xylene, chlorobenzene or dichlorobenzene in the presence of a phase transfer catalyst such as hexaethylguanidinium chloride at a temperature in the range of about 110 to about 180°C as taught in U.S. Patent No. 5,132,423, which is incorporated by reference herein. Displacement may also occur in the melt phase with the substituted N-alkyphthalimide.
• an inert solvent such as toluene, xylene, chlorobenzene or dichlorobenzene
• a phase transfer catalyst such as hexaethylguanidinium chloride
• a particularly preferred dihydroxy compound is bis(phenol) (NIII)
• T is a single bond linking the two aryl groups, or a divalent radical, for example a straight or branched chain alkylene group having from one to about 20 carbon atoms; a cycloalkylene group having from about 3 to about 20 carbon atoms; or an arylene group having from 6 to about 20 carbon atoms, and halogenated derivatives thereof.
• the alkylene, cycloalkylene, and arylene groups may be further substituted alkyl, halogenated alkyl, fiuoro, alkoxy, nitro, phenyl, phenoxy, aryl or other groups, provided that such substitutions do not interfere with synthesis or reaction.
• T further includes divalent functional groups such as sulfide, carbonyl, sulfoxide, and ether and divalent radicals of formula (XV)
• bis(phenol)s of formula (NIII) include 2,2-bis[4- hydroxyphenyl]propane; 4,4'-bis(4-hydroxyphenyl)diphenyl ether; 4,4'-bis(4- phenoxy)diphenyl sulf ⁇ de; 4,4'-bis(4-hydroxyphenyl)benzophenone ; 4,4'-bis(4- hydroxyphenyl)diphenyl sulfone; 2,2-bis[4-(3-hydroxyphenyl)phenyl]propane; 4,4'- bis(3-hydroxyphenyl)diphenyl ether; 4,4'-bis(3-hydroxy ⁇ henyl)diphenyl sulfide; 4,4'- bis(3-hydroxyphenyl)benzophenone; 4,4'-bis(3-hydroxyphenyl)diphenyl sulfone; 4- (3-hydroxyphenyl)-4'-(4-hydroxyphenyl)diphenyl-2,2-propan
• Useful substituted phthalic anhydrides have a nitro, chloro, bromo, or fiuoro group in the 3 or 4 position although chloro and bromo substituents are preferred. Also preferred are mixtures of structural isomers, for example a mixture comprising 3-halophthalic anhydride and 4-halophthalic anhydride.
• reaction conditions may be adjusted so as to minimize the formation of the ⁇ -alkylamino- ⁇ -alkylphthalimide (from the displacement of the halo group with alkylamine), a highly colored by-product which can impart an undesirable color to the product dianhydride.
• the YI of the product is less than about 25, and more preferably less than about 15 as measured by the UN spectrum of the product.
• a desired by-product of this reaction is substituted ⁇ -alkylphthalimide (III), which may be isolated and used for reaction with a dihydroxy compound (Nil) as described above.
• transimidization of bis(imide) (IN) is effected in the presence of 4-substituted tetrahydrophthalic anhydride (X)
• Useful substituents are nitro, chloro, fiuoro and bromo. Chloro and bromo substituents are preferred.
• 4-substituted tetrahydrophthalic anhydride (X) is available from the Diels-Alder condensation of the dienophile maleic anhydride with the 2- substitu ted- 1,3 -butadiene. Conditions for this reaction are known in the chemical literature.
• Aromatization may be achieved by any method known in the art such as those taught by U.S. Patent Nos. 5,233,054, 5,003,088, 5,059,697, and 4,978,760. Alternately, aromatization can be achieved in the presence of a transition metal oxide catalyst such as vanadium oxide (V 2 O 5 ) at a temperature in the range of about 250°C to about 270°C.
• a transition metal oxide catalyst such as vanadium oxide (V 2 O 5 ) at a temperature in the range of about 250°C to about 270°C.
• Transimidization with either substituted phthalic anhydrides (IX) or 4-substituted tetrahydrophthalic anhydride (X) may be conducted in an inert solvent such as water in the presence of a base such as triethylamine at a temperature in the range from about 150 to about 250°C, and preferably in the range from about 160 to about 180°C.
• an inert solvent such as water
• a base such as triethylamine
• transimidation is effected by reaction of bis(imide) (IV) with a 6-7 fold molar excess of substituted phthalic anhydride (IX) or 4-substituted tetrahydrophthalic anhydride (X) in water in the presence of at least one mole of base, e.g., triethylamine, per mole of anhydride at about 170°C for about one to about 1 to 2 hours.
• base e.g., triethylamine
• the aqueous reaction mixture is then continuously extracted in a packed column with an organic solvent, e.g., toluene, containing a base such as triethylamine to remove unconverted bis(imide) (IV) and the formed substituted N-alkylphthalimide (III) or 4-substituted N-alkyltetrahydrophthalimide (XI). Transimidation may continue within the column.
• the aqueous eluent from the column contains the tetraacid of dianhydride (V) and substituted phthalic diacid, both present as base conjugated salts.
• the aqueous solution is fed to a flash distillation vessel whereby a majority of the water and some of the base is removed.
• the bottoms from this vessel are fed to a wiped film evaporator under vacuum, where the base conjugated salts crack to liberate base with concomitant ring closure of diacids and tetraacids to anhydride and dianhydride.
• Water, base, and substituted phthalic anhydride or 4- substituted tetrahydrophthalic anhydride are taken overhead.
• the dianhydride is isolated as a molten liquid from the bottom of the wiped film evaporator.
• the base, water, and the substituted phthalic anhydride or 4-substituted tetrahydrophthalic anhydride from the flash vessel and from the wiped film evaporator are recycled back to the exchange reactor.
• the organic eluent from the extraction process is fed to a flash vessel wherein the solvent and the base are removed from the heavier organics. These overheads are recycled back to the bottom of the exchange column.
• the bottom from this flash vessel is fed to another flash vessel where substituted N-alkylphthalimide, when present, (or 4-substituted N-alkyltetrahydrophthalimide) is (III) taken over head.
• substituted N-alkylphthalimide may then be purified before being reused in the displacement reaction.
• 4-substituted N-alkyltetrahydrophthalimide When 4-substituted N-alkyltetrahydrophthalimide is present it must first be converted by aromatization to 4-substituted N-alkyl phthalimide then used in the displacement reaction.
• the bottom of the flash vessel primarily contains primarily recycled bis(imide) (IV), imide-anhydride (bisimide wherein only one of the imides has been converted to an anhydride), and some substituted N-alkylphthalimide (III) or 4-substituted N-alkyl phthalimide. These may be cycled back to the exchange reactor.
• Dianhydride (V) may then be reacted with diamine (VI) to yield poly(etherimide)s.
• Diamine (VI) has the structure
• R in formula (VI) includes but is not limited to substituted or unsubstituted divalent organic radicals such as: (a) aromatic hydrocarbon radicals having about 6 to about 20 carbon atoms and halogenated derivatives thereof; (b) straight or branched chain alkylene radicals having about 2 to about 20 carbon atoms; (c) cycloalkylene radicals having about 3 to about 20 carbon atoms, or (d) divalent radicals of the general formula (XII)
• Q includes but is not limited to divalent a divalent moiety selected from the group consisting of -O-, -S-, -C(O)-, -SO 2 -, C y H 2 k- (y being an integer from 1 to 5), and halogenated derivatives thereof, including perfluoroalkylene groups.
• Any diamino compound may be employed.
• suitable compounds are ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12- dodecanediamine, 1 ,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4- dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5- methylnonamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5- dimethylheptamethylenediamine, 2, 2-dimethylpropylenediamine, N-methyl-bis (3- aminopropyl) amine, 3-methoxyhexamethylenediamine, l,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sul
• a second, 2-liter Parr apparatus equipped with a magnetic, water-cooled agitator, a thermocouple, and a dip tube was used for pre-mixing the anhydride, triethylamine, and water.
• the line from the 2-liter Parr to the 600 mL Parr was % inch 316 stainless wrapped with electrical heat tape and insulated. The temperature of the vessel was controlled at 190°C.
• the contents of the 2-liter Parr were then transferred to the 600 mL Parr with nitrogen pressure, except for about 14 g, which remained in the second Parr.
• the contents of 600 mL Parr were maintained at 170°C.
• the reaction mixture went clear within 22 minutes.
• Approximately 2-mL samples of the reaction mixture were taken through a long dip tube while maintaining an inert atmosphere.
• the dip tube temperature was also maintained at about 180°C.
• the cooled samples were analyzed by infrared spectroscopy to determine the percent exchange.
• Percent solids are defined as the weight of BPA bis(imide) (XIII) divided by the total weight of solution.
• Transimidation reactions followed by continuous extraction to isolate the product dianhydride were conducted in an apparatus similar to that used for batch transimidation, except that the dip tube protruded into the reactor only about one-third of the way, and the reactor was further fitted with a 1 /8-inch 316 stainless steel tube extending to the bottom of the reactor.
• This tube was connected to a high pressure liquid chromatography (HPLC) system capable of delivering 40 mL per minute via of V ⁇ -inch 316 stainless steel tubing wrapped with electrical heating tape.
• HPLC high pressure liquid chromatography
• a recirculation loop on the toluene feed line was used to purge oxygen from the toluene feed equipment.
• the reactor was charged with the reactants as described above, (typically 17.0 g of bis(imide) (XIII) (Bl) and 9.0 g of anhydride (4-chlorophthalic anhydride unless otherwise indicated) in 100 g of an aqueous solution comprising 18 wt.% triethylamine, 16.5 wt.% anhydride, with the balance being water), yielding a final molar ratio of TEA:anhydride of about 1.1:1.
• reactants typically 17.0 g of bis(imide) (XIII) (Bl) and 9.0 g of anhydride (4-chlorophthalic anhydride unless otherwise indicated) in 100 g of an aqueous solution comprising 18 wt.% triethylamine, 16.5 wt.% anhydride, with the balance being water
• a portion of the aqueous phase (typically 17 to 25 mL) was then devolatized by charging to a clean 250-mL one-necked round-bottomed flask which was maintained under an inert atmosphere.
• the flask was placed in a GC oven and attached to a glass dual bulb Kugelrohr type extension on the outside of the oven using a glass extension piece.
• the dual bulb was cooled with an external dry ice/methylene chloride bath and attached to a Kugelrohr oscillating drive which was itself connected to a direct drive vacuum pump protected by a dry ice trap.
• the flask was placed slowly under full vacuum (generally 0.1 mm Hg or less) and the GC oven temperature program was slowly heated to 240°C. The total time in the oven was about one hour. The oven door was opened at the conclusion of the temperature program and the flask was allowed to air cool. Solidified dianhydride was removed from the flask and analyzed by IR spectroscopy to determine the percent exchange and the composition, respectively. Yellowness Index was determined by ASTM D1925.
• product dianhydride (XIV) having low color (YI 15.4) was isolated from a batch exchange reaction run at a 6:1 molar ratio of anhydride:bis(imide) (XIII) at 170°C, using a molar ratio of 1.1:1 triethylamine:anhydride for one hour, followed by toluene extraction and laboratory dianhydride isolation.
• Product dianhydride (XIV) having even lower color (YI 7) was isolated from a batch exchange reaction run at a 5:1 molar ratio of anhydride:bis(imide) (XIII), with a molar ratio of 1.1:1 triethylamine:anhydride and using 14.46% solids in the exchange reaction for 1 hour at 170°C, followed by 2% triethylamine in toluene extraction. Extent of exchange was about 52%.
• Conventional laboratory transimidation using phthalic anhydride and bis(imide) (XIII) yield product dianhydrides with a YI of 8 to 12.
• a Parr apparatus was charged with 100 mL of water, 12.0 g of bisimide (XIII), 32.8 g of 4-chlorotetrahydrophthalic anhydride, and 21.4 g of triethylamine.
• the molar ratio of 4-chlorotetrahydrophthalic anhydride:triethylamine:bisimide was 8:9.63:1.
• the vessel atmosphere was replaced with nitrogen, pressurized with 30 psi of nitrogen and then heated to 170°C. The reaction continued at 170°C for 2.3 hours with agitation. The reaction mixture was cooled to 80°C and the reactor was vented.
• reaction mixture was transferred to a separatory funnel and extracted once with 500 ml of toluene containing 30 ml of triethylamine at 80°C.
• a portion of the extracted aqueous phase was heated at 350°C on a hot plate for 10 minutes to remove 4-chlorotetrahydrophthalic anhydride, the N-methyl imide of 4- chlorotetrahydrophthalic anhydride, water and triethylamine.
• Infrared spectroscopy of the extracted aqueous phase residue showed that approximately 86% exchange had occurred.
• transimidation of a bisimide (IV) with either a substituted phthalic anhydride or a 4-subsituted tetrahydrophthalic anhydride provides a convenient, cost effective, and efficient route to poly(etherirnide)s and eliminates the nitration step required in previous poly(etherimide) syntheses. Additionally, transimidation can result in dianhydrides with a YI of less than about 25.

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