METHODS FOR THE PREPARATION OF POLY(ETHERIMIDES) S
BACKGROUND OF THE INVENTION
This invention relates to a method for the manufacture of poly(ethenmide)s More particularly, it relates to a method for the manufacture of poly(ethenmide)s which eliminates the need for an intermediate nitration step
Polyethenmides are high heat engineering plastics having a variety of uses As disclosed in US Patent Nos 4,417,044, 4,599,429, 4,902,809, and 4,921,970, the present commercial process for the synthesis of polyethenmides requires nitration of N-methylphthahmide 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
(Formula Removed)
Suitable displacement reactions are disclosed in U S Patent No 4,257,953 Displacement is also disclosed in US Patent Nos 5,132,423 and 5,872,294 Bisimide (I) is then reacted with a phthalic anhydride in an exchange reaction as disclosed in US Patent Nos 4,318,857, 4,329,291, 4,329,292, 4,329,496, and 4,340,545 to yield the dianhydnde (II)
(Formula Removed)
Reaction of dianhydnde (II) with a diamine results in polymenzation to a poly(ethenmide) Methods which improve or even eliminate any of the preceding steps would result in an improved synthesis of poly(ethenmide)s
BRIEF SUMMARY OF THE INVENTION
A new method for the synthesis of poly(ethenmide)s which eliminates the nitration step comprises synthesis and reaction of a substituted N-alkylphthahmide (III)
(Formula Removed)
with the disodium salt of a dihydroxy compound such as a bis(phenol) to yield the bis(imide) (IV)
(Formula Removed)
Bis(imide) (IV) is then subjected to transimidation to yield the dianhydnde (V)
(Formula Removed)
Transimidation is effected in the presence of a substituted phthahc anhydride, which yields a substituted N-alkylphthalimide that corresponds to the substituted phthahc anhydride as a by-product By-product substituted N-alkylphthahmide may then be recycled for use in the formation bisimide (IV)
In another embodiment, transimidation is effected in the presence of 4-substituted tetrahydrophthalic anhydride, which yields a 4-substituted N-alkyltetrahydrophthalunide as a by-product The by-product 4-substituted N-alkyltetrahydrophthahmide may be converted by aromatization to a 4-substituted N-alkylphthalimide, which may be used in the formation of bis(imide) (IV)
Finally, the reaction of dianhydnde (V) with a diamine (VI) having the structure
(Formula Removed)
yields poIy(ethenmide)s This route obviates the need for the intermediate nitration step required by the prior art synthesis
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A convenient route for the manufacture of poly(ethenmide)s comprises synthesis and reaction of a substituted N-alkylphthahmide (III)
(Formula Removed)
wherein the alkyl group is a branched or straight chain alkyl group having from one to about 18 carbons Preferably, 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 phthahc anhydride with a primary amine having the formula H2N-alkyl via a melt reaction, for example by contact of a gaseous primary amine such as methylamme with molten 4-halophthalic anhydride Halophthahc anhydrides may be obtained by aromatization of the corresponding halotetrahydrophthahc anhydrides as disclosed in US Patent Nos 5,233,054, 5,003,088, 5,059,697 and 4,978,760, which are incorporate by reference herein Halophthahc 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 phthahc anhydrides may be obtained by the nitration of phthahc anhydrides as taught in U S Patent No 5,155,234
Displacement of the substituent of the substituted N-alkylphthahmide (ITT) may be effected by treatment with the disodium salt of a dihydroxy compound having the formula (VII)
(Formula Removed)
to yield the bis(imide) (IV)
(Formula Removed)
wherein S is a divalent radical, for example a straight or branched cham 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, fluoro, alkoxy, mtro, 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 N-alkylphthalimide may be conducted in an inert solvent such as toluene, xylene, chJorobenzene or dichlorobenzene in the presence of a phase transfer catalyst such as hexaethylguanidimum 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 m the melt phase with the substituted N-alkyphthahmide
A particularly preferred dihydroxy compound is bis(phenol) (VIII)
(Formula Removed) ‘
wherein T is a single bond linking the two aryl groups, oi 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, fluoro, alkoxy, mtro, 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)
(Formula Removed)
Illustrative examples of bis(phenol)s of formula (VIII) include 2,2-bis[4-
hydroxyphenyljpropane, 4,4'-bis(4-hydroxyphenyl)diphenyl ether, 4,4'-bis(4-
phenoxy)diphenyl sulfide, 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-hydroxyphenyl)diphenyl sulfide, 4,4'-
bis(3-hydroxyphenyl)benzophenone, 4,4'-bis(3-hydroxyphenyl)diphenyl sulfone, 4-
(3-hydroxyphenyl)-4'-(4-hydroxyphenyl)diphenyl-2,2-propane, 4-(3-hydroxyphenyl)-
4'-(4-hydroxyphenyl)diphenyl ether, 4-(3-hydroxyphenyl)-4'-(4-
hydroxyphenyl)diphenyl sulfide, 4-(3-hydroxyphenyI)-4'-(4-
hydroxyphenyl)benzophenone, and 4-(hydroxyphenyl)-4'-(4-hydroxyphenyl)diphenyl sulfone dianhydnde, as well as various mixtures thereof These and other bis(phenol)s and dihydroxy compounds are described m U S Patent Nos 3,972,902 and 4,455,410
Bis(imide) (IV) is treated with a substituted phthalic anhydride (IX)
(Formula Removed)
via transimidation to yield dianhydnde (V)
(Formula Removed)
wherein S is as described above Useful substituted phthalic anhydrides have a nitro, chloro, bromo, or fluoro 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-halophthahc anhydride and 4-haiophthahc anhydride Surprisingly, reaction conditions may be adjusted so as to minimize the formation of the N-alkylammo-N-alkylphthalimide (from the displacement of the halo group with alkylamine), a highly colored by-product which can impart an undesirable color to the product dianhydnde Preferably, the YI of the product is less than about 25, and more preferably less than about 15 as measured by the UV spectrum of the product
A desired by-product of this reaction is substituted N-alkylphthahmide (III), which ma> be isolated and used for reaction with a dihydroxy compound (VII) as described above
In an alternative embodiment, transimidization of bis(imide) (IV) is effected in the presence of 4-substituted tetrahydrophthahc anhydride (X)
(Formula Removed)
Useful substituents are nitro, chloro, fluoro and bromo Chloro and bromo substituents are preferred 4-substituted tetrahydrophthahc anhydride (X) is available
from the Diels-Alder condensation of the dienophile maleic anhydnde with the 2-substituted-l,3-butadiene Conditions for this reaction are known in the chemical literature
The by-product of this transimidization is a 4-substituted N-alkyltetrahydrophthahmide (XI)
(Formula Removed)
4-substituted N-alkyltetrahydropbthahmide (XI) may be converted by aromatization to 4-substituted N-alkylphthalunide, which can be used in the displacement reaction with the dihydroxy compound as described above Aromatization may be achieved by any method known in die 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 (V2O5) at a temperature in the range of about 250°C to about 270°C
Transimidization with either substituted phthalic anhydrides (IX) or 4-substituted tetrahydrophthahc anhydnde (X) may be conducted m an inert solvent such as water in the presence of a base such as tnethylamine 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 For example, transimidation is effected by reaction of bis(imide) (TV) with a 6-7 fold molar excess of substituted phthalic anhydnde (IX) or 4-substituted tetrahydrophthahc anhydnde (X) in water in the presence of at least one mole of base, e g, tnethylamine, per mole of anhydnde at about I70°C for about one to about 1 to 2 hours
Preferably, the aqueous reaction mixture is then continuously extracted in a packed column with an organic solvent, e g, toluene, containing a base such as tnethylamine to remove unconverted bis(imide) (IV) and the formed substituted N-alkylphthahmide (HI) or 4-substituted N-alkyltetrahydrophthahmide (XI) Transimidation may continue withm the column The aqueous eluent from the column contains the
tetraacid of dianhydnde (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 evaporatoi under vacuum, where the base conjugated salts crack to liberate base with concomitant ring closure of diacids and tetraacids to anhydride and dianhydnde Water, base, and substituted phthalic anhydride or 4-substituted tetrahydrophthahc anhydride are taken overhead The dianhydnde 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 tetrahydrophthahc anhydride from the flash vessel and from the wiped film evaporator are recycled back to the exchange reactor
Preferably 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 lecycled back to the bottom of the exchange column The bottom from this flash vessel is fed to another flash vessel where substituted N-alkylphthahmide, when present, (or 4-substituted N-alkyltetrahydrophthahmide) is (III) taken over head Substituted N-alkylphthahmide may then be purified before being reused in the displacement reaction When 4-substituted N-alkyltetrahydrophthahmide is present it must first be converted by aiomatization to 4-substituted N-alkyl phthahmide then used in the displacement reaction The bottom of the flash vessel primarily contains primarily recycled bis(imide) (IV), lmide-anhydnde (bisimide wherein only one of the lmides has been converted to an anhydride), and some substituted N-alkylphthahmide (III) or 4-substituted N-alkyl phthahmide These may be cycled back to the exchange reactor
Dianhydnde (V) may then be reacted with diamine (VI) to yield poly(ethenmide)s Diamine (VI) has the structure
(Structure Removed)
wherein 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)
(Formula Removed)
wherein Q includes but is not limited to divalent a divalent moiety selected from the group consisting of -0-, -S-, -C(O)-, -S02-, CyH2k- (y being an integer from 1 to 5), and halogenated derivatives thereof, including perfluoroalkylene groups
Any diamino compound may be employed Examples of suitable compounds are
ethyl enediamme, propylenediamine, tnmethylenediamine, diethylenetnamine,
tnethylenetetramine, hexamethylenediamine, heptamethylenediamine,
octamethylenediamine, nonamethylenediarrune, decamethylenediamine, 1,12-
dodecanediamme, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-
dimethylheptamethylenediamme, 4-methylnonamethylenediamine, 5-
methylnonamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-
dimethylheptamethylenediamme, 2, 2-dimethylpropylenedianune, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, l,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide, 1,4-cyclohexanediamine, bis-(4-ammocyclohexyl) methane, m-phenylenediamine, p-phenylenediamme, 2,4-diammotoluene, 2,6-diammotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-l,3-phenylene-diamine, 5-methyl-4,6-diethyl-l,3-pheny]ene-diamine, benzidine, 3,3'-dimethylbenzidme, 3,3'-dimethoxybenzidme, 1,5-diaminonaphthalene, bis(4-aminophenyl) methane, bis(2-chloro-4-amino-3, 5-diethylphenyl) methane, bis(4-ammophenyl) propane, 2,4-bis(b-amino-t-buty]) toluene, bis(p-b-ammo-t-butylphenyl) ether, bis(p-b-methyl-o-ammophenyl) benzene, bis(p-b-methyl-o-ammopentyl) benzene, ), 3-diamino-4-isopropy]berjzene, bis(4-aminophenyl) sulfide, bis (4-ammophenyl) sulfone, bis(4-ammophenyl) ether and 1,3-bis(3-aminopropyl) tetramethyldisiloxane Mixtures of these compounds may also be present The
preferred diamino compounds are aromatic diamines, especially m- and p-phenylenediamine and mixtures thereof
All patents cited herein are incorporated by reference
The invention is further described by the following non-limiting examples
EXAMPLES
Batch transimidation (exchange) reactions were conducted in a Parr apparatus of 600 mL capacity with two quartz oblong windows on the opposite sides of the vessel, equipped with a glass liner, a water cooled magnetic drive device (modified such that all internal bearing surfaces were Teflon) which was speed controlled and a heating mantle controlled by a temperature controller A thermocouple was fitted to one of the ports on the reactor head, another port was fitted with a 680 psi rupture disc (rated at 170°C), and another port was fitted with a dip tube (1/8 inch 316 stainless steel) running to the bottom of the reactor The dip tube port was used for the aqueous phase manipulation, introduction of the organic phase to the reactor, and for maintaining pressure during the extraction procedure A zero volume coupling was connected to a nitrogen line equipped with a pressure indicator, a 580 psi relief spring valve, and appropriate needle valves for purging and placing the reactor under an inert atmosphere, e g, nitrogen
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, triethylamme, and water The line from the 2-liter Parr to the 600 mL Parr was VA inch 316 stainless wrapped with electrical heat tape and insulated The temperature of the vessel was controlled at 190°C
A typical experimental procedure is as follows Finely ground bis(imide) (XIII)
(Formula Removed)
(typically 25 7 g) was charged to the 600 mL Parr, and after replacing the atmosphere with nitrogen, the temperature of the Parr was raised to 170°C The contents of the vessel were isolated with needle valves and agitated The second, 2-liter Parr was charged with an aqueous mixture of phthahc anhydride or 4-chlorophthalic anhydride, tnethylamine (TEA) and water, and any additional anhydride (typically 320 grams of aqueous solution comprising 19 8% anhydride, 17 9% tnethylamine, balance water, 5 5 grams of additional anhydride) The water was degassed with nitrogen or helium prior to the addition of 4-chlorophthahc anhydride, which was followed by the addition of tnethylamine The contents of this vessel were isolated using the needle valves, placed under an inert atmosphere and then heated to 180°C Pressure typically rose to 190 psi
The contents of the 2-hter Parr were then transferred to the 600 mL Parr with nitrogen pressure, except for about 14 g, which remained m 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
Example 1 Batch Transimidation with 4-Chlorophthahc Anhydnde
4-Chlorophthahc anhydnde was reacted as descnbed above on a laboratory scale with bis(imide) (XIII) in water and m the presence of TEA, in which the molar ratio of 4-chlorophthahc anhydnde tnethylamine bis(imide) was 7 7 11 55 1 at 7 3% solids About 70% exchange occurred in one hour at 170°C to ultimately yield product dianhydnde (XIV)
(Formula Removed)
Percent solids are defined as the weight of BPA bis(imide) (XIII) divided by the total weight of solution
Example 2 Optimization of Transimidation Using 4-Chlorophthalic Anhydride
A series of batch laboratory exchange reactions were performed in order to define optimal operating parameters for transimidation using 4-chlorophthahc anhydride (C1PA), and in particular to determine the reaction rate and molar ratio of 4-chlorophthalic anhydride bis(imide) (XIII) (BI) required to achieve 65-70% exchange Formulations are shown in Table 1, and results are shown in Table 2
Table 1, 2 (Table Removed)
As the above data show, a molar ratio of about 6 1 of anhydride to bis(imide) was required to achieve 62 8% exchange in one hour, and a molar ratio of 7 67 1 is required to achieve 69 5% exchange in 70 minutes
Example 3 Transimidation/Extraction
Transimidation reactions followed by continuous extraction to isolate the product dianhydnde 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 '/i-mch 316 stainless steel tubmg wrapped with electrical heating tape This allowed delivery of the toluene/tnethylamine extraction solution to the bottom of the reactor, while the organic phase exited through the dip tube, which had a needle valve plumbed to an external cooling bath, and then to a collection vessel A recirculation loop on the toluene feed line was used to purge oxygen from the toluene feed equipment
In a typical procedure, the reactor was charged with the reactants as described above, (typically 17 0 g of bis(imide) (XIII) (BI) and 9 0 g of anhydride (4-chlorophthahc anhydride unless otherwise indicated) in 100 g of an aqueous solution comprising 18 wt % tnethylamme, 16 5 wt % anhydride, with the balance being water), yielding a final molar ratio of TEA anhydride of about 1 1 1
After reaction was completed, agitation was decreased to 10%, and about 1 liter of solution comprising about 2-3 wt % tnethylamme in toluene sparged with nitrogen was pumped into the Parr reactor at 20 ml/minute at 160-170°C The toluene phase exited the reactor through the dip pipe The exit flow rate was controlled by a needle valve on the exit line The exit flow rate was made to match the feed rate of the toluene/TEA solution Extraction was allowed to proceed for about 1 hour Aftei extraction, agitation was decreased and the contents of the reactor were cooled to about 85°C The contents of the reactor were then transferred under an inert
atmosphere to a 500-mL flask equipped with a bottom drain, and the phases were allowed to separate
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 m 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 piogram and the flask was allowed to air cool Solidified dianhydnde was removed from the flask and analyzed by IR spectroscopy to determine the percent exchange and the composition, respectively Yellowness Index was determined by ASTMD1925
Formulations and results are shown in Table 3 below
(Table Removed)
* Control using phthahc anhydride
**Percent Exchange on final product after completion of extraction
Further analysis indicated that product dianhydnde (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 170CC, using a molar ratio of 111 tnethylamine anhydride for one hour, followed by toluene extraction and laboratory dianhydnde isolation Product dianhydnde (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 tnethylamine anhydnde and using 14 46% solids in the exchange reaction for 1 hour at 170oC, followed by 2% tnethylamine in toluene extraction Extent of exchange was about 52% Conventional laboratory rransimidation using phthalic anhydride and bis(imide) (XIII) yield product dianhydndes with a YI of 8 to 12
Example 4 Transsudation with 4-halotetrahydrophthahc anhydnde
A Parr apparatus was charged with 100 mL of water, 12 0 g of bisimide (XIII), 32 8 g of 4-chlorotetrahydrophthahc anhydnde, and 21 4 g of tnethylamine The molar ratio
of 4-chIorotetrahydrophthahc anhydride triethylamme 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 A sample of the aqueous phase was removed from the reaction vessel and heated at 350°C on a hot plate for 10 minutes to remove 4-chlorotetrahydrophthalic anhydride, the N-methyl lmide of 4-chlorotetrahydrophthahc anhydride, water and triethylamme Infrared spectroscopy of the residue showed that approximately 75% exchange had occurred
The remaining reaction mixture was transferred to a separatory funnel and extracted once with 500 ml of toluene containing 30 ml of rnethylamme 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 lmide of 4-chlorotetrahydrophthahc anhydride, water and triethylamme Infrared spectroscopy of the extracted aqueous phase residue showed that approximately 86% exchange had occurred
As can be seen by the preceding examples transimidation of a bisimide (IV) with either a substituted phthahc anhydride or a 4-subsituted tetrahydrophthalic anhydride provides a convenient, cost effective, and efficient route to poly(ethenmide)s and eliminates the nitration step required in previous poly(ethenmide) syntheses Additionally, transimidation can result m dianhydndes with a YI of less than about 25
Example 5 Conversion of 4-chloro-N-methyl-tetrahydrophthalimide to 4-chloro-N-methyl-phthalimide
Gas phase reactions were earned out in a hot-tube reactor that was packed with about 13 grams of a catalyst containing V2O5 The inlet of the hot-tube reactor was connected to a flow controller and heated syringe pump The flow controller managed the flow of purified air The heated syringe pump contained 4-chloro-N-methyl tetrahydrophthahmide and delivered it to the hot tube reactor at a constant rate of 0 05 milliliters per minute The outlet of the hot tube reactor was connected to a
receiver cooled in an ice-bath where the reaction products were collected The hot-tube reactor was maintained at the 260°C The reaction product was analyzed by gas chromatographic techniques after the system had equilibrated for 10-20 minutes At a flow rate of 90ml/min all of the N-rnethyl-4-chlorotetrahydiophthalimide was converted to N-methyl-4-chlorophthahmide
While preferred embodiments have been shown and described, vanous modifications and substitutions may be made thereto without departing from the spirit and scope of the invention Accordingly, it is to be understood that the present invention has been described by way of illustration and not limitation

WHAT IS CLAIMED IS
1 A method for the synthesis of poly(ethenmide)s, comprising transimidation of a bis(imide) (IV)
(Formula Removed)
wherein the alkyl moiety is a straight or branched chain alkyl group having from 1 to about 18 carbon atoms, and S is a divalent radical selected from the group consisting of 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, an arylene group having from 6 to about 20 carbon atoms, and halogenated derivatives thereof, with a substituted phthalic anhydride having a subshtuent selected from the group consisting of nitro, bromo, fluoro and chloro to yield a dianhydnde (V)
(Formula Removed)
and reaction of dianhydnde (V) with diamine (VI)
(Formula Removed)
wherein R is selected from the group consisting divalent substituted or unsubstituted aromatic hydrocarbon radicals having about 6 to about 20 carbon atoms and halogenated derivatives thereof, divalent substituted or unsubstituted straight or branched chain alkylene radicals having about 2 to about 20 carbon atoms, divalent substituted or unsubstituted cycloalkylene radicals having about 3 to about 20 carbon atoms, and divalent radicals of the general formula (XII)
(Formula Removed)
wherein Q is a divalent moiety selected from the group consisting of-0-, -S-, -C(O)-, -SO2-, CyH2y- wherein y is an integer from 1 to 5, and halogenated derivatives thereof
2 The method of claim 1, wherein transimidation with the substituted phthalic anhydride yields a substituted N-alkylphthahmide
3 The method of claim 2 wherein the substituted N-alkylphthalimide is recycled for use in the formation of bisimide (IV)
4 The method of claim 1 wherein the substituted phthalic anhydride is a mixture of 3-substituted phthalic anhydride and 4-substituted phthalic anhydride
5 The method of claim 4 wherein the 3-substituted phthalic anhydride is 3-chlorophthahc anhydride and the 4-substituted phthalic anhydride is 4-chlorophthahc anhydride
6 The method of claim 4, wherein transimidation yields a mixture of 3-substituted N-alkylphthahmide and 4-substituted N-alkylphthalimide
7 The method of claim 6 wherein the mixture of 3-substituted N-alkylphthahmide and 4-substituted N-alkylphthahmide is recycled for use in the formation of bisimide (IV)
8 The method of claim 1 wherein the substituted phthalic anhydride is 4-chlorophthahc anhydride
9 The method of claim 8 wherein the transimidation yields N-alkyl-4-chlorophthalimide

10 The method of claim 9 wherein the N-alkyl-4-chlorophthahmide is recycled for use in the formation of bisimide (IV)
11 The method of claim 1, wherein the YI of the product dianhydnde is less than about 25
12 The method of claim 1, wherein the alkyl moiety is methyl
13 The method of claim 1, wherein S is derived from bisphenols having the formula
(VIII)
(Formula Removed)
wherein T is a single bond linking the two aryl groups, or a divalent, straight or branched chain alkylene radical having from one to about 20 carbon atoms, or a
divalent cycloalkylene group having from about 3 to about 20 carbon atoms, or a divalent arylene group having from 6 to about 20 carbon atoms, a divalent sulfide, carbonyl, sulfoxide, a divalent radicals of formula (XV)
(Formula Removed)
or a mixture thereof
14 The method of claim 13, wherein the bis(phenol) is selected from the group
consisting of 2,2-bis[4-bydroxyphenylJpropane, 4,4'-bis(4-hydroxyphenyl)diphenyl
ether, 4,4'-bis(4-phenoxy)diphenyl sulfide, 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)dipheny] ether, 4,4'-bis(3-
hydroxyphenyl)diphenyl sulfide, 4,4'-bis(3-hydioxyphenyl)benzophenone, 4,4'-bis(3-
hydroxyphenyl)diphenyl sulfone, 4-(3-hydroxyphenyl)-4'-(4-
hydroxyphenyl)diphenyl-2,2-propane, 4-(3-hydroxyphenyl)-4'-(4-
hydroxyphenyl)diphenyl ether, 4-(3-hydroxyphenyl)-4'-(4-hydroxyphenyl)diphenyl sulfide, 4-(3-hydroxyphenyl)-4'-(4-hydroxyphenyl)benzophenone, and 4-(hydroxyphenyl)-4'-{4-hydroxyphenyl)diphenyl sulfone dianhydnde, as well as vanous mixtures thereof
15 The method of claim 1, wherein diamine (VI) is selected from the group
consisting of ethylenediamine, propylenediamine, tnmethylenediamine,
diethylenetnamine, tnethylenetetramine, hexamethylenediamme,
heptamethylenediamine, octamethylenediamine, nonamethylenediamine,
decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-
methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-
methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-
dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamme, 2, 2-dimethylpropylenediamme, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, l,2-bis(3-aminopropoxy) ethane, bis(3-armnopropyl) sulfide, 1,4-cyclohexanediamuie, bis-(4-aminocyclohexyl) methane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamme, p-xylylenediamine, 2-methyl-4,6-diethyl-l,3-phenylene-diamme, 5-methyl-4,6-diethyl-l,3-phenylene-diamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 1,5-diammonaphthalene, bis(4-aminophenyl) methane, bis(2-chloro-4-ammo-3, 5-diethylphenyl) methane, bis(4-ammophenyl) propane, 2,4-bis(b-amino-t-butyl) toluene, bis(p-b-ammo-t-butylphenyl) ether, bis(p-b-methyl-o-ammophenyl) benzene, bis(p-b-methyl-o-aminopentyl) benzene, l,3-diamino-4-lsopropylbenzene, bis(4-aminophenyl) sulfide, bis (4-ammophenyl) sulfone, bis(4-aminophenyi) ether 1,3-bis(3-aminopropyl) tetramethyldisiloxane, and mixtures thereof
16 The method of claim 1, wherein diamine (VI) is m-phenylenediamme, p-phenylenediamme, or a mixture thereof
17 A method for the synthesis of a dianhydnde, comprising transimidation of a bis(imide) (IV)
(Formula Removed)
wherein the alkyl is moiety is a straight or branched chain alkyl group having from 1 to about 18 carbon atoms, and S is a divalent radical selected from the group consisting of 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, an arylene group having from 6 to about 20 carbon atoms in the presence of a substituted phthahc anhydride having a substituent selected from the group consisting of nitro, bromo, fluoro and chloro, to yield a dianhydnde (V)
18 (Formula Removed)
19 The method of claim 17, wherein the transimidation m the presence of the substituted phthahc anhydride yields a substitued N-alkylphthahmide
20 The method of claim 18 wherein the substituted N-alkylphthahmide is recycled for use m the formation of bisimide (IV)
21 The method of claim 17 wherein the substituted phthahc anhydride is a mixture of 3-substituted phthahc anhydride and 4-substituted phthahc anhydride
22 The method of claim 20 wherein the 3-substituted phthahc anhydride is 3-chlorophthahc anhydride and the 4-substituted phthahc anhydride is 4-chlorophthahc anhydride
22 The method of claim 21, wherein transimidation yields a mixture of 3-substituted N-alkylphthalimide and 4-substituted N-alkylphthahmide
23 The method of claim 22 wherein the mixture of 3-substituted N-alkylphthahmide and 4-substituted N-alkyJphthalimide is recycled for use in the formation of bisimide (IV)
24 The method of claim 17 wherein the substituted phthahc anhydride is 4-chlorophthahc anhydride
25 The method of claim 24 wherein the transimidation yields N-alkyl-4-
chlorophthahmide
26 The method of claim 25 wherein the N-alkyl-4-chlorophthahmide is recycled for use in the formation of bisimide (IV)
27 The method of claim 17, wherein the YI of the product dianhydnde is less than about 25
28 The method of claim 17, wherein the alkyl moiety is methyl
29 The method of claim 17, wherein S is derived from bisphenols having the formula (VIII)
(Formula Removed)
wherein T is a single bond linking the two aryl groups, a divalent straight or branched chain alkylene radical having from one to about 20 carbon atoms, a divalent cycloalkylene group having from about 3 to about 20 carbon atoms, a divalent arylene group having from 6 to about 20 carbon atoms, a divalent sulfide, carbonyl, sulfoxide, a divalent radicals of formula (XV)
(Formula Removed)
or a mixture thereof
30 The method of claim 29, wherein the bis(phenol) is selected from the group
consisting of 2,2-bis[4-hydroxyphenyl]propane, 4,4'-bis(4-hydroxyphenyl)diphenyl
ether, 4,4'-bis(4-phenoxy)diphenyl sulfide, 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-
hydroxyphenyl)diphenyl sulfide, 4,4'-bis(3-hydroxyphenyl)benzophenone, 4,4'-bis(3-
hydroxyphenyl)diphenyl sulfone, 4-(3-hydroxyphenyl)-4'-(4-
hydroxyphenyl)diphenyl-2,2-propane, 4-(3-hydroxyphenyl)-4'-(4-
hydroxyphenyl)diphenyl ether, 4-(3-hydroxyphenyl)-4'-(4-hydroxyphenyl)diphenyl sulfide, 4-(3-hydroxyphenyl)-4'-(4-hydroxyphenyl)benzophenone, and 4-(hydroxyphenyl)-4'-(4-hydroxyphenyl)diphenyl sulfone dianhydnde, as well as various mixtures thereof
31 A method for the synthesis of po]y(ethenmjde)s, comprising transimidation of a bis(imide) (IV)
(Formula Removed)
wherein the alkyl is moiety is a straight or branched chain alkyl group having from 1 to about 18 carbon atoms, and S is a divalent radical selected from the group consisting of 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, an arylene group having from 6 to about 20 carbon atoms, and halogenated derivatives thereof, with a 4-substituted tetrahydrophthahc anhydride having a substituent selected from the group consisting of nitro, chloro, fluoro, and bromo, to yield a dianliydnde (V
(Formula Removed)
and reaction of dianhydnde (V) with diamine (VI)
(Formula Removed)
wherein R is selected from the group consisting divalent substituted or unsubstituted aromatic hydrocarbon radicals having about 6 to about 20 carbon atoms and halogenated derivatives thereof, divalent substituted or unsubstituted straight or branched chain alkylene radicals having about 2 to about 20 carbon atoms, divalent substituted or unsubstituted cycloalkylene radicals having about 3 to about 20 carbon atoms, and divalent radicals of the general formula (X)
(Formula Removed)
wherein Q is a divalent moiety selected from the group consisting of -0-, -S-, -C(O)-, -SO2-, CyH2y- wherein y is an integer from 1 to 5, and halogenated denvatives thereof
32 The method of claim 31, wherein transimidation with the 4-substituted tetrahydrophthalic anhydride yields 4-substituted N-alkyltetrahydrophthalimide
33 The method of claim 32 wherem the 4-substituted N-alkyltetrahydrophthalimide is converted to the 4-substituted N-akyl phthahmide for use in the formation of bisimide (IV)
34 The method of claim 33 wherein the 4-substituted N-alkyltetrahydrophthalimide is converted to 4-substituted N-akyl phthahmide m the presence of vanadium oxide
35 The method of claim 31 wherein the 4-substituted tetrahydrophthalic anhydride is 4-chlorotetrahydrophthahc anhydride
36 The method of claim 35 wherein the transimidation yields N-alkyl-4-chloiotetrahydrophthahmide

37 The method of claim 31 wherein the N-alkyl-4-chIorotetrahydrophthalimide is converted to 4-chloro-N-alkyl-phthahmide for use in the formation of bisimide (IV)
38 The method of claim 31, wherein the YI of the dianhydnde is less than about 25
39 The method of claim 31 wherein the alkyl moiety is methyl
40 The method of claim 31, wherein S is derived from bisphenols having the formula (VIII)
(Formula Removed)
wherein T is a single bond linking the two aryl groups, or a divalent, straight or branched chain alkylene radical having from one to about 20 carbon atoms, or a divalent cycloalkylene group having from about 3 to about 20 carbon atoms, or a
divalent arylene group having from 6 to about 20 carbon atoms, a divalent sulfide, carbonyl, sulfoxide, a divalent radicals of formula (XV)
(Formula Removed)
or a mixture thereof
41 The method of claim 40, wherein the bis(phenol) is selected from the group
consisting of 2,2-bis[4-hydroxyphenyl]propane, 4,4'-bis(4-hydroxyphenyl)diphenyl
ether, 4,4'-bis(4-phenoxy)diphenyl sulfide, 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-
hydroxyphenyl)diphenyl sulfide, 4,4'-bis(3-hydroxyphenyl)benzophenone, 4,4'-bis(3-
hydroxyphenyl)diphenyl sulfone, 4-(3-hydroxyphenyl)-4'-(4-
hydroxyphenyl)diphenyl-2,2-propane, 4-(3-hydroxyphenyl)-4'-(4-
hydroxyphenyl)diphenyl ether, 4-(3-hydroxyphenyl)-4*-(4-hydroxyphenyl)diphenyl sulfide, 4-(3-hydroxyphenyl)-4'-(4-hydroxyphenyi)benzophenone, and 4-
(hydroxyphenyl)-4'-(4-hydroxyphenyl)diphenyl sulfone dianhydnde, as well as various mixtures thereof
42 The method of claim 31, wherem diamine (VI) is selected from the group consisting of ethylenediamine, propylenediamine, tnmethylenediamme, diethylenetriamine, tnethylenetetramine, hexamethylenediamine, heptamethylenediamme, octamethylenediamine, nonamethylenediamme, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamme, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamme, 4-methylnonamethylenediarnine, 5-methylnonamethylenediamme, 2,5-dimethylhexamethylenediarrune, 2,5-dimethylheptamethylenediamine, 2, 2-dimethylpropylenediamme, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide, 1,4-cyclohexanediamine, bis-(4-ammocyclohexyl) methane, m-phenylenediamine, p-phenylenediamme, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamme, 2-methyl-4,6-diethyl-l,3-phenylene-diamine, 5-methyl-4,6-diethyl-I,3-phenylene-diamme, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 1,5-diammonaphthalene, bis(4-aminophenyl) methane, bis(2-chloro-4-ammo-3, 5-diethylphenyl) methane, bis(4-ammophenyl) propane, 2,4-bis(b-amino-t-butyl) toluene, bis(p-b-amino-t-butylphenyl) ether, bis(p-b-methyl-o-aminophenyl) benzene, bis(p-b-methyl-o-aminopentyl) benzene, l,3-diammo-4-lsopropylbenzene, bis(4-aminophenyl) sulfide, bis (4-aminophenyl) sulfone, bis(4-ammophenyl) ether l,3-bis(3-ammopropyl) tetramethyldisiloxane, and mixtures thereof
43 The method of claim 31, wherein diamine (VI) is m-phenylenediamine, p-phenylenediamine, or a mixture thereof
44 A method for the synthesis of a dianhydnde, comprising transimidation of a bis(imide) (IV)
(Formula Removed)
wherein the alkyl is moiety is a straight or branched chain alkyl group having from 1 to about 18 carbon atoms, and S is a divalent radical selected from the group consisting of 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, an arylene group having from 6 to about 20 carbon atoms in the presence of a 4-substituted tetrahydrophthalic anhydride having a substituent selected from the group consisting of chloro, bromo, fluoro, and nitro, to yield a dianhydnde (V)
(Formula Removed)
45 The method of claim 44, wherein the transimidation in the presence of the 4-substituted tetrahydrophthalic anhydride yields a 4-substituted N-alkyltetrahydrophthahmide
46 The method of claim 45 wherein the 4-substituted N-alkyltetrahydrophthahmide is converted to the 4-substituted N-alkyl phthahmide for use in the formation of bisimide (IV)
47 The method of claim 46 wherein the 4-substituted N-alkyltetrahydrophthahmide is converted to the 4-substituted N-alkyl phthahmide in the presence of vanadium oxide
48 The method of claim 44 wherein the 4-substituted tetrahydrophthalic anhydride is 4-chlorotetrahydrophthahc anhydride
49 The method of claim 48 wherein the transimidation yields N-alkyl-4-chlorotetrahydrophthalimide
50 The method of claim 49 wherein the N-alkyl-4-chlorotetrahydrophthahmide is converted to 4-chloro N-a!kyl phthalimide for use m the formation of bisimide (IV)
51 The method of claim 44, wherein the YI of the product poly(ethenmide) is less than about 25
52 The method of claim 44 wherein the alkyl moiety is methyl
53 The method of claim 44, wherein S is derived from bisphenols having the formula (VIII)
(Formula Removed)
wherein T is a single bond linking the two aryl groups, a divalent straight or branched chain alkylene radical having from one to about 20 carbon atoms, a divalent cycloalkylene group having from about 3 to about 20 carbon atoms, a divalent arylene group having from 6 to about 20 carbon atoms, a divalent sulfide, carbonyl, sulfoxide, a divalent radicals of formula (XV)
(Formula Removed)
or a mixture thereof
54 The method of claim 53, wherein the bis(phenol) is selected from the group
consisting of 2,2-bis[4-hydroxyphenyl]propane, 4,4'-bis(4-hydroxyphenyl)diphenyl
ether, 4,4'-bis(4-phenoxy)diphenyl sulfide, 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-
hydroxyphenyl)diphenyl sulfide, 4,4'-bis(3-hydroxyphenyl)benzophenone, 4,4'-bis(3-
hydroxyphenyl)diphenyl sulfone, 4-(3-hydroxyphenyl)-4'-(4-
hydroxyphenyl)diphenyl-2,2-propane, 4-(3-hydroxyphenyl)-4'-(4-
hydroxyphenyl)diphenyl ether, 4-(3-hydroxyphenyl)-4'-(4-hydroxyphenyl)diphenyl sulfide, 4-(3-hydroxyphenyl)-4'-(4-hydroxyphenyl)benzophenone, and 4-(hydroxyphenyl)-4'-(4-hydroxyphenyl)diphenyl sulfone dianhydnde, as well as various mixtures thereof
55 A method for the synthesis of poly(ethenmide)s substantially as herein descnbed with reference to the foregoing examples
56 A method for the synthesis of a dianhydnde substantially as herein described with reference to the foregoing examples