Title of Invention	METHOD TO PREPARE BIS (HALOIMIDES)
Abstract	A method for preparing a bis(halophthalimide), said method comprising: preparing a mixture comprising a halophthalic anhydride and a solvent, adding to the mixture formed in step (A) a molten diamine to form a reaction mixture, said reaction mixture being characterized by "an initial molar ratio of halophthalic anhydride to diamine", wherein the molten diamine has the formula H2N-A1-NH2 wherein A1 is a C2-C40 divalent aromatic radical; heating the reaction mixture formed in step (B) to a temperature of at least 100°C, optionally in the presence of an imidization catalyst, and removing the water of imidization; analyzing the reaction mixture formed by the combination of steps (A)-(C) to determine the initial molar ratio of halophthalic anhydride to diamine; and adding anhydride or diamine to the mixture formed by the combination of steps (A)-(C) to achieve a "corrected molar ratio" of halophthalic anhydride to diamine, said corrected molar ratio being in a range between about 2.01 and about 2.3, and heating to a temperature of at least 100°C to obtain a bis(halophthalimide) product mixture that is substantially free of water.

Title of Invention

METHOD TO PREPARE BIS (HALOIMIDES)

Abstract

A method for preparing a bis(halophthalimide), said method comprising: preparing a mixture comprising a halophthalic anhydride and a solvent, adding to the mixture formed in step (A) a molten diamine to form a reaction mixture, said reaction mixture being characterized by "an initial molar ratio of halophthalic anhydride to diamine", wherein the molten diamine has the formula H2N-A1-NH2 wherein A1 is a C2-C40 divalent aromatic radical; heating the reaction mixture formed in step (B) to a temperature of at least 100°C, optionally in the presence of an imidization catalyst, and removing the water of imidization; analyzing the reaction mixture formed by the combination of steps (A)-(C) to determine the initial molar ratio of halophthalic anhydride to diamine; and adding anhydride or diamine to the mixture formed by the combination of steps (A)-(C) to achieve a "corrected molar ratio" of halophthalic anhydride to diamine, said corrected molar ratio being in a range between about 2.01 and about 2.3, and heating to a temperature of at least 100°C to obtain a bis(halophthalimide) product mixture that is substantially free of water.

Full Text	METHOD TO PREPARE BIS(HALOIMIDES) BACKGROUND OF THE INVENTION This invention relates to an improved method for the preparation of bis(halophthalimides), monomers useful for the preparation of polyetherimides. Various types of polyethers, such as polyetherimides, poiyethersulfones, polyetherketones, and polyethertherketoncs, have become important as engineering resins by reason of their excellent properties. These polymers are typically prepared by the reaction of dihydroxyaromatic compounds, such as bisphenol A disodium salt, with dihaloaromatic compounds. For example, polyetherimides arc conveniently prepared by the reaction of salts of dihydroxyaromatie compounds with bis(halophthalimides). U.S. Pat. Nos. 5,229,482 and 5,830,974, disclose the preparation of aromatic polyethers in relatively non-polar solvents, using a phase transfer catalyst which is substantially stable under the polymerization conditions. Solvents disclosed in U.S. Pat. No. 5,229,482 include o-dichlorobenzene, dichlorotoluene, 1,2,4- trichlorobenzene and diphenyl sulfone. U.S. Pat. No. 5,830,974 discloses the use of solvents such as anisole, diphenylether, and phenetole. Solvents of the same type may be used for the preparation of bis(halophthalimidc) intermediates for polyetherimides. In each of U.S. Pat. Nos. 5,229,482 and 5,830,974 the bis(halophthalimidc) is introduced into the polymerization reaction as a substantially pure, isolated compound. This process step is often difficult, since solid bis(halophthalimdes) are typically of very low density and fluffy, making weighing and handling burdensome. U.S. Pat. No. 6,235,866 teaches a method of slurry preparation of bis(halophthalimides) by the reaction between diamine compounds and halophfhalic anhydride, in equimolar proportions and use of that slurry as such to prepare polyether polymers. But in the disclosed process, considerable caking of the product bis(halophthalimides) occurs, rendering the product difficult to isolate as a pure slurry, resulting in unacceptable levels of residual starting material in the polymer. Also, the presence of water in the resulting product has a deleterious effect on the molecular weight of the polymer. If proper stoichiometric balance between the diamine and the halophthalic anhydride is not maintained, several undesirable by-products remain in the slurry which limit the molecular weight of the polymer, and/or result in polymers with amine end groups Thus there is a need in the art to develop a facile process for the preparation of bis(halophthalimides) having suitable characteristics for conversion to polyefherimide polymers without isolation which overcomes the shortcomings of current synthetic methods. BRIEF SUMMARY OF THE INVENTION The present invention provides a method for preparing a bis(halophthalimide), said method comprising: (A) preparing a mixture comprising at least one halophthalic anhydride and at least one solvent, (B) adding to the mixture formed in step (A) at least one diamine, to form a reaction mixture, said reaction mixture being characterized by "an initial molar ratio of halophthalic anhydride to diamine"; (C) heating the reaction mixture formed in step (B) to a temperature of at least 100°C, optionally in the presence of an imidization catalyst; (D) analyzing the reaction mixture formed by the combination of steps (A)-(C) to determine the initial molar ratio of halophthalic anhydride to diamine; and (E) performing one step selected from the group consisting of: (i) adding anhydride or diamine to the mixture formed by the combination of steps (A)-(C) to achieve a "corrected molar ratio" of halophthalic anhydride to diamine, said corrected molar ratio being in a range between about 2.01 and about 2.3, and heating to a temperature of at least 100°C to obtain a bis(halophthalimide) product mixture that is substantially free of water; and(ii) heating to a temperature of at least 100°C the reaction mixture formed by the combination of steps (A)-(C) to obtain a bis(halophthalimide) product mixture that is substantially free of water. DETAILED DESCRIPTION OF THE INVENTION The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. In the following specification and the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings: The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not. As used herein the term "integer" means a whole number which includes zero. For example, the expression "n is an integer from 0 to 4" means "n" may be any whole number from 0 to 4 including 0 and 4. Similarly, the expression "an integer ranging from 1 to 4 inclusive" means an integer in a range from 1 to 4 , said range including the integer 1 and the integer A., As used herein the term "aliphatic radical" refers to a radical having a valence of at least one comprising a linear or branched array of atoms which is not cyclic. The array may include heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen or may be composed exclusively of carbon and hydrogen. Aliphatic radicals may be "substituted" or "unsubstituted". A substituted aliphatic radical is defined as an aliphatic radical which comprises at least one substituent. A substituted aliphatic radical may comprise as many substituents as there are positions available on the aliphatic radical for substitution. Substituents which may be present on an aliphatic radical include but are not limited to halogen atoms such as fluorine, chlorine, bromine, and iodine. Substituted aliphatic radicals include trifluoromethyl, hexafluoroisopropylidene, chloromethyl; difluorovinylidene; triehloromethyl, bromoethyl, bromotrimethylene (e.g. -CH2CHBrCH2-), and the like. For convenience, the term "unsubstituted aliphatic radical" is defined herein to encompass, as part of the "linear or branched array of atoms which is not cyclic" comprising the unsubstituted aliphatic radical, a wide range of functional groups. Examples of unsubstituted aliphatic radicals include ally], carbonyl, dicyanoisopropylidene (i.e. - CH2C(CN)2CH2-), methyl (i.e. -CH3), methylene (i.e. -CH2-), ethyl, ethylene, formyl,, hexyl, hexamethylene, hydroxymethyl (i.e.-CH2OH), mercaptomcthyl (i.e. -CH2SH), methylthio (i.e. -SCH3), methylthiomethyl (i.e. -CH2SCH3), methoxy. methoxycarbonyl (CH3OCO) , nitromethyl (i.e. -CH2NO2), thiocarbonyl, trimethylsilyl, t-butyldimethylsilyl, trimethyoxysilylpropyl, vinyl, vinylidene, and the like. Aliphatic radicals are defined to comprise at least one carbon atom. A C1- C10 aliphatic radical includes substituted aliphatic radicals and unsubstituted aliphatic radicals containing at least one but no more than 10 carbon atoms. As used herein, the term "aromatic radical" refers to an array of atoms having a valence of at least one comprising at least one aromatic group. The array of atoms having a valence of at least one comprising at least one aromatic group may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen. As used herein, the term "aromatic radical" includes but is not limited to phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene, and biphenyl radicals. As noted, the aromatic radical contains at least one aromatic group. The aromatic group is invariably a cyclic structure having 4n+2 "delocalized" electrons where "n" is an integer equal to 1 or greater, as illustrated by phenyl groups (n = 1), thienyl groups (n = 1), furanyl groups (n = 1), naphthyl groups (n = 2), azulenyl groups (n = 2), anthraceneyl groups (n = 3) and the like. The aromatic radical may also include nonaromatic components. I •"or example, a ben/.yl group is an aromatic radical which comprises a phenyl ring (the aromatic group) and a methylene group (the nonaromatic component). Similarly a tctrahydronaphthyl radical is an aromatic radical comprising an aromatic group (C6H3) fused to a nonaromatic component -(CH2)4-. Aromatic radicals may be "substituted" or "unsubstituted". A substituted aromatic radical is defined as an aromatic radical which comprises at least one substituent. A substituted aromatic radical may comprise as many substituents as there are positions available on the aromatic radical for substitution. Substituents which may be present on an aromatic radical include, but arc not limited to halogen atoms such as fluorine, chlorine, bromine, and iodine. Substituted aromatic radicals include trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phenyloxy) (i.e. - OPhC(CF3)2PhO-), chloromethylphenyl; 3-trifluorovinyl-2~thienyl; 3- trichloromethylphenyl (i.e. 3-CCl3ph-), bromopropylphenyl (i.e. BrCH2CH2CFI2Ph-), and the like. For convenience, the term "unsubstituted aromatic radical" is defined herein to encompass, as part of the "array of atoms having a valence of at least one comprising at least one aromatic group", a wide range of functional groups. Examples of unsubstituted aromatic radicals include 4-allyloxyphenoxy, 4-benzoylphenyl, dicyanoisopropylidenebis(4-phenyloxy) (i.e. -OPhC(CN)2PhO-), 3-methylphenyl, methylenebis(4-phenyloxy) (i.e. -OPhCH2PhO-), ethylphenyl, phenylethenyl, 3- formyl,-2-thienyl, 2-nexyl-5-furanyl; hexamethylcne-l,6-bis(4-phenyloxy) (i.e. - OPh(CH2)6PhO-); 4-hydroxymethylphenyl (i.e. 4-HOCH2Ph-), 4- mercaptomethylphemyl, (i.e. 4-HSCH2Ph-), 4-methylthiophenyl (i.e. 4-CH3SPh-), methoxyphenyl, methoxycarbonylphenyloxy (e.g. methyl salicyl), nitromethylphenyl (i.e. -PhCH2NO2), trim ethyl silylphenyl, t-butyldimefhylsilylphenyl, vinylphenyl, vinylidenebis(phenyl), and the like. The term "a C3 ~ Cio aromatic radical" includes substituted aromatic radicals and unsubstituted aromatic radicals containing at least three but no more than 10 carbon atoms. The aromatic radical 1-imidazolyl (C3112N2-) represents a C3 aromatic radical. The benzyl radical (C7I-V) represents a C7 aromatic radical. As used herein the term "cycloaliphatic radical" refers to a radical having a valence of at least one, and comprising an array of atoms which is cyclic but which is not aromatic. As defined herein a "cycloaliphatic radical" does not contain an aromatic group. A "cycloaliphatic radical" may comprise one or more noncyclic components. For example, a cyclohexylmethyl group (C6H11CH2-) is a cycloaliphatic radical which comprises a cyclohexyl ring (the array of atoms which is cyclic but which is not aromatic) and a methylene group (the noncyclic component). The cycloaliphatic radical may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen. Cycloaliphatic radicals may be "substituted" or "unsubstituted". A substituted cycloaliphatic radical is defined as a cycloaliphatic radical which comprises at least one substituent. A substituted cycloaliphatic radical may comprise as many substituents as there are positions available on the cycloaliphatic radical for substitution. Substituents which may be present on a cycloaliphatic radical include but are not limited to halogen atoms such as fluorine, chlorine, bromine, and iodine. Substituted cycloaliphatic radicals include trifluoromethylcyclohexyl, hexafluoroisopropylidenebis(4-cyclohexyloxy) (i.e. -O C6HioC(CF3)2 CfJiioO-), chloromethylcyclohcxyl; 3-trifluorovinyl-2-cyclopropyl; 3-trichloromethylcyclohexyl (i.e. 3-CCl3C6H]0-), bromopropylcyclohexyl (i.e. BrCH2CH2CH2 C(,H\o-), and the like. For convenience, the term "unsubstituted cycloaliphatic radical" is defined herein to encompass a wide range of functional groups. Examples of unsubstituted cycloaliphatic radicals include 4- allyloxycyclohexyl, 4-acetyloxycyclohexyl, dicyanoisopropylidcncbis(4- cyclohexyloxy) (i.e. -O C6H]oC(CN)2 C6HioO-), 3-methylcyclohexyl, methylenebis(4- cyclohexyloxy) (i.e. -O C6H10CH2 C6H10O-), ethylcyclobutyl, cyclopropylethenyl, 3- formyl,-2-terahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl; hexamefhylene-1,6-bis(4- cyclohexyloxy) (i.e. -O Ce,Hjo (CH2)6 C6HioO-); 4-hydroxymethylcyclohexyl (i.e. 4- HOCH2 C6H,o-), 4-mercaptomethylcyclohexyl (i.e. 4-HSCH2 C6HK,-), 4- mefhylthiocyclohexyl (i.e. 4-CH3S C(,U]0-), 4-methoxycyclohcxyl. 2- methoxycarbonylcyclohexyloxy (2-CH3OCO C6H10O-), nitromcthylcyclohcxyl (i.e. NO2CH2C6H10-), trimethylsilylcyclohexyl, t-butyldimcthylsilylcyclopentyl: 4- trimethoxysilylethylcyclohexyl (e.g. (CHsO^SiCI-kCI-kCfJ-Iio-), vinylcyclohexenyi, vinylidenebis(cyclohexyl), and the like. The term "a C3 - C\0 cycloaliphatic radical" includes substituted cycloaliphatic radicals and unsubstituted cycloaliphatic radicals containing at least three but no more than 10 carbon atoms. The cycloaliphatic radical 2-tetrahydrofuranyl (C4H7O-) represents a C4 cycloaliphatic radical. The cyclohexylmethyl radical (C6MnCH2-) represents a C7 cycloaliphatic radical. As noted the present invention relates to a method for the efficient preparation of bis(halophthalimides). In one embodiment the present invention relates to a method for the prepartion of bis(halophfhalimides) having structure 1 wherein X is independently in each instance, a fluorine, chlorine, bromine or iodine group; and Q is a C2-C20 divalent aliphatic radical, a C2-C40 divalent aromatic radical, or a C4-C20 divalent cycloaliphatic radical; p is independently at each occurrence an integer in a range from 1 to 4 inclusive. Bis(halophthalimides) having structure 1 are illustrated by l,3-bis[N-(4- chlorophthalimido)]benzene (hereinafter sometimes "C1PAMI"). It should be noted that bis(halophthalimides) prepared from a mixture of 3-chlorophthalic anhydride and 4-chlorophthalic anhydride are also at times referred to as "C1PAMI". There is no particular limitation on the diamine component. Any diamine compound may be employed and used according to the method of this invention. Typically, the diamine compound comprisies at least one compound having structure 11: H2N-A1-NH2 II wherein A is a C2-C20 divalent aliphatic radical, a C2-C40 divalent aromatic radical, or a C4-C20 divalent cyloaliphatic radical. Suitable aliphatic diamine compounds represented by structure II (A1 is a C2-C20 divalent aliphatic radical) include efhylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, and 1, 10-diaminodecane. Suitable aromatic diamine compounds represented by structure II (A1 is a C2-C40 divalent aromatic radical) include 1, 4-dimainonaphthalene, 2, 6- dimainonaphthalene, 4, 4'-diaminobiphenyl, and the like. Suitable cycloaliphatic diamine compounds represented by structure II (A1 is a C4-Q>o divalent cycloaliphatic radical) include trans-l,2-diaminocyelopentane, trans- l,4-(bis aminomethyl)cyclohexane, and the like. In one embodiment, the diamine compound is selected from the group consisting of oxydianiline, bis(4-aminophenyl)sulfone, meta-phenylendiarnine and para- phenylenediamine and mixtures thereof. In a preferred embodiment of the invention, the diamine compound is selected from the group represented by structures III and IV wherein R and R are independently at each occurrence a halogen atom, a nitro group, a cyano group, a C2-C20 aliphatic radical, a C2-C40 aromatic radical, or a C4-C?o divalent aliphatic radical; and "n" and "m" are independently integers ranging from about 0 to about 4. Examples of suitable compounds are meta-phenylenediaminc, para-phenylenediaminc, 2,4-diaminotoluene, 2,6-diaminotolucne, 2-mcthyl-4,6- diethyl-1,3-phenylenediamine, 5-methyl-4,6-diethyl-l ,3-phenylenediamine, 1,3- diamino-4-isopropylbenzene, and combinations thereof. The halophthalic anhydrides employed according to the method of the present invention are typically cyclic anhydrides represented by structure V wherein X1 is chloro, bromo, or fluoro, and p is an integer in a range from 1 to 4 includive. 4-chlorophthalic anhydride (CAS 11 118-45-6) is a preferred anhydride. As noted, the method of the present invention employs a solvent. Thus, in step (A) of the method of the present invention a mixture comprising at least one halophthalic anhydride and at least one solvent is prepared. Preferably the solvent is an inert solvent. Suitable solvents include dichlorobenzenes, dimethyl formamide, dimethylacetamide, N-methylpyrrolidone, dichlorotoluene, 1,2,4-trichlorobenzene, diphenyl sulfone, monoalkoxybenzencs such as anisole, and the like, and mixtures thereof. In a preferred embodiment, the inert solvent is chosen such that the boiling point of the solvent system is at least about 20°C higher than the boiling point of water under the prevailing reaction conditions. The prevailing reaction conditions include the temperature and pressure at which the imidization reaction is carried out. In one embodiment, the imidization reaction is canned out under superatmospheric pressure (i.e. the pressure is greater than 1 atmosphere). Ortho-dichlorobenzene (o- DCB) is frequently a the solvent of choice for the reaction. In one embodiment, the halophthalic anhydrideis added to the solvent of choice with vigorous stirring while keeping the mixture hot. Temperatures greater than 150°C are preferred. The solvent, the diamine and the halophthalic anhydride are typically combined in amounts such that the total solids content during the reaction to form the bis(halophthalimide) does not exceed about 25 percent by weight, more preferably the total solids content during the reaction to form the bis(halophthalimide) does not exceed about 17 percent by weight. "Total solids content" expresses the proportion of the reactants as a percentage of the total weight including liquids present in the reaction at any given time. In one embodiment, as solvent and water arc distilled from the reaction mixture, additional solvent is added to maintain the total solids content within the preferred range. The terms total solids content and "% solids" are used interchangeable herein. This is effected by the addition of solvent to compensate for any increase in solids content. In a second step, step (B), at least one diamine is added to the mixture comprising the halophthalic anhydride and the solvent prepared in step (A) to form a reaction mixture. The diamine compound is metered into the mixture formed in step (A). The diamine compound may be added either as a solid, a melt, or in solution in an inert solvent. In a preferred embodiment, the diamine compound is added as a hot melt at a an addition rate which is sufficiently slow to ensure sufficient mixing of the reactants and to avoid undue caking of solids in the reaction medium. The addition of the diamine compound is were also carried out in such a fashion so that the solids content of the reaction mixture is maintained at less than about 25% by weight, more preferably less than about 17% by weight. The reaction mixture formed in step (B) is said to be characterized by an "initial molar ratio of halophthalic anhydride to diamine". The "initial molar ratio of halophthalic anhydride to diamine" is the "actual" or "true" ratio of halophthalic anhydride moieties to diamine moieties present in the reaction mixture in step (B). As a result of the uncertainty in the weights of reactants used the "initial molar ratio of halophthalic anhydride to diamine" typically has a value which is different than the ratio calculated based upon the weights of halophthalic anhydride and diamine added in steps (A) and (B). Uncertainty in the weights of halophthalic anhydride and diamine used can be pronounced when large- scale reactions are being carried out. Moreover, a stoichiometric imbalance can lead to undesired consequences such as "clumping" of the product bis(halophthalimide). The "actual" molar ratio can be determined by performing an high performance liquid chromatography (HPLC) analysis on the reaction mixture after most of the reactants have been converted to the bis(halophfhalirnide) product. With respect to the amounts of halophthalic anhydride and diamine employed, it is preferable to have an excess of the halophthalic anhydride in the reaction mixture. Preferably, 2.01 to 3.0 molar equivalents of the halophthalic anhydride with respect to the diamine compounds are employed, more preferably 2.01 to 2.5 molar equivalents of the halophthalic anhydride with respect to the diamine compound are employed. Typically, the bis(halophthalimide) product is produced in a slurry form that is largely free from by-products and unreacted reactants, and isolation and purification of the bis(halophthalimide) product from the slurry is not required prior to polymerization to form polyetherimide. In some embodiments an imidization catalyst may be added to the reaction mixture. Suitable imidization catalysts are known in the art. They include salts of organophosphorus acids, particularly phosphinates such as sodium phenylphosphinate (SPP) and heterocyclic amines such as 4-dimethylaminopyridine (DMAP). Organic and inorganic acids may also be used to catalyze this reaction. Suitable organic acids include chlorophthalic acid, phthalic acid, and acetic acid. Sodium phenylphosphinate is generally preferred. The catalyst, when opted for, may be added before the diamine compound has been added, after the diamine compound has been added, or together with the diamine compound. In a preferred embodiment of the present invention, the catalyst, when used in the reaction mixture, is added after the addition of the diamine compound. Step (C) of the method of the present invention comprises heating the reaction mixture formed in step (B) to a temperature of at least 100°C , optionally in the presence of the imidization catalyst described. Typically the reaction mixture is heated to a temperature of at least 150°C, preferably in a range from about 150°C to about 250°C, and more preferably in a range from about 175°C to about 225"C. It should be note that the reaction mixture may be heated at atmospheric pressure, subatomsphheric pressure or superatomospheric pressure. When superatmospheric pressures are employed the pressure is typically up to about 5 atmospheres, to facilitate the conversion starting materials product bis(halophthalimide). Typically, step (C) also provides for the removal of at least some of the water of imidization resulting from reaction of the halophthalic anhydride with the diamine. In one embodiment, about 95 % of the water of imidization is removed in step (C). In step (D) the reaction mixture formed by the combination of steps (A)-(C) is analyzed to determine the "initial molar ratio of halophthalic anhydride to diamine". As note, in conventional methods for the production of bis(halophfhalnnides), the amount of halophthalic anhydride present in the reaction mixture can only be roughly estimated based on the initial added amount. In one aspect of the invention, a suitable analytical tool may be employed to determine accurately the amount of each the reactants initially employed. This information may then be used to determine if any of the reactants need to be added to compensate for the deficiency of the same. In one embodiment of the invention, the analytical tool used to determine the initial molar ratio of halophthalic anhydride to diamine is a chromatographic method. In a typical embodiment of the present invention, a high performance liquid chromatography (HPLC) technique is used. Other analytical methods such as, but not limited to, gas chromatography, infra-red spectroscopy, ultraviolet spectroscopy, and the like may be used to monitor the reaction. In step (E) any stoichiometric deficiency revealed by determining the initial molar ratio halophthalic anhydride to diamine is corrected by the addition of halophthalic anhydride or diamine to achieve a "corrected molar ratio" of halophthalic anhydride to diamine. Typically, because the quantity of halophthalic anhydride or diamine needed to correct the stoichiometry is small, weighing errors can be minimized using small more reliable mass measuring equipment. The corrected molar ratio is generally much closer to the molar ratio of reactants intended initially than is the initial molar ratio. In a further embodiment of the invention, the analytical tool used to monitor the reaction mixture is also coupled to a controlling unit that is capable of automatically monitoring and maintaining the stoichiometry between the reactants. A further feature of the present invention is the solids content of the reaction mixture which at any given time during the course of the reaction should be typically less than 25% by weight, preferably in the range from about 10% to about 17% by weight. By "solids content" is meant the proportion of the reactants as a percentage of the total weight including liquids. This is effected by the addition of solvent to compensate for any increase in solids content. Another embodiment of the present invention involves the removal of water from the reaction mixture, lire water may be present in the system from a variety of sources; the reactor, or as a component of one or more of the reactants or solvents employed. Moreover, water is also produced as the by-product of the imidization reaction. Regardless of its origin, the presence of residual water in the product bis(halophfhalimide) is detrimental to the polymerization reaction for which the bis(halophthalimide) is typically intended. Thus, in one aspect, the present invention provides a bis(halophthalimide) product which is suitable for use in a polymerization reaction to form polyefherimide. Typically, at least 95% of the water present during step (C) of the reaction is removed from the reaction mixture during step (C) and the remaining water is removed during step (D). Water removal may be accomplished using means well-known in the art such as a distillation process. In one embodiment of the invention, the reactor is designed such that water is removed efficiently using flush mounted valves , wherein the valves are properly designed with low volume configuration and the reaction vessel is devoid of any water retention zones. In one embodiment, the reaction vessel comprises spray nozzles from which hot solvent (e.g. hot o-DCB) is directed at the reactor walls outlets in order to "chase" water from the reactor directing a spray of hot solvent on the interior surfaces of the reactor (typically surfaces which are above the level of the contents of the reaction vessel) serves to drive water adhering to the walls of the reactor from the reactor, and has the added benefit of washing solid reactants and product off of the reactor walls and back into the reaction mixture. In one embodiment, the solvent is o-DCB that is maintained at a temperature of at least about 18()°C. In another embodiment of the invention, the water removal is also effected by a "partial condensation" process. Partial condensation is a technique in which a multi- component vapor stream is subjected to a selective partial condensation by passage through a condenser maintained at a temperature greater than the boiling point of one or more of the lower boiling components but less than the boiling point of at least one higher boiling component. As the multi-component vapor stream encounters the condenser, the higher boiling components condense back to the liquid phase and may be returned to the source, whereas the components which boil at a temperature less than the temperature at which the condenser is maintained pass through the condenser, largely without condensing. It should be noted that this is extremely useful when trying to dry reaction mixtures comprising water and orthodichlorobenzene (o-DCB). Typically to dry such a reaction mixture by a simple distillation technique, roughly 10 volumes of o-DCB must be distilled per unit volume water distilled in order to dry the reaction mixture. The use of the partial condensation technique significantly lowers the amount of o-DCB which must be taken overhead with the water and thereafter separated from the water. It will be understood by those skilled in the art that the boiling points referred to are the boiling points of water and solvent under the conditions in the system. Water may be boiling at a temperature greater than or less than 100°C. Those skilled in the art will understand that as a mixture of water and solvent are removed from the reaction vessel by distillation, at least a portion of the reactants and product may be entrained out of the reaction vessel with the water and solvent. Thus, in a further embodiment of this invention, the monomers and solvent that may have been entrained from the reaction vessel during the reaction are separated from a water phase and/or otherwise dried to remove water. The monomers and solvent are then recycled to the same reaction mixture or to a subsequent reaction mixture. The bis(halophthalimide) produced from the reaction between the halophthalic anhydride and the diamine compound in an inert solvent may optionally be isolated through conventional techniques such as filtration, centrifugation and the like; or the slurry may be used as such for the next step viz. polymerization. It is within the scope of the present invention to use the slurry as such for making polymers. In a further embodiment of the present invention, a phase transfer catalyst is added as a solution in the same inert solvent or in a different inert solvent or mixtures thereof, to the mixture comprising the product and an inert solvent and the resulting mixture is dried until it contains less than 20ppm water. The phase transfer catalyst is necessary to effect polymerization. The drying is done under superatmospheric pressures at high temperatures, preferably at about 220°C and 20 psig. ' In one aspect of the invention, the bishalophthalimide is prepared using a stainless steel hot oil jacketed reaction vessel comprising the following features: (A) a 4-blade turbine agitator (B) reactor baffles (C) re-pad nozzles on the top of the reactor to reduce space where water can get trapped (D) zero volume agitator housing to reduce space where water can get trapped (E) spray nozzles in the top of the tank that deliver a spray of hot (180°C) o-DCB (F) electro-polished sides to reduce the tendency of solids to adhere to the side of the vessel (G) a zero-volume sample tap (H) sufficient insulation to insure that the top of the vessel remains hot (I) a second oil jacket that can be employed to heat the top of the reactor if necessary (J) tempered oil loops that can control the temperature of the upper and lower jacket. The agitator and the baffles were designed as described to ensure there is efficient mixing of the reaction mixture. This also ensures that there is sufficient contact between the reactants and that no local hot spots will be created. In one embodiment the baffles are approximately one inch in width and are separated from the reactor wall by a gap of about 7.6 cm (3 inches). In a further embodiment, the baffles have a height that does not exceed the operating liquid level in the tank. In one embodiment the reactor is equipped with re-pad nozzles and zero volume agitator housing thereby further limiting undesired retention of water within the interior spaces of the reactor. In certain embodiments of the present invention the reactor is equipped with a "sample tap", which is used to draw samples out for analysis, said sample tap being "zero volume" to ensure no moisture can get trapped in the spaces (e.g. piping) associated with the sample tap. The zero volume sample tap is also provides that there is no wastage during the withdrawal of samples. In one embodiment, the reactor comprises at least one hot-oil jacket. In certain embodiments, the top of the reactor is provided with a dedicated oil jacket to ensure greater control of the temperature. Typically, The reactor is provided with tempered oil loops that are capable of controlling the temperature of all sides of the reactor. Extra insulation is advantageously provided to ensure accurate control of the temperature. In one embodiment, the oil jacket is capable of maintaining the internal temperature of the reactor at least about 220°C (425°F). In one embodiment, the internal surfaces of of the reactor are made of stainless steel and are optionally electropolished. Electropolishing is a process that is used to smooth, polish, deburr and clean stainless steel by selectively removing irregular features on the metal surface. When electropolishing stainless steel, elemental iron is removed, and a layer of chromium-rich oxide forms on the surface. This oxide film is thickest over depressions and thinnest over projections. At the projections the electrical resistance is least and current density greatest; therefore, the effects of electropolishing are also the greatest in these locations. The oxide layer also provides for minimal moisture absorption, surface cleanliness and high corrosion resistance. Thus, in reactors which have been subjected to electropolishing the reactor walls arc- typically free of cracks and pits. In addition, solids typically do not adhere to the walls, thereby reducing caking of solids within the reactor. Each of the reactor features discussed provide a greater measure of control over the reaction to form bis(halophthalimides). Thus, the reactor features disclosed help to endure that (a) the reaction goes to completion; (b) by-products formation is minimized ; (c) caking of solids or solids adhering to the walls of the reactor is minimized ; and (d) the product bis(halophthalimide) comprises less than 20ppm water. It is also within the scope of the invention to produce polyetherimides from a mixture of solvent and bis(halophthalimide) produced according to the method of the present invention. In one embodiment, at least one comonomer as a slurry or a solution is added to the mixture of solvent and bis(halophthalimide). The at least one comonomer typically comprises a metal salt (e.g. the disodium salt of bisphenol A ) of at least one bisphenol having tructure VI wherein R is a halogen atom, a nitro group, a cyano group, a Cj-C12 aliphatic radical, C3-C12 cyeloaliphatic radical, or a C3-C12 aromatic radical; q is independently at each occurrence an integer 'from 0 to 4 inclusive; W is a bond, an oxygen atom, a sulfur atom or a selenium atom, an SO2 group, an SO group, a CO group, a C1-C20 aliphatic radical, C3-C20 cyeloaliphatic radical, or a C3-C20 aromatic radical. The reaction of the metal salt of biphenol VI with the bis(halophthalimide) prepared according to the method of the present invention affords polyetherimide compositions. Typically, the metal salt of the bisphenol is an alkali metal salt or an alkaline earth metal salt of the bisphenol. In an alternate embodiment, the at least one comonomer comprises a metal salt (e.g. the disodium salt of resorcinol) of a dihydroxy benzene. Dihydroxy benzenes are illustrated by resorcinol, hydroquinone, methylhydroquinone and the like. EXAMPLES The following examples are set forth to provide those of ordinary skill in the art with a detailed description of how the methods claimed herein are evaluated, and are not intended to limit the scope of what the inventors regard as their invention. Unless indicated otherwise, parts are by weight, temperature is in ° C. A 500-gallon stainless steel hot oil jacketed reactor with the configuration as described in the specifications was used for the reaction. The vessel was charged with chlorophthalic anhydride (ClPA)/o-dichlorobenzene (o-DCB) at about 12% solids content, 355.9 pounds of dry weight C1PA. The material was heated to reflux before analysis by High Performance Liquid Chromatography (HPLC) to determine the molar ratio of diacids to anhydrides. The solution was also analyzed for 3- and 4- C1PA and phthalic anhydride. Phthalic anhydride was added at this stage as chain stopper. Molten meta-phenylene diamine (mPD) (103.5 pounds) was then slowly metered, over a 2 to 4 hour period to the reaction mixture that was maintained at a temperature in the range of about 175°C to about 180°C (350°F to 356°F), with agitation. The temperature of the oil on the jacket of the reactor was set at 204°C (400°F). The water of imidization and o-DCB was taken overhead and condensed. The % solids of C1PAMI in the reactor was not allowed to surpass 17% solids. Hot o-DCR was added to the reactor to keep the solids at the desired level (15 to 17%). The initial mPD charge was 1.5 pounds deficient relative to the required amount of mPD so that the C1PAMI product was anhydride rich. This was done to prevent sticking of the material to the sides of the vessel. At this level of solids content, the non-Newtonian mixture stirred with sufficient efficiency where the material was mixing well in the reactor and there were no stagnant areas in the tank. Upon the completion of the mPD addition and after the bulk of the water had been removed from the tank, a sample of the reaction mixture was taken, and the stoichiometry of the reaction mixture was determined using HPLC. Additional C1PA solution was added until the stoichiometry of the C1PAMI was 0.05 to 0.3 mole% rich in C1PA with respect to the amount of mPD charged to the reactor. The analytical method worked very well when the bulk of the water had been removed. Running the reaction near reflux facilitated this. This resulted in a clean HPLC trace, and generally, there was no chlorophthalic acids present to complicate the determination of the stoichiometry. Additionally, most of the bis-amide-acids were ring closed, and most of the monoamine had reacted with C1PA. The C1PA and monoimides were clearly delineated in the HPLC trace resulting from running the reaction as described above. Once the C1PAM1 had been adjusted to the desired stoichiometry, Sodium Phenylphosphinate (SPP) imidization catalyst was added to the reaction mixture and the C1PAM1 was dried in the level control mode at atmospheric pressure in the presence of the imidization catalyst. In this manner, o-DCB was removed from the tank while hot dry o-DCB was sprayed into the headspace of the reactor, while maintaining a constant level (weight) in the reactor. Any water lingering in the head of the reactor was thus forced up and out of the reactor. After the overheads of the reactor are dry ( afford C1PAMI at 20 to 25% solids. This procedure resulted in insignificant amounts of C1PAM1 adhered to the walls of the vessel. Any C1PAM1 that did adhere to the wall were removed with a spray nozzle or was dissolved during the subsequent polymerization reaction (i.e., it is not strongly adhered to the walls). This led to polymer with very low and acceptable levels of residual C1PAM1. Example 2 The general procedure as described in Example 1 was followed. In the final step, SPP imidization catalyst was left out of the reaction, and the C1PAM1 was dried under pressure (18 to 25 psig), at a temperature in a range of from about 218°C to about 250°C (425°F to 480°F), at a solids contents of from about 15% to 17%. Hot o-DCB spray was used to chase water from the vessel in the level control mode. Once the overhead o-DCB was found to contain less than 20 ppm water, the pressure was relieved from the vessel and the amount of solid C1PAM1 in the slurry was adjusted to a range of from about 20% to about 25% solids just prior to the polymerization reaction. Once the polymerization reaction was completed in the imidization/polymeri/ation vessel, the reaction mixture was transferred to the quench vessel. The polymerization vessel was then washed with hot o-DCB to clean the tank. This rinse was found to contain undetectable amounts of C1PAMI and was then sent forward to the quench tank as long as there was no residual C1PAM1 adhered to the wall. The polymer made from this process contained less than 100 ppm C1PAM1. Batches where these conditions were not followed (high solids, higher oil temperature, no stoic control during mPD addition) contained 1000 to 3000 ppm C1PAMJ. The o-DCB/water collected off the condenser of the reactor contained a 'precipitate thought to comprise C1PA and mPD adducts. o-DCB comprising this precipitate was subsequently used in the preparation of an additional batch of C1PAM1. The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood by those skilled in the art that variations and modifications can be effected within the spirit and scope of the invention. WE CLAIMS: 1. A method for preparing a bis(halophthalimide), said method comprising: (A) preparing a mixture comprising at least one halophthalic anhydride and at least one solvent, (B) adding to the mixture formed in step (A) at least one molten diamine to form a reaction mixture, said reaction mixture being characterized by "an initial molar ratio of halophthalic anhydride to diamine", said adding being carried out at a temperature of at least 100°C; wherein the at least one molten diamine has the formula H2N-A1-NH2 wherein A1 is a C2-C40 divalent aromatic radical; (C) heating the reaction mixture formed in step (B) to a temperature of at least 100°C, optionally in the presence of an imidization catalyst, and removing at least 95% of the water of imidization; (D) analyzing the reaction mixture formed by the combination of steps (A)-(C) to determine the initial molar ratio of halophthalic anhydride to diamine; and (E) adding anhydride or diamine to the mixture formed by the combination of steps (A)~ (C) to achieve a "corrected molar ratio" of halophthalic anhydride to diamine, said corrected molar ratio being in a range between about 2.01 and about 2.3, and heating to a temperature of at least 100°C to obtain a bis(halophthalimide) product mixture that is substantially free of water. 2. The method according to claim 1 wherein said analyzing the reaction mixture formed by the combination of steps (A)-(C) to determine the initial molar ratio of halophthalic anhydride to diamine, comprises determining a concentration of halophthalic anhydride, a concentration of by-product halophthalic acid, and a concentration of intermediate monophthalimide monoamine in the reaction mixture formed by the combination of steps (A)-(C). 3. The method according to claim 1 wherein said bis(halophthalimide) has structuture I wherein X and X are independently fluorine, chlorine, bromine or iodine; and Q is a C2-C20 divalent aliphatic radical, a C2-C40 divalent aromatic radical, or a C4-C20 divalent cycloaliphatic radical; p is independently at each occurrence an integer ranging from 1 to 4. 4. The method according to claim 1 wherein the halophthalic anhydride is 4- chlorophthalic anhydride, 3-chlorophthalic anhydride, 4-fluorophthalic anhydride, 3- fluorophthalic anhydride, or a mixture comprising at least two of the foregoing. 5. The method according to claim 1 wherein the at least one diamine is selected from the group consisting of oxydianiline, and bis(4-aminophenyl)sulfone. 6. The method according to claim 1 wherein said diamine is selected from the group consisting of aromatic diamines III and diamines IV wherein R1 and R2 are independently at each occurrence a halogen atom, a nitro group, a cyano group, a C2-C20 aliphatic radical, a C2-C40 aromatic radical, or a C4-C20 cycloaliphatic radical; and "n" and "m" are independently integers ranging from 0 to 4. 7. The method according to claim 1 wherein each of steps (A)-(C) and (E) is characterized by a percent solids content, said percent solids content being less than about 17% solids. 8. The method according to claim 1 wherein step (C) and optionally step (E) further comprises distilling water from the reaction mixture through a condenser maintained at a temperature greater than the boiling point of water and less than the boiling point of the solvent, wherein the boiling point of the solvent is greater than the boiling point of water. 9. The method of claim 1 wherein the halophthalic anhydride comprises 3-chlorophthalic anhydride and 4-chlorophthalic anhydride. 10. The method of claim 1 wherein the halophthalic anhydride comprises 4-chlorophthalic anhydride, the solvent comprises orthodichlorobenzene and the diamine comprises meta- phenylene diamine and para-phenylene diamine. ABSTRACT Title: Method to prepare Bis(Haloimides) A method for preparing a bis(halophthalimide), said method comprising: preparing a mixture comprising a halophthalic anhydride and a solvent, adding to the mixture formed in step (A) a molten diamine to form a reaction mixture, said reaction mixture being characterized by "an initial molar ratio of halophthalic anhydride to diamine", wherein the molten diamine has the formula H2N-A1-NH2 wherein A1 is a C2-C40 divalent aromatic radical; heating the reaction mixture formed in step (B) to a temperature of at least 100°C, optionally in the presence of an imidization catalyst, and removing the water of imidization; analyzing the reaction mixture formed by the combination of steps (A)-(C) to determine the initial molar ratio of halophthalic anhydride to diamine; and adding anhydride or diamine to the mixture formed by the combination of steps (A)-(C) to achieve a "corrected molar ratio" of halophthalic anhydride to diamine, said corrected molar ratio being in a range between about 2.01 and about 2.3, and heating to a temperature of at least 100°C to obtain a bis(halophthalimide) product mixture that is substantially free of water.

Full Text

METHOD TO PREPARE BIS(HALOIMIDES)
BACKGROUND OF THE INVENTION
This invention relates to an improved method for the preparation of
bis(halophthalimides), monomers useful for the preparation of polyetherimides.
Various types of polyethers, such as polyetherimides, poiyethersulfones,
polyetherketones, and polyethertherketoncs, have become important as engineering
resins by reason of their excellent properties. These polymers are typically prepared by
the reaction of dihydroxyaromatic compounds, such as bisphenol A disodium salt,
with dihaloaromatic compounds. For example, polyetherimides arc conveniently
prepared by the reaction of salts of dihydroxyaromatie compounds with
bis(halophthalimides).
U.S. Pat. Nos. 5,229,482 and 5,830,974, disclose the preparation of aromatic
polyethers in relatively non-polar solvents, using a phase transfer catalyst which is
substantially stable under the polymerization conditions. Solvents disclosed in U.S.
Pat. No. 5,229,482 include o-dichlorobenzene, dichlorotoluene, 1,2,4-
trichlorobenzene and diphenyl sulfone. U.S. Pat. No. 5,830,974 discloses the use of
solvents such as anisole, diphenylether, and phenetole. Solvents of the same type may
be used for the preparation of bis(halophthalimidc) intermediates for polyetherimides.
In each of U.S. Pat. Nos. 5,229,482 and 5,830,974 the bis(halophthalimidc) is
introduced into the polymerization reaction as a substantially pure, isolated
compound. This process step is often difficult, since solid bis(halophthalimdes) are
typically of very low density and fluffy, making weighing and handling burdensome.
U.S. Pat. No. 6,235,866 teaches a method of slurry preparation of
bis(halophthalimides) by the reaction between diamine compounds and halophfhalic
anhydride, in equimolar proportions and use of that slurry as such to prepare polyether
polymers. But in the disclosed process, considerable caking of the product
bis(halophthalimides) occurs, rendering the product difficult to isolate as a pure slurry,
resulting in unacceptable levels of residual starting material in the polymer. Also, the
presence of water in the resulting product has a deleterious effect on the molecular

weight of the polymer. If proper stoichiometric balance between the diamine and the
halophthalic anhydride is not maintained, several undesirable by-products remain in
the slurry which limit the molecular weight of the polymer, and/or result in polymers
with amine end groups Thus there is a need in the art to develop a facile process for
the preparation of bis(halophthalimides) having suitable characteristics for conversion
to polyefherimide polymers without isolation which overcomes the shortcomings of
current synthetic methods.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a method for preparing a bis(halophthalimide), said
method comprising:
(A) preparing a mixture comprising at least one halophthalic anhydride and at least
one solvent,
(B) adding to the mixture formed in step (A) at least one diamine, to form a reaction
mixture, said reaction mixture being characterized by "an initial molar ratio of
halophthalic anhydride to diamine";
(C) heating the reaction mixture formed in step (B) to a temperature of at least 100°C,
optionally in the presence of an imidization catalyst;
(D) analyzing the reaction mixture formed by the combination of steps (A)-(C) to
determine the initial molar ratio of halophthalic anhydride to diamine; and
(E) performing one step selected from the group consisting of:
(i) adding anhydride or diamine to the mixture formed by the combination of steps
(A)-(C) to achieve a "corrected molar ratio" of halophthalic anhydride to diamine,
said corrected molar ratio being in a range between about 2.01 and about 2.3, and
heating to a temperature of at least 100°C to obtain a bis(halophthalimide) product
mixture that is substantially free of water; and(ii) heating to a temperature of at least
100°C the reaction mixture formed by the combination of steps (A)-(C) to obtain a
bis(halophthalimide) product mixture that is substantially free of water.

DETAILED DESCRIPTION OF THE INVENTION
The present invention may be understood more readily by reference to the following
detailed description of preferred embodiments of the invention and the examples
included therein. In the following specification and the claims which follow, reference
will be made to a number of terms which shall be defined to have the following
meanings:
The singular forms "a", "an" and "the" include plural referents unless the context
clearly dictates otherwise.
"Optional" or "optionally" means that the subsequently described event or
circumstance may or may not occur, and that the description includes instances where
the event occurs and instances where it does not.
As used herein the term "integer" means a whole number which includes zero. For
example, the expression "n is an integer from 0 to 4" means "n" may be any whole
number from 0 to 4 including 0 and 4. Similarly, the expression "an integer ranging
from 1 to 4 inclusive" means an integer in a range from 1 to 4 , said range including
the integer 1 and the integer A.,
As used herein the term "aliphatic radical" refers to a radical having a valence of at
least one comprising a linear or branched array of atoms which is not cyclic. The
array may include heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen
or may be composed exclusively of carbon and hydrogen. Aliphatic radicals may be
"substituted" or "unsubstituted". A substituted aliphatic radical is defined as an
aliphatic radical which comprises at least one substituent. A substituted aliphatic
radical may comprise as many substituents as there are positions available on the
aliphatic radical for substitution. Substituents which may be present on an aliphatic
radical include but are not limited to halogen atoms such as fluorine, chlorine,
bromine, and iodine. Substituted aliphatic radicals include trifluoromethyl,
hexafluoroisopropylidene, chloromethyl; difluorovinylidene; triehloromethyl,
bromoethyl, bromotrimethylene (e.g. -CH2CHBrCH2-), and the like. For convenience,
the term "unsubstituted aliphatic radical" is defined herein to encompass, as part of

the "linear or branched array of atoms which is not cyclic" comprising the
unsubstituted aliphatic radical, a wide range of functional groups. Examples of
unsubstituted aliphatic radicals include ally], carbonyl, dicyanoisopropylidene (i.e. -
CH2C(CN)2CH2-), methyl (i.e. -CH3), methylene (i.e. -CH2-), ethyl, ethylene, formyl,,
hexyl, hexamethylene, hydroxymethyl (i.e.-CH2OH), mercaptomcthyl (i.e. -CH2SH),
methylthio (i.e. -SCH3), methylthiomethyl (i.e. -CH2SCH3), methoxy.
methoxycarbonyl (CH3OCO) , nitromethyl (i.e. -CH2NO2), thiocarbonyl,
trimethylsilyl, t-butyldimethylsilyl, trimethyoxysilylpropyl, vinyl, vinylidene, and the
like. Aliphatic radicals are defined to comprise at least one carbon atom. A C1- C10
aliphatic radical includes substituted aliphatic radicals and unsubstituted aliphatic
radicals containing at least one but no more than 10 carbon atoms.
As used herein, the term "aromatic radical" refers to an array of atoms having a
valence of at least one comprising at least one aromatic group. The array of atoms
having a valence of at least one comprising at least one aromatic group may include
heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be
composed exclusively of carbon and hydrogen. As used herein, the term "aromatic
radical" includes but is not limited to phenyl, pyridyl, furanyl, thienyl, naphthyl,
phenylene, and biphenyl radicals. As noted, the aromatic radical contains at least one
aromatic group. The aromatic group is invariably a cyclic structure having 4n+2
"delocalized" electrons where "n" is an integer equal to 1 or greater, as illustrated by
phenyl groups (n = 1), thienyl groups (n = 1), furanyl groups (n = 1), naphthyl groups
(n = 2), azulenyl groups (n = 2), anthraceneyl groups (n = 3) and the like. The
aromatic radical may also include nonaromatic components. I •"or example, a ben/.yl
group is an aromatic radical which comprises a phenyl ring (the aromatic group) and a
methylene group (the nonaromatic component). Similarly a tctrahydronaphthyl radical
is an aromatic radical comprising an aromatic group (C6H3) fused to a nonaromatic
component -(CH2)4-. Aromatic radicals may be "substituted" or "unsubstituted". A
substituted aromatic radical is defined as an aromatic radical which comprises at least
one substituent. A substituted aromatic radical may comprise as many substituents as
there are positions available on the aromatic radical for substitution. Substituents
which may be present on an aromatic radical include, but arc not limited to halogen

atoms such as fluorine, chlorine, bromine, and iodine. Substituted aromatic radicals
include trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phenyloxy) (i.e. -
OPhC(CF3)2PhO-), chloromethylphenyl; 3-trifluorovinyl-2~thienyl; 3-
trichloromethylphenyl (i.e. 3-CCl3ph-), bromopropylphenyl (i.e. BrCH2CH2CFI2Ph-),
and the like. For convenience, the term "unsubstituted aromatic radical" is defined
herein to encompass, as part of the "array of atoms having a valence of at least one
comprising at least one aromatic group", a wide range of functional groups. Examples
of unsubstituted aromatic radicals include 4-allyloxyphenoxy, 4-benzoylphenyl,
dicyanoisopropylidenebis(4-phenyloxy) (i.e. -OPhC(CN)2PhO-), 3-methylphenyl,
methylenebis(4-phenyloxy) (i.e. -OPhCH2PhO-), ethylphenyl, phenylethenyl, 3-
formyl,-2-thienyl, 2-nexyl-5-furanyl; hexamethylcne-l,6-bis(4-phenyloxy) (i.e. -
OPh(CH2)6PhO-); 4-hydroxymethylphenyl (i.e. 4-HOCH2Ph-), 4-
mercaptomethylphemyl, (i.e. 4-HSCH2Ph-), 4-methylthiophenyl (i.e. 4-CH3SPh-),
methoxyphenyl, methoxycarbonylphenyloxy (e.g. methyl salicyl), nitromethylphenyl
(i.e. -PhCH2NO2), trim ethyl silylphenyl, t-butyldimefhylsilylphenyl, vinylphenyl,
vinylidenebis(phenyl), and the like. The term "a C3 ~ Cio aromatic radical" includes
substituted aromatic radicals and unsubstituted aromatic radicals containing at least
three but no more than 10 carbon atoms. The aromatic radical 1-imidazolyl (C3112N2-)
represents a C3 aromatic radical. The benzyl radical (C7I-V) represents a C7 aromatic
radical.
As used herein the term "cycloaliphatic radical" refers to a radical having a valence of
at least one, and comprising an array of atoms which is cyclic but which is not
aromatic. As defined herein a "cycloaliphatic radical" does not contain an aromatic
group. A "cycloaliphatic radical" may comprise one or more noncyclic components.
For example, a cyclohexylmethyl group (C6H11CH2-) is a cycloaliphatic radical which
comprises a cyclohexyl ring (the array of atoms which is cyclic but which is not
aromatic) and a methylene group (the noncyclic component). The cycloaliphatic
radical may include heteroatoms such as nitrogen, sulfur, selenium, silicon and
oxygen, or may be composed exclusively of carbon and hydrogen. Cycloaliphatic
radicals may be "substituted" or "unsubstituted". A substituted cycloaliphatic radical
is defined as a cycloaliphatic radical which comprises at least one substituent. A

substituted cycloaliphatic radical may comprise as many substituents as there are
positions available on the cycloaliphatic radical for substitution. Substituents which
may be present on a cycloaliphatic radical include but are not limited to halogen atoms
such as fluorine, chlorine, bromine, and iodine. Substituted cycloaliphatic radicals
include trifluoromethylcyclohexyl, hexafluoroisopropylidenebis(4-cyclohexyloxy) (i.e.
-O C6HioC(CF3)2 CfJiioO-), chloromethylcyclohcxyl; 3-trifluorovinyl-2-cyclopropyl;
3-trichloromethylcyclohexyl (i.e. 3-CCl3C6H]0-), bromopropylcyclohexyl (i.e.
BrCH2CH2CH2 C(,H\o-), and the like. For convenience, the term "unsubstituted
cycloaliphatic radical" is defined herein to encompass a wide range of functional
groups. Examples of unsubstituted cycloaliphatic radicals include 4-
allyloxycyclohexyl, 4-acetyloxycyclohexyl, dicyanoisopropylidcncbis(4-
cyclohexyloxy) (i.e. -O C6H]oC(CN)2 C6HioO-), 3-methylcyclohexyl, methylenebis(4-
cyclohexyloxy) (i.e. -O C6H10CH2 C6H10O-), ethylcyclobutyl, cyclopropylethenyl, 3-
formyl,-2-terahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl; hexamefhylene-1,6-bis(4-
cyclohexyloxy) (i.e. -O Ce,Hjo (CH2)6 C6HioO-); 4-hydroxymethylcyclohexyl (i.e. 4-
HOCH2 C6H,o-), 4-mercaptomethylcyclohexyl (i.e. 4-HSCH2 C6HK,-), 4-
mefhylthiocyclohexyl (i.e. 4-CH3S C(,U]0-), 4-methoxycyclohcxyl. 2-
methoxycarbonylcyclohexyloxy (2-CH3OCO C6H10O-), nitromcthylcyclohcxyl (i.e.
NO2CH2C6H10-), trimethylsilylcyclohexyl, t-butyldimcthylsilylcyclopentyl: 4-
trimethoxysilylethylcyclohexyl (e.g. (CHsO^SiCI-kCI-kCfJ-Iio-), vinylcyclohexenyi,
vinylidenebis(cyclohexyl), and the like. The term "a C3 - C\0 cycloaliphatic radical"
includes substituted cycloaliphatic radicals and unsubstituted cycloaliphatic radicals
containing at least three but no more than 10 carbon atoms. The cycloaliphatic radical
2-tetrahydrofuranyl (C4H7O-) represents a C4 cycloaliphatic radical. The
cyclohexylmethyl radical (C6MnCH2-) represents a C7 cycloaliphatic radical.
As noted the present invention relates to a method for the efficient preparation of
bis(halophthalimides). In one embodiment the present invention relates to a method
for the prepartion of bis(halophfhalimides) having structure 1

wherein X is independently in each instance, a fluorine, chlorine, bromine or iodine
group; and Q is a C2-C20 divalent aliphatic radical, a C2-C40 divalent aromatic radical,
or a C4-C20 divalent cycloaliphatic radical; p is independently at each occurrence an
integer in a range from 1 to 4 inclusive.
Bis(halophthalimides) having structure 1 are illustrated by l,3-bis[N-(4-
chlorophthalimido)]benzene (hereinafter sometimes "C1PAMI"). It should be noted
that bis(halophthalimides) prepared from a mixture of 3-chlorophthalic anhydride and
4-chlorophthalic anhydride are also at times referred to as "C1PAMI".
There is no particular limitation on the diamine component. Any diamine compound
may be employed and used according to the method of this invention. Typically, the
diamine compound comprisies at least one compound having structure 11:
H2N-A1-NH2
II
wherein A is a C2-C20 divalent aliphatic radical, a C2-C40 divalent aromatic radical, or
a C4-C20 divalent cyloaliphatic radical. Suitable aliphatic diamine compounds
represented by structure II (A1 is a C2-C20 divalent aliphatic radical) include
efhylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, and 1,
10-diaminodecane. Suitable aromatic diamine compounds represented by structure II
(A1 is a C2-C40 divalent aromatic radical) include 1, 4-dimainonaphthalene, 2, 6-
dimainonaphthalene, 4, 4'-diaminobiphenyl, and the like. Suitable cycloaliphatic
diamine compounds represented by structure II (A1 is a C4-Q>o divalent

cycloaliphatic radical) include trans-l,2-diaminocyelopentane, trans- l,4-(bis
aminomethyl)cyclohexane, and the like.
In one embodiment, the diamine compound is selected from the group consisting of
oxydianiline, bis(4-aminophenyl)sulfone, meta-phenylendiarnine and para-
phenylenediamine and mixtures thereof.
In a preferred embodiment of the invention, the diamine compound is selected from
the group represented by structures III and IV

wherein R and R are independently at each occurrence a halogen atom, a nitro
group, a cyano group, a C2-C20 aliphatic radical, a C2-C40 aromatic radical, or a C4-C?o
divalent aliphatic radical; and "n" and "m" are independently integers ranging from
about 0 to about 4. Examples of suitable compounds are meta-phenylenediaminc,
para-phenylenediaminc, 2,4-diaminotoluene, 2,6-diaminotolucne, 2-mcthyl-4,6-
diethyl-1,3-phenylenediamine, 5-methyl-4,6-diethyl-l ,3-phenylenediamine, 1,3-
diamino-4-isopropylbenzene, and combinations thereof.
The halophthalic anhydrides employed according to the method of the present
invention are typically cyclic anhydrides represented by structure V

wherein X1 is chloro, bromo, or fluoro, and p is an integer in a range from 1 to 4
includive. 4-chlorophthalic anhydride (CAS 11 118-45-6) is a preferred anhydride.
As noted, the method of the present invention employs a solvent. Thus, in step (A) of
the method of the present invention a mixture comprising at least one halophthalic
anhydride and at least one solvent is prepared. Preferably the solvent is an inert
solvent. Suitable solvents include dichlorobenzenes, dimethyl formamide,
dimethylacetamide, N-methylpyrrolidone, dichlorotoluene, 1,2,4-trichlorobenzene,
diphenyl sulfone, monoalkoxybenzencs such as anisole, and the like, and mixtures
thereof. In a preferred embodiment, the inert solvent is chosen such that the boiling
point of the solvent system is at least about 20°C higher than the boiling point of
water under the prevailing reaction conditions. The prevailing reaction conditions
include the temperature and pressure at which the imidization reaction is carried out.
In one embodiment, the imidization reaction is canned out under superatmospheric
pressure (i.e. the pressure is greater than 1 atmosphere). Ortho-dichlorobenzene (o-
DCB) is frequently a the solvent of choice for the reaction.
In one embodiment, the halophthalic anhydrideis added to the solvent of choice with
vigorous stirring while keeping the mixture hot. Temperatures greater than 150°C are
preferred. The solvent, the diamine and the halophthalic anhydride are typically
combined in amounts such that the total solids content during the reaction to form the
bis(halophthalimide) does not exceed about 25 percent by weight, more preferably the
total solids content during the reaction to form the bis(halophthalimide) does not
exceed about 17 percent by weight. "Total solids content" expresses the proportion

of the reactants as a percentage of the total weight including liquids present in the
reaction at any given time. In one embodiment, as solvent and water arc distilled from
the reaction mixture, additional solvent is added to maintain the total solids content
within the preferred range. The terms total solids content and "% solids" are used
interchangeable herein. This is effected by the addition of solvent to compensate for
any increase in solids content.
In a second step, step (B), at least one diamine is added to the mixture comprising the
halophthalic anhydride and the solvent prepared in step (A) to form a reaction
mixture. The diamine compound is metered into the mixture formed in step (A). The
diamine compound may be added either as a solid, a melt, or in solution in an inert
solvent. In a preferred embodiment, the diamine compound is added as a hot melt at a
an addition rate which is sufficiently slow to ensure sufficient mixing of the reactants
and to avoid undue caking of solids in the reaction medium. The addition of the
diamine compound is were also carried out in such a fashion so that the solids content
of the reaction mixture is maintained at less than about 25% by weight, more
preferably less than about 17% by weight. The reaction mixture formed in step (B) is
said to be characterized by an "initial molar ratio of halophthalic anhydride to
diamine". The "initial molar ratio of halophthalic anhydride to diamine" is the
"actual" or "true" ratio of halophthalic anhydride moieties to diamine moieties present
in the reaction mixture in step (B). As a result of the uncertainty in the weights of
reactants used the "initial molar ratio of halophthalic anhydride to diamine" typically
has a value which is different than the ratio calculated based upon the weights of
halophthalic anhydride and diamine added in steps (A) and (B). Uncertainty in the
weights of halophthalic anhydride and diamine used can be pronounced when large-
scale reactions are being carried out. Moreover, a stoichiometric imbalance can lead
to undesired consequences such as "clumping" of the product bis(halophthalimide).
The "actual" molar ratio can be determined by performing an high performance liquid
chromatography (HPLC) analysis on the reaction mixture after most of the reactants
have been converted to the bis(halophfhalirnide) product.
With respect to the amounts of halophthalic anhydride and diamine employed, it is
preferable to have an excess of the halophthalic anhydride in the reaction mixture.

Preferably, 2.01 to 3.0 molar equivalents of the halophthalic anhydride with respect to
the diamine compounds are employed, more preferably 2.01 to 2.5 molar equivalents
of the halophthalic anhydride with respect to the diamine compound are employed.
Typically, the bis(halophthalimide) product is produced in a slurry form that is largely
free from by-products and unreacted reactants, and isolation and purification of the
bis(halophthalimide) product from the slurry is not required prior to polymerization
to form polyetherimide.
In some embodiments an imidization catalyst may be added to the reaction mixture.
Suitable imidization catalysts are known in the art. They include salts of
organophosphorus acids, particularly phosphinates such as sodium phenylphosphinate
(SPP) and heterocyclic amines such as 4-dimethylaminopyridine (DMAP). Organic
and inorganic acids may also be used to catalyze this reaction. Suitable organic acids
include chlorophthalic acid, phthalic acid, and acetic acid. Sodium phenylphosphinate
is generally preferred. The catalyst, when opted for, may be added before the diamine
compound has been added, after the diamine compound has been added, or together
with the diamine compound. In a preferred embodiment of the present invention, the
catalyst, when used in the reaction mixture, is added after the addition of the diamine
compound.
Step (C) of the method of the present invention comprises heating the reaction
mixture formed in step (B) to a temperature of at least 100°C , optionally in the
presence of the imidization catalyst described. Typically the reaction mixture is
heated to a temperature of at least 150°C, preferably in a range from about 150°C to
about 250°C, and more preferably in a range from about 175°C to about 225"C. It
should be note that the reaction mixture may be heated at atmospheric pressure,
subatomsphheric pressure or superatomospheric pressure. When superatmospheric
pressures are employed the pressure is typically up to about 5 atmospheres, to
facilitate the conversion starting materials product bis(halophthalimide). Typically,
step (C) also provides for the removal of at least some of the water of imidization
resulting from reaction of the halophthalic anhydride with the diamine. In one
embodiment, about 95 % of the water of imidization is removed in step (C).

In step (D) the reaction mixture formed by the combination of steps (A)-(C) is
analyzed to determine the "initial molar ratio of halophthalic anhydride to diamine".
As note, in conventional methods for the production of bis(halophfhalnnides), the
amount of halophthalic anhydride present in the reaction mixture can only be roughly
estimated based on the initial added amount. In one aspect of the invention, a suitable
analytical tool may be employed to determine accurately the amount of each the
reactants initially employed. This information may then be used to determine if any of
the reactants need to be added to compensate for the deficiency of the same. In one
embodiment of the invention, the analytical tool used to determine the initial molar
ratio of halophthalic anhydride to diamine is a chromatographic method. In a typical
embodiment of the present invention, a high performance liquid chromatography
(HPLC) technique is used. Other analytical methods such as, but not limited to, gas
chromatography, infra-red spectroscopy, ultraviolet spectroscopy, and the like may be
used to monitor the reaction.
In step (E) any stoichiometric deficiency revealed by determining the initial molar
ratio halophthalic anhydride to diamine is corrected by the addition of halophthalic
anhydride or diamine to achieve a "corrected molar ratio" of halophthalic anhydride to
diamine. Typically, because the quantity of halophthalic anhydride or diamine needed
to correct the stoichiometry is small, weighing errors can be minimized using small
more reliable mass measuring equipment. The corrected molar ratio is generally
much closer to the molar ratio of reactants intended initially than is the initial molar
ratio. In a further embodiment of the invention, the analytical tool used to monitor the
reaction mixture is also coupled to a controlling unit that is capable of automatically
monitoring and maintaining the stoichiometry between the reactants.
A further feature of the present invention is the solids content of the reaction mixture
which at any given time during the course of the reaction should be typically less than
25% by weight, preferably in the range from about 10% to about 17% by weight. By
"solids content" is meant the proportion of the reactants as a percentage of the total
weight including liquids. This is effected by the addition of solvent to compensate for
any increase in solids content.

Another embodiment of the present invention involves the removal of water from the
reaction mixture, lire water may be present in the system from a variety of sources;
the reactor, or as a component of one or more of the reactants or solvents employed.
Moreover, water is also produced as the by-product of the imidization reaction.
Regardless of its origin, the presence of residual water in the product
bis(halophfhalimide) is detrimental to the polymerization reaction for which the
bis(halophthalimide) is typically intended. Thus, in one aspect, the present invention
provides a bis(halophthalimide) product which is suitable for use in a polymerization
reaction to form polyefherimide. Typically, at least 95% of the water present during
step (C) of the reaction is removed from the reaction mixture during step (C) and the
remaining water is removed during step (D). Water removal may be accomplished
using means well-known in the art such as a distillation process. In one embodiment
of the invention, the reactor is designed such that water is removed efficiently using
flush mounted valves , wherein the valves are properly designed with low volume
configuration and the reaction vessel is devoid of any water retention zones.
In one embodiment, the reaction vessel comprises spray nozzles from which hot
solvent (e.g. hot o-DCB) is directed at the reactor walls outlets in order to "chase"
water from the reactor directing a spray of hot solvent on the interior surfaces of the
reactor (typically surfaces which are above the level of the contents of the reaction
vessel) serves to drive water adhering to the walls of the reactor from the reactor, and
has the added benefit of washing solid reactants and product off of the reactor walls
and back into the reaction mixture. In one embodiment, the solvent is o-DCB that is
maintained at a temperature of at least about 18()°C.
In another embodiment of the invention, the water removal is also effected by a
"partial condensation" process. Partial condensation is a technique in which a multi-
component vapor stream is subjected to a selective partial condensation by passage
through a condenser maintained at a temperature greater than the boiling point of one
or more of the lower boiling components but less than the boiling point of at least one
higher boiling component. As the multi-component vapor stream encounters the
condenser, the higher boiling components condense back to the liquid phase and may
be returned to the source, whereas the components which boil at a temperature less

than the temperature at which the condenser is maintained pass through the condenser,
largely without condensing. It should be noted that this is extremely useful when
trying to dry reaction mixtures comprising water and orthodichlorobenzene (o-DCB).
Typically to dry such a reaction mixture by a simple distillation technique, roughly 10
volumes of o-DCB must be distilled per unit volume water distilled in order to dry the
reaction mixture. The use of the partial condensation technique significantly lowers
the amount of o-DCB which must be taken overhead with the water and thereafter
separated from the water. It will be understood by those skilled in the art that the
boiling points referred to are the boiling points of water and solvent under the
conditions in the system. Water may be boiling at a temperature greater than or less
than 100°C.
Those skilled in the art will understand that as a mixture of water and solvent are
removed from the reaction vessel by distillation, at least a portion of the reactants and
product may be entrained out of the reaction vessel with the water and solvent. Thus,
in a further embodiment of this invention, the monomers and solvent that may have
been entrained from the reaction vessel during the reaction are separated from a water
phase and/or otherwise dried to remove water. The monomers and solvent are then
recycled to the same reaction mixture or to a subsequent reaction mixture.
The bis(halophthalimide) produced from the reaction between the halophthalic
anhydride and the diamine compound in an inert solvent may optionally be isolated
through conventional techniques such as filtration, centrifugation and the like; or the
slurry may be used as such for the next step viz. polymerization. It is within the scope
of the present invention to use the slurry as such for making polymers.
In a further embodiment of the present invention, a phase transfer catalyst is added as
a solution in the same inert solvent or in a different inert solvent or mixtures thereof,
to the mixture comprising the product and an inert solvent and the resulting mixture is
dried until it contains less than 20ppm water. The phase transfer catalyst is necessary
to effect polymerization. The drying is done under superatmospheric pressures at high
temperatures, preferably at about 220°C and 20 psig. '

In one aspect of the invention, the bishalophthalimide is prepared using a stainless
steel hot oil jacketed reaction vessel comprising the following features:
(A) a 4-blade turbine agitator
(B) reactor baffles
(C) re-pad nozzles on the top of the reactor to reduce space where water can get
trapped
(D) zero volume agitator housing to reduce space where water can get trapped
(E) spray nozzles in the top of the tank that deliver a spray of hot (180°C) o-DCB
(F) electro-polished sides to reduce the tendency of solids to adhere to the side of the
vessel
(G) a zero-volume sample tap
(H) sufficient insulation to insure that the top of the vessel remains hot
(I) a second oil jacket that can be employed to heat the top of the reactor if necessary
(J) tempered oil loops that can control the temperature of the upper and lower jacket.
The agitator and the baffles were designed as described to ensure there is efficient
mixing of the reaction mixture. This also ensures that there is sufficient contact
between the reactants and that no local hot spots will be created. In one embodiment
the baffles are approximately one inch in width and are separated from the reactor
wall by a gap of about 7.6 cm (3 inches). In a further embodiment, the baffles have a
height that does not exceed the operating liquid level in the tank.
In one embodiment the reactor is equipped with re-pad nozzles and zero volume
agitator housing thereby further limiting undesired retention of water within the
interior spaces of the reactor. In certain embodiments of the present invention the
reactor is equipped with a "sample tap", which is used to draw samples out for
analysis, said sample tap being "zero volume" to ensure no moisture can get trapped

in the spaces (e.g. piping) associated with the sample tap. The zero volume sample tap
is also provides that there is no wastage during the withdrawal of samples.
In one embodiment, the reactor comprises at least one hot-oil jacket. In certain
embodiments, the top of the reactor is provided with a dedicated oil jacket to ensure
greater control of the temperature. Typically, The reactor is provided with tempered
oil loops that are capable of controlling the temperature of all sides of the reactor.
Extra insulation is advantageously provided to ensure accurate control of the
temperature. In one embodiment, the oil jacket is capable of maintaining the internal
temperature of the reactor at least about 220°C (425°F).
In one embodiment, the internal surfaces of of the reactor are made of stainless steel
and are optionally electropolished. Electropolishing is a process that is used to
smooth, polish, deburr and clean stainless steel by selectively removing irregular
features on the metal surface. When electropolishing stainless steel, elemental iron is
removed, and a layer of chromium-rich oxide forms on the surface. This oxide film is
thickest over depressions and thinnest over projections. At the projections the
electrical resistance is least and current density greatest; therefore, the effects of
electropolishing are also the greatest in these locations. The oxide layer also provides
for minimal moisture absorption, surface cleanliness and high corrosion resistance.
Thus, in reactors which have been subjected to electropolishing the reactor walls arc-
typically free of cracks and pits. In addition, solids typically do not adhere to the
walls, thereby reducing caking of solids within the reactor.
Each of the reactor features discussed provide a greater measure of control over the
reaction to form bis(halophthalimides). Thus, the reactor features disclosed help to
endure that (a) the reaction goes to completion; (b) by-products formation is
minimized ; (c) caking of solids or solids adhering to the walls of the reactor is
minimized ; and (d) the product bis(halophthalimide) comprises less than 20ppm
water.
It is also within the scope of the invention to produce polyetherimides from a mixture
of solvent and bis(halophthalimide) produced according to the method of the present
invention. In one embodiment, at least one comonomer as a slurry or a solution is

added to the mixture of solvent and bis(halophthalimide). The at least one comonomer
typically comprises a metal salt (e.g. the disodium salt of bisphenol A ) of at least one
bisphenol having tructure VI

wherein R is a halogen atom, a nitro group, a cyano group, a Cj-C12 aliphatic radical,
C3-C12 cyeloaliphatic radical, or a C3-C12 aromatic radical; q is independently at each
occurrence an integer 'from 0 to 4 inclusive; W is a bond, an oxygen atom, a sulfur
atom or a selenium atom, an SO2 group, an SO group, a CO group, a C1-C20 aliphatic
radical, C3-C20 cyeloaliphatic radical, or a C3-C20 aromatic radical. The reaction of the
metal salt of biphenol VI with the bis(halophthalimide) prepared according to the
method of the present invention affords polyetherimide compositions. Typically, the
metal salt of the bisphenol is an alkali metal salt or an alkaline earth metal salt of the
bisphenol. In an alternate embodiment, the at least one comonomer comprises a metal
salt (e.g. the disodium salt of resorcinol) of a dihydroxy benzene. Dihydroxy benzenes
are illustrated by resorcinol, hydroquinone, methylhydroquinone and the like.
EXAMPLES
The following examples are set forth to provide those of ordinary skill in the art with a
detailed description of how the methods claimed herein are evaluated, and are not
intended to limit the scope of what the inventors regard as their invention. Unless
indicated otherwise, parts are by weight, temperature is in ° C.
A 500-gallon stainless steel hot oil jacketed reactor with the configuration as
described in the specifications was used for the reaction. The vessel was charged with
chlorophthalic anhydride (ClPA)/o-dichlorobenzene (o-DCB) at about 12% solids
content, 355.9 pounds of dry weight C1PA. The material was heated to reflux before
analysis by High Performance Liquid Chromatography (HPLC) to determine the

molar ratio of diacids to anhydrides. The solution was also analyzed for 3- and 4-
C1PA and phthalic anhydride. Phthalic anhydride was added at this stage as chain
stopper.
Molten meta-phenylene diamine (mPD) (103.5 pounds) was then slowly metered, over
a 2 to 4 hour period to the reaction mixture that was maintained at a temperature in the
range of about 175°C to about 180°C (350°F to 356°F), with agitation. The
temperature of the oil on the jacket of the reactor was set at 204°C (400°F). The water
of imidization and o-DCB was taken overhead and condensed. The % solids of
C1PAMI in the reactor was not allowed to surpass 17% solids. Hot o-DCR was added
to the reactor to keep the solids at the desired level (15 to 17%). The initial mPD
charge was 1.5 pounds deficient relative to the required amount of mPD so that the
C1PAMI product was anhydride rich. This was done to prevent sticking of the
material to the sides of the vessel. At this level of solids content, the non-Newtonian
mixture stirred with sufficient efficiency where the material was mixing well in the
reactor and there were no stagnant areas in the tank.
Upon the completion of the mPD addition and after the bulk of the water had been
removed from the tank, a sample of the reaction mixture was taken, and the
stoichiometry of the reaction mixture was determined using HPLC. Additional C1PA
solution was added until the stoichiometry of the C1PAMI was 0.05 to 0.3 mole% rich
in C1PA with respect to the amount of mPD charged to the reactor. The analytical
method worked very well when the bulk of the water had been removed. Running the
reaction near reflux facilitated this. This resulted in a clean HPLC trace, and
generally, there was no chlorophthalic acids present to complicate the determination
of the stoichiometry. Additionally, most of the bis-amide-acids were ring closed, and
most of the monoamine had reacted with C1PA. The C1PA and monoimides were
clearly delineated in the HPLC trace resulting from running the reaction as described
above.
Once the C1PAM1 had been adjusted to the desired stoichiometry, Sodium
Phenylphosphinate (SPP) imidization catalyst was added to the reaction mixture and
the C1PAM1 was dried in the level control mode at atmospheric pressure in the

presence of the imidization catalyst. In this manner, o-DCB was removed from the
tank while hot dry o-DCB was sprayed into the headspace of the reactor, while
maintaining a constant level (weight) in the reactor. Any water lingering in the head
of the reactor was thus forced up and out of the reactor. After the overheads of the
reactor are dry ( afford C1PAMI at 20 to 25% solids. This procedure resulted in insignificant amounts
of C1PAM1 adhered to the walls of the vessel. Any C1PAM1 that did adhere to the
wall were removed with a spray nozzle or was dissolved during the subsequent
polymerization reaction (i.e., it is not strongly adhered to the walls). This led to
polymer with very low and acceptable levels of residual C1PAM1.
Example 2
The general procedure as described in Example 1 was followed. In the final step, SPP
imidization catalyst was left out of the reaction, and the C1PAM1 was dried under
pressure (18 to 25 psig), at a temperature in a range of from about 218°C to about
250°C (425°F to 480°F), at a solids contents of from about 15% to 17%. Hot o-DCB
spray was used to chase water from the vessel in the level control mode. Once the
overhead o-DCB was found to contain less than 20 ppm water, the pressure was
relieved from the vessel and the amount of solid C1PAM1 in the slurry was adjusted to
a range of from about 20% to about 25% solids just prior to the polymerization
reaction.
Once the polymerization reaction was completed in the imidization/polymeri/ation
vessel, the reaction mixture was transferred to the quench vessel. The polymerization
vessel was then washed with hot o-DCB to clean the tank. This rinse was found to
contain undetectable amounts of C1PAMI and was then sent forward to the quench
tank as long as there was no residual C1PAM1 adhered to the wall. The polymer made
from this process contained less than 100 ppm C1PAM1. Batches where these
conditions were not followed (high solids, higher oil temperature, no stoic control
during mPD addition) contained 1000 to 3000 ppm C1PAMJ.

The o-DCB/water collected off the condenser of the reactor contained a 'precipitate
thought to comprise C1PA and mPD adducts. o-DCB comprising this precipitate was
subsequently used in the preparation of an additional batch of C1PAM1.
The invention has been described in detail with particular reference to preferred
embodiments thereof, but it will be understood by those skilled in the art that
variations and modifications can be effected within the spirit and scope of the
invention.

WE CLAIMS:
1. A method for preparing a bis(halophthalimide), said method comprising:
(A) preparing a mixture comprising at least one halophthalic anhydride and at least one
solvent,
(B) adding to the mixture formed in step (A) at least one molten diamine to form a reaction
mixture, said reaction mixture being characterized by "an initial molar ratio of halophthalic
anhydride to diamine", said adding being carried out at a temperature of at least 100°C;
wherein the at least one molten diamine has the formula H2N-A1-NH2 wherein A1 is a C2-C40
divalent aromatic radical;
(C) heating the reaction mixture formed in step (B) to a temperature of at least 100°C,
optionally in the presence of an imidization catalyst, and removing at least 95% of the water of
imidization;
(D) analyzing the reaction mixture formed by the combination of steps (A)-(C) to determine
the initial molar ratio of halophthalic anhydride to diamine; and
(E) adding anhydride or diamine to the mixture formed by the combination of steps (A)~
(C) to achieve a "corrected molar ratio" of halophthalic anhydride to diamine, said corrected
molar ratio being in a range between about 2.01 and about 2.3, and heating to a temperature of
at least 100°C to obtain a bis(halophthalimide) product mixture that is substantially free of
water.
2. The method according to claim 1 wherein said analyzing the reaction mixture
formed by the combination of steps (A)-(C) to determine the initial molar ratio of
halophthalic anhydride to diamine, comprises determining a concentration of
halophthalic anhydride, a concentration of by-product halophthalic acid, and a
concentration of intermediate monophthalimide monoamine in the reaction mixture
formed by the combination of steps (A)-(C).
3. The method according to claim 1 wherein said bis(halophthalimide) has
structuture I

wherein X and X are independently fluorine, chlorine, bromine or iodine; and Q is a C2-C20
divalent aliphatic radical, a C2-C40 divalent aromatic radical, or a C4-C20 divalent cycloaliphatic
radical; p is independently at each occurrence an integer ranging from 1 to 4.
4. The method according to claim 1 wherein the halophthalic anhydride is 4-
chlorophthalic anhydride, 3-chlorophthalic anhydride, 4-fluorophthalic anhydride, 3-
fluorophthalic anhydride, or a mixture comprising at least two of the foregoing.
5. The method according to claim 1 wherein the at least one diamine is selected from the
group consisting of oxydianiline, and bis(4-aminophenyl)sulfone.
6. The method according to claim 1 wherein said diamine is selected from the group
consisting of aromatic diamines III and diamines IV

wherein R1 and R2 are independently at each occurrence a halogen atom, a nitro group, a cyano
group, a C2-C20 aliphatic radical, a C2-C40 aromatic radical, or a C4-C20 cycloaliphatic radical; and
"n" and "m" are independently integers ranging from 0 to 4.
7. The method according to claim 1 wherein each of steps (A)-(C) and (E) is characterized
by a percent solids content, said percent solids content being less than about 17% solids.
8. The method according to claim 1 wherein step (C) and optionally step (E) further
comprises distilling water from the reaction mixture through a condenser maintained at a
temperature greater than the boiling point of water and less than the boiling point of the
solvent, wherein the boiling point of the solvent is greater than the boiling point of water.
9. The method of claim 1 wherein the halophthalic anhydride comprises 3-chlorophthalic
anhydride and 4-chlorophthalic anhydride.
10. The method of claim 1 wherein the halophthalic anhydride comprises 4-chlorophthalic
anhydride, the solvent comprises orthodichlorobenzene and the diamine comprises meta-
phenylene diamine and para-phenylene diamine.

ABSTRACT

Title: Method to prepare Bis(Haloimides)
A method for preparing a bis(halophthalimide), said method comprising: preparing a mixture
comprising a halophthalic anhydride and a solvent, adding to the mixture formed in step (A) a
molten diamine to form a reaction mixture, said reaction mixture being characterized by "an
initial molar ratio of halophthalic anhydride to diamine", wherein the molten diamine has the
formula H2N-A1-NH2 wherein A1 is a C2-C40 divalent aromatic radical; heating the reaction
mixture formed in step (B) to a temperature of at least 100°C, optionally in the presence of an
imidization catalyst, and removing the water of imidization; analyzing the reaction mixture
formed by the combination of steps (A)-(C) to determine the initial molar ratio of halophthalic
anhydride to diamine; and adding anhydride or diamine to the mixture formed by the
combination of steps (A)-(C) to achieve a "corrected molar ratio" of halophthalic anhydride to
diamine, said corrected molar ratio being in a range between about 2.01 and about 2.3, and
heating to a temperature of at least 100°C to obtain a bis(halophthalimide) product mixture that
is substantially free of water.

METHOD TO PREPARE BIS (HALOIMIDES)

Documents:

Inventors:

PCT Conventions: