DE3212163A1 - METHOD FOR PRODUCING AROMATIC BIS (AETHERPHTHALIC ACID) OR AROMATIC BIS (AETHERANE HYDROID) - Google Patents

Description

Process for the production of aromatic bis (ether phthalic acid) or aromatic Bis (ethereal anhydride)

Prior to the present invention, as suggested by Heath et al. commonly assigned U.S. Patents 3,879,428 and 3,957,862 shown, aromatic bis (ether anhydrides) (hereinafter referred to as "bisanhydrides") of the general formula

I.

O-R-i

produced by a multistage process, including the base hydrolysis of an aromatic bis (ether-N-organosubstituted Phthalimides) of the formula

II.

IN

Ο — Χ

belonged to. A more specific compound of these is 2,2-bis [4- (3,4-dicarboxy) phenyl] propane-bis-N-methylimide

the formula

II A.

where R is a divalent aromatic radical with 6 to 30

1
Carbon atoms and R is a monovalent organic radical from the class of the C .., “.-Alkyl radicals and organic radicals with 6 to 20 carbon atoms, for example aromatic hydrocarbon radicals and their halogenated derivatives. This procedure led to a tetra-acid salt, which was then acidified to the tetra-acid and this was then dehydrated to the aromatic bis (ether anhydride) of the formula I.

Although the method of Heath et al. a valuable route to both the aromatic bis (ether phthalic acids) as well as the aromatic bis (etherphthalic anhydrides), it requires the base hydrolysis of the aromatic Bis (ether-N-organo-substituted phthalimides) of the formula II and the conversion of the resulting salt into the tetraacid as well as their subsequent dehydration. Besides the need for a number of steps to convert the Bisimides in a bisanhydride result in inorganic salts which pose problems of removal. Efforts are directed therefore to the creation of a simplified procedure for the preparation of the bisanhydride of the formula I or its Tetraacid precursor.

U.S. Patent 4,128,574 discloses an imide-anhydride exchange reaction which leads to the production of organic polycarboxylic acids, their anhydrides or organic imides. For example, in special cases, a bisimide is the

/ OK

Formula HA heated with phthalic anhydride in the presence of water to achieve an exchange between the aforementioned To effect bisimide and the phthalic anhydride and to produce the corresponding tetraacid or its anhydride.

Although the method known from the latter patent specification has many of the disadvantages of the prior art eliminated, e.g. the rapid conversion of N-alkyl substituted Bisimides, the direct production of cyclic anhydrides, the formation of inorganic salts or the Requiring a multi-step procedure, this known method is essentially an approach or Batch process. The recovery of a tetraacid or a bisanhydride in a satisfactory yield, 80% or above that, requires several heating and insulating cycles. It is also difficult to achieve a substantial transformation of the To achieve bisimides in the tetraacid or the bisanhydride without recycling excess amounts of phthalic acid or to take refuge in phthalic anhydride. Due to the nature of the exchange between the bisimide and the phthalic acid or the phthalic anhydride, optimal conversion cannot be realized unless the N-organophthalimide the general formula

III. liii "n — ä ⁽

wherein R is as defined above, also in the implementation arises, is separated from the mixture.

U.S. Patent 4,116,980 has shown that optimal conversion of the bisimide into the tetraacid or its dianhydride on the basis of the imide-anhydride exchange in the presence of water can be done as by the following equation

Λ *

reproduced:

A + B ^

wherein A and A ^{1 are} imides and B and B ^{1 are} anhydrides when dcu; Imide A ^{1 is} selectively removed from the reaction during the exchange. For example, in the above equation, A can be a bisimide, B can be phthalic acid, B ^{1 can be} a bisanhydride or tetraacid, and A ^{1 can be} an N-organophthalimide. According to the latter patent, these results were achieved by venting part of the vapor phase during the exchange. The vapor phase consisted essentially of water and N-organophthalimides with very little phthalic acid, so that by continuously letting off the vapor phase during the exchange, the reaction is shifted to the right side of the equation. The starting bisimide can therefore be converted into the corresponding tetraacid or bisanhydride without completely closing off the reactor or recycling excessively large amounts of phthalic acid.

The invention is based on the development of a new two-phase Imide-anhydride exchange process in which a solution of an aromatic bis (ether-N-organo-substituted Phthalimide), hereinafter also identified as "BI", in an inert organic solvent with an aqueous one Solution of phthalic acid, hereinafter also referred to as "PA", and an exchange catalyst at an elevated temperature is brought into contact. The imide-anhydride exchange occurs and a major portion of the bis-compound goes from the organic phase to the aqueous phase, where it is used as a salt of the aromatic bis (etherphthalic acid), below also as "TA" of the general formula:

IV. Ο ο

C-OH

wherein R is as previously defined, denotes. This connection becomes easy after conventional measures converted into the aromatic bis (ether phthalic anhydride), hereinafter also referred to as "DA" of the formula I. The N-organophthalimide, also referred to below as "PI" and formed by the exchange, emerges from the aqueous Phase into the organic phase and enables or facilitates an increased conversion of BI into TA. Unimplemented (Excess) phthalic acid remains in the aqueous phase as a salt.

All imides (PI and BI) are in front of the exchange reaction in the organic phase and all acids and catalysts in the aqueous phase. After the exchange reaction, after the equilibrium has been established, the main part of BI has passed from the organic phase into the aqueous phase, where it is present as the salt of TA. That which is also referred to as "PI" in the following and is formed by the exchange Phthalimide goes into the organic phase along with unreacted BI and some aromatic bis (ether-N-organosubstituted Phthalimide ether anhydride), hereinafter referred to as "IA" of the general formula

V.

wherein R and R 'are as previously defined. Thus, apart from the presence of one, there is equilibrium small amount IA in both phases, the original state before, with all imides in the organic phase and all Acids or salts of acids in the aqueous phase

are in hand.

Corrosion problems associated with previous processes can be eliminated by neutralizing all acids using a Amine catalyst can be practically eliminated, and moreover The two-phase exchange process enables a clean separation of the N-organophthalimide from the phthalic acid. Of the Exchange can also be catalyzed rapidly, requires considerably less process energy than the previous processes and receives reaction components, solvent and catalyst.

The invention relates to a two-phase imide-anhydride exchange process for the preparation of aromatic bis (ether phthalic acid) from aromatic bis (ether phthalimide), the following Steps include:

(A) heating at elevated temperature, for example from 170-260 ⁰ C and under superatmospheric pressure, for example 14-35 bar (200-500 psi) of a mixture of (i) aromatic bis (ätherphthalimid) of the formula II, (ii ) 2 to 20 moles of phthalic anhydride or phthalic acid per mole (i),

(iii) a sufficient and effective amount of a replacement catalyst ,

(iv) 0.01 to 100 parts of water per part by weight of (i), (v) 0.01 to 100 parts of a water immiscible, inert organic solvent per part by weight (i),

to an equilibrated liquid, two-phase reaction mixture with an aqueous phase and the aromatic bis (etherphthalic acid), the exchange catalyst, formed in the exchange reaction, selectively dissolved therein together with unreacted phthalic acid,

- AHr

and with an organic phase selectively dissolved therein N-organo-substituted Phthalimide of the formula III, which was also formed in the exchange reaction, together with unreacted aromatic bis (etherphthalimide),

B) separating the organic phase from the aqueous phase and

C) Obtaining the aromatic bis (etherphthalic acid) from the aqueous phase.

R residues are e.g.

CH, Br Bf CH,

CH ₁ Bf Br CH,

OCH,),

and divalent organic radicals of the general formula;

PWo

wherein X is a member of the class of divalent radicals

ι
Formulas: -CH ₃ ,> C = 0, O = S = O, -0-, -S-, where m is O or 1

and y is an integer from 1 to 5 inclusive.

Residues R are e.g. phenyl, tolyl, XyIyI, naphthyl, chlorophenyl, Bromonaphthyl etc., and alkyl radicals such as methyl, ethyl,

Propyl etc.

The bisimides of Formula II and a process for their preparation are detailed in the aforementioned US Pat 3 879 428, based on the initial BiI, Formation of N-organo-substituted phthalimide of the formula:

VI.

wherein X is a radical from the class nitro, halogen, e.g., chlorine, fluorine, bromine, etc., and R is as previously defined. That Phthalimide of the formula VI can by a reaction between X-substituted phthalic anhydride and an organic Amine, such as aniline, toluidine, methylamine, ethylamine, etc., are formed.

Of the phthalimides of the formula VI, e.g. N-methyl-4-nitrophthaliniid, N-phenyl-3-nitrophthalimide, N-phenyl-4-nitrophthalimide, N-methyl-3-nitrophthalimide, N-butyl-4-nitrophthalimide etc., includes. As further shown in US Pat. No. 3,879,428, the aromatic bis (etherphthalimide) of the formula II by reaction between phthalimides of the formula VI and an alkali metal diphenoxide of the general Formula:

VII. M-O-R-O-M,

wherein R is as previously defined and M is a metal ion of an alkali metal, e.g. sodium, potassium, lithium, etc., is to be produced.

The alkali diphenoxides of the formula VII include sodium and potassium salts of the following dihydric phenols:

2,2-Bi S (2-hydroxyphenyl) propane; 2,4'-dihydroxydiphenylmethane; Bis (2-hydroxyphenyl) methane; 2,2-bis- (4-hydroxyphenyl) propane, hereinafter referred to as "bis-

phenol-A "or" BPA "denotes 1,1-bis- (4-hydroxyphenyl) ethane; 1,1-bis- (4-hydroxyphenyl) propane; 2,2-bis- (4-hydroxyphenyl) pentane; 3 , 3-bis (4-hydroxyphenyl) pentane; 4,4'-dihydroxybiphenyl;4,4'-dihydroxy-3,3,5,5'-tetramethylbiphenyl;2,4'-dihydroxybenzophenone;4,4'-dihydroxydiphenylsulfone;2,4'-dihydroxydiphenylsulfone;4,4'-dihydroxydiphenylsulfoxide; 2,4 "-dihydroxydiphenyl sulfoxide; 4,4'-dihydroxydiphenyl sulfide; Hydroquinone;
Resorcinol;

3,4'-dihydroxydiphenylmethane; 4,4'-dihydroxybenzophenone; 4,4'-dihydroxydiphenyl ether etc.

Exchange catalysts which can be used according to the invention are acids such as sulfuric, phosphoric, hydrochloric, methanesulphonic, fluoroboronic, toluenesulphonic, acetic, butyric, trifluoroacetic acid, etc .; Metal salts such as FeCl ₃ , ZnC ^, SnCl ^, AlCl ₃ and their bromides; Trialkylamines, hereinafter also referred to as “R ₃ N ¹¹ , such as trimethylamine, triethylamine, tripropylamine, tributylamine, etc., the preferred catalysts being triethylamine and trimethylamine.

Organic solvents which can be used according to the invention are inert, water-immiscible solvents, any

-Xf-

initially present or formed during the exchange reaction Selectively dissolve imide, e.g. toluene, benzene, xylene, chlorobenzene and o-dichlorobenzene.

The following broad and preferred parameters are for the two-phase imide-anhydride process has been determined:

1. Temperature range 170 ° to 260 ⁰ C

preferably 185 to 225 ^° C

2. pressure determined by temperature,

Range 14-35 bar (200-500 psi)

3. PA / BI molar ratio range 2: 1 to 20: 1

preferably 4-6: 1

4. Catalyst / PA Molver range 1: 1 to 3: 1 ratio preferably approx. 2: 1

5. organic solution range 0: 1 to 10: 1 medium / water weight - preferably approx. 4: 1 relationship

6. Solids content range 1 to 70%

preferably about 10-15%.

A better understanding of the practice of the invention can be obtained by referring to the figures will.

In Fig. 1 is a continuous three-step imide-anhydride exchange process, comprising the method of the invention; shown, the 2,2-bis-4- (3,4-dicarboxyphenoxy) phenylpropane of at least 97 mole percent purity by providing the imide-anhydride exchange between PA and BI takes place in the presence of an organic solvent, which the Imide selectively absorbed, the organic phase separated

and removed, then the equilibration separation is repeated two or more times with organic solvent to form TA in the aqueous phase. The organic phase is used in the third, second, then first equilibrium separation stage, after which it is distilled to remove the imides and recycled to the third equilibration stage. From the imides removed during the distillation, PI is recovered and can be nitrated and used to make more BI while the remaining BI and IA are recycled. After TA has been recovered from the aqueous phase by distillation of HUO, R ₃ N and unreacted PA, these materials are returned to the first stage of equilibration.

In detail, the first equilibrium setting tank is shown at 10, in which an aqueous solution of PA in excess and 2 moles of R ^ N catalyst per mole of PA are heated together with a toluene solution of BI. Phthalic acid (PA) or phthalic anhydride is fed to 10 via a line 3 from a PA storage container 2 together with recirculated water, R ₃ N and unconverted PA from the previous cycle via a line 12. Toluene is recycled from stage 2 of the previous cycle via line 13. BI stock material is fed from a container 1 via a line 11 to the first container 10 for equilibrium adjustment together with unreacted BI and partially converted IA, which are separated from the toluene in the distillation units 4 and 6 and transferred via lines 5 and 8. The two phases are ^{heated together at about 200 °} C. and 21 to 35 bar (300 to 500 psi) pressure, depending on the exact temperature, for 1 to 2 hours in order to give a mixture which is chemically in equilibrium.

The mixture is now pumped from the container 10 to establish the equilibrium via a line 14 to the phase separator or to the decanting device 20 of the first stage. While the mixture is still hot, it can settle and separate, the toluene phase is drawn off and pumped via a line 22 to a deep distillation unit 4, in which the toluene is drawn off and condensed for later recycling. The distillation residues from 4, which contain BI, IA and PI, are pumped via a line 5 to a second distillation plant 6, where PI is distilled off for possible subsequent production of BI. The distillation residues from 6, which contain BI and IA, are returned via line 8 to the first container 10 for equilibrium adjustment. The aqueous phase from the phase separator 20 of the first stage is pumped via a line 21 to a second container 30 for equilibrium adjustment, where it is mixed with toluene which has been decanted by the phase separator 60 of the third stage. When this has taken place in the second container 30 for equilibration, the mixture is pumped via a line 31 to a phase separator 40 of the second stage, where, after settling, the toluene layer is returned to the container 10 for the first equilibrium via line 13, and the aqueous phase is pumped via a line to the container 50 of the third equilibrium setting. Toluene from the distillation device 4 is pumped via a line 52 to the container 50 of the third equilibrium setting and the mixture is brought into equilibrium again and pumped to the last phase separator or decanter 60. After it has passed over, the toluene layer of 60 is returned via a line 32 to the container 30 of the second equilibrium and the aqueous phase is fed via a line 61 to a third distillation device 70, in which PA, HO and R ₃ N are distilled off, condensed and via line 12 to the container 10 of the first equilibrium can be returned. The still bottoms from 70 are removed to give DA.

-ys- 20

The following examples serve to better understand the practical implementation of the invention to illustrate, in no way limiting.

Each of the nine equilibrium adjustments were made in batches as described below. The toluene phases were handled as indicated in Fig. 2, which is easily understood.

Example I.

A 1 1 autoclave was filled with 35.7 g (0.24 mol) of phthalic anhydride, 21.84 g (0.04 mol) of the bisimide of the formula HA, hereinafter also referred to as "BPA-BI", 67 ml (0, 48 mol) of triethylamine, 80 ml of water and 320 ml of toluene are charged. The autoclave was flushed with N2, closed and ^{heated to 200 °} C. for 2 h. Then it was cooled and opened. The organic and aqueous phases were separated and samples were taken from each. The aqueous phase was returned to the autoclave together with the next suitable portion of toluene according to FIG. II. This was flushed again with N2, closed and ^{heated again to 200 °} C. for 2 h. It was worked up again as described for the initial equilibrium.

The samples of both phases from each cycle were removed under vacuum (about 25 mm) at 200 ⁰ C of solvent removed and analyzed by liquid chromatography (Waters Associates LC, Corisol-I, column 1/8 "χ 2 ', solvent = 40% CH ₃ Cl ₂ , 59.5% CHCl ₃ and 0.5% Et ₃ O; flow rate = 2 ml / min, detector = UV, Λ254) The results are shown in the following tables, with the compositions of the constituents in the aqueous phase are given in mol%.

η Ψ -m

Table I.

Product composition of the amide-anhydride exchange

(Mol%)

First cycle BI IA TA Balance adjustment 0.02 15.2 84.8 1 0.02 1.8 98.2 2 0.02 0.6 99.4 3 Second cycle BI IA TA Balance; !setting 0.02 6.0 84.0 1 0.02 2.4 97.6 2 0.02 0.4 99.6 3 Third cycle BI IA TA Balance adjustment 0.02 11.2 88.8 1 0.02 2.4 97.6 2 0.02 0.5 99.5 3

The above results show that there is a two-phase exchange reaction is able to deliver a product with at least about 85 mole percent TA after only one balance weight adjustment. Two and three steps resulted in about 98 and about 99.5 mole percent products, respectively.

The third equilibrium on all three cycles yielded about 18 grams (0.035 moles) of over 99 mole percent TA, which corresponds to an approximately 86% total conversion of the BI of the formula II into TA of the formula IV, which is easy to DA of the formula I is dewaterable.

ZX

The invention also includes the development of a continuous two-phase imide-anhydride exchange process, in which the solution of an aromatic bis (ether-N-organosubstituted Phthalimide), hereinafter also referred to as "BI", in the inert organic solvent the aqueous solution of phthalic acid, hereinafter also referred to as "PA", and an exchange catalyst at increased Temperature is brought together in a heating coil reactor. The imide-anhydride exchange occurs, and a major part the bis-compound passes from the organic phase to the aqueous phase, where it acts as a salt of the aromatic Bis (ether phthalic acid), hereinafter also referred to as "TA", the general formula

o - »- ^o " 4 ~ \ 3 J

is present. The conditions of elevated temperature and pressure for the imide-anhydride exchange reaction are im Laboratory easily adjusted by simple autoclaves. On an industrial scale, however, such a heavy-walled printing system becomes very expensive. In addition, stirring the contents of the autoclave will allow shorter reaction times would be very difficult as this type of plant has moving parts and high pressure seals around rotating shafts around is very expensive and difficult to work with. Mixing is a major problem in achieving equilibrium in the two-phase system according to the invention. Mixing can be accomplished by passing the two-phase mixture through can be reached by a horizontally held pipe coil. Due to differences in density, the organic phase through the aqueous phase on the ascending side of the snake and the aqueous phase falls through the organic phase on the descending side of the snake. The process runs the length of the queue and results good contact between the two phases and accelerated

consequently the process of establishing equilibrium.

Thus, it becomes a continuous, two-phase imide-anhydride exchange process for the production of aromatic bis (ether phthalic acid) from aromatic bis (ether phthalimide) with created the following stages:

A) Passing through a heated coil reactor at elevated temperature, for example 170-260 ⁰ C, and under superatmospheric pressure, for example between 14 and 49 bar (200-700 psi), a mixture with

(i) aromatic bis (ether phthalimide) of the formula II, (ii) 2 - 20 mol of phthalic anhydride or phthalic acid per Mole (i),

(iii) a sufficient and effective amount of a replacement catalyst ,

(iv) 0.01 to 100 parts of water per part by weight of (i), (v) 0.01 to 100 parts of "water immiscible" inert organic solvent per part by weight (i),

to an equilibrated liquid two-phase reaction mixture with an aqueous phase therein selectively dissolved the aromatic bis (etherphthalic acid) formed in the exchange reaction, the exchange catalyst together with unreacted phthalic acid, and with an organic phase, selectively dissolved therein N-organo-substituted phthalimide of the formula III, which was also formed in the exchange reaction with unreacted aromatic bis (etherphthalimide),

B) Separating the organic phase from the aqueous phase and

C) Obtaining the aromatic bis (etherphthalic acid) from the aqueous phase.

The tube coil reactor of this embodiment can be made of any tube, which the temperatures and pressures the reaction withstands and is not attacked by the two-phase reaction mixture. Examples of usable Pipes are those made of stainless steel 3.16, 347, glass, etc.

The length of the pipe (1), the cross-section of the pipe (a) and the flow velocity (r) influence the Rate of exchange reaction and therefore the residence time (t) that is required to reach equilibrium approximate. These parameters are linked by the relationship la / r = t. Kinetic Studies showed that a residence time of about 2 hours was required.

The tube coil reactor is, for example, powered by an oil-filled heating jacket or other conventional equipment. heats.

The following broad and preferred parameters are for the two-phase, continuous imide-anhydride hot tube reactor process has been determined.

1. · Temperature range 170-260 ⁰ C

preferably 185 to 225 ⁰ C

2. Pressure determined by temperature

Range 14-49 bar (200-700 psi)

3. PA / BI molar ratio range 2: 1 to 20: 1

preferably 4-6: 1

4. Catalyst / PA Molver range 1: 1 to 3: 1 ratio preferably approx. 2: 1

5. organic solvent / water range 0: 1 to 10: 1 Weight ratio preferably approx. 4: 1

6. Solids content range 1 to 60%

preferably approx. 10-15%

7. PA concentration in the aqueous phase 0.2-6 mol / l preferably approx. 3 mol / l

8. BI concentration in the organic range 0.02-1 mol / l see phase preferably about 0.2 mol / l

In the practical implementation of the continuous process, an aqueous solution, the PA and an exchange catalyst contains, and an organic solution containing BI, brought together and fed to the coil reactor under pressure. A warming of both reaction component phases is generally required to maintain more concentrated solutions. After the passage through the reactor, the phases are separated in a conventional manner and the solvents, reaction components and catalysts optionally distilled for recycling. The PI obtained from the organic phase can be nitrided and used for the production of further BI. The TA product in the aqueous phase delivers after dehydration, the DA product.

Example II

The hot tube reactor was a 347 stainless steel tube of 7.3 m (24 feet) inside diameter 10.9 mm in volume with a volume of 640 cm ³ in the form of a multiple coiled serpentine 16 cm in diameter positioned horizontally with respect to the axis of the serpentine. The reactor coil was enclosed in a copper jacket and was heated ^{to 200 ° C. with flowing hot oil.} The pressure in

The reactor was held at 35 bar (500 psi) to avoid boiling of the contents.

An aqueous solution of 2.98 mol / l of PA and 4.5 mol / l of triethylamine catalyst was heated to 65 ⁰ C, in order to avoid crystallization, and to the hot coil reactor at a rate of 3 ml / min pumped.

A toluene solution of 0.22 mol / l BI was heated to 80 ⁰ C and pumped at 7 ml / min to the hot tube reactor. These flow rates lead to a PA / BI molar ratio of 5.75: 1.

Total run time was about 6 hours at total flow rate of 10 ml / min, and samples were taken every 6 min after the calculated residence time.

The reactor was initially filled with aqueous PA solution.

The samples of both phases were liberated under vacuum (about 25 mm) at 200 ⁰ C of solvent and liquid chromatography analyzes (Waters Associates LC, Corisol-I, column 1/8 "χ 2 ^1, solvent = 40% CH ₂ Cl ₂ , 59.5% CHCl ₃ and 0.5% Et ₂ O; flow rate = 2 ml / min, detector = UV, X254).

The results are given in Table II below, where the concentration of Bis compounds (BI + IA + TA) is given in g / l and the concentration of TA in the bis compounds in mol%.

The data show that at about 120 minutes a steady state or was an equilibrium and thereafter no further material was transferred from the organic phase and the mol% TA remained unchanged at about 75%.

Table II

Product composition of the imide-anhydride exchange from the hot coil reactor

Time (min) To connections *,
g / i Mol% TA in
Up connections 39 8.99 43 50 33.33 70 60 87.66 83 72 119.33 81 81 146.33 79 93 163.33 76 105 170.66 75 120 182.00 75 135 184.03 77 152 186.60 74 - 170 188.00 '74 189 186.66 74 205 183.30 75

* Bis connections = BI + IA + TA

The above results show that one in a hot coil reactor carried out continuous two-phase exchange reaction a product with at least about 75 mol% TA is able to deliver after one reactor passage. The product from the first pass was among the same Conditions except that the toluene did not contain BI was again passed through the reactor. This led to a product with about 95 mole percent TA. A third pass, again with only toluene in the organic phase, provides one Product with at least 97 mol% TA,

Example III

The initial conditions and concentrations were the same as in Example I, but the flow rates were for the aqueous phase and the organic phase both 5 ml / min. This results in a PA / BI molar ratio from 13.42: 1.

The results are given in Table III below.

Table III Hot Coil Reactor Product Composition

Time (min) Up connection,
Concentration, g / l Mol% TA in
Up connections 56 67.6 88 68 94.9 88 81 100.0 88 93 102.0 88 105 104.0 88 116 100.6 88 128 100.3 88 141 101.1 88

These data show that a steady state after about 81 min is reached and provides a product with about 88 mol% TA. The shorter time to achieve equality weight, 81 min versus 120 min in Example II, and the higher mole percentage of TA, 88% versus 77% in Example II, based on the higher PA / BI molar ratio, 13.42: 1 versus 5.75: 1 in Example II.

Claims (19)

Dr. rer. nat. Horst Schüler ⁶⁰⁰ ° Frankfurt / Main 1.31 March 1982 PATENT Attorney Kaiserstrasse 41 Dr.Sch / Pr / Hk Telephone (0611) 235555 Telex 04-16759 mapat d Postal check account> 282420-602 Frankfurt / M. Bank account 225/0389 Deutsche Bank AG, Frankfurt / M. 8886-RD-10503 / RD-10521 GENERAL ELECTRIC COMPANY 1, River Road
Schenectady, NY, USA Claims Two-phase imide-anhydride exchange process for production aromatic bis (etherphthalic acid) of the formula O-R- or its anhydride, characterized by A) heating a mixture with (i) aromatic bis (ether phthalimide) of the formula (ii)
(üi)
(iv)
(v) hO-K — O- NO'. Il
ο Phthalic anhydride or phthalic acid, a replacement catalyst,
Water, a water-immiscible inert organic solvent to an equilibrium brought liquid, two-phase reaction mixture with an aqueous phase, therein selectively dissolved the aromatic bis (etherphthalic acid) formed in the exchange reaction, the catalyst, along with excess phthalic acid, and with an organic phase, selectively therein ? 1 row dissolved N-Qrgano-substituted phthalimide of the formula N-If which was also formed in the exchange reaction, together with unreacted aromatic bis (etherphthalimide), B) separating the organic phase from the aqueous phase and C) Obtaining the aromatic bis (ether phthalic acid) from the aqueous phase and optionally dehydrating to the dianhydride, where R is a divalent aromatic radical with 6 to 30 carbon atoms and R is a monovalent one Organo radical is selected from C ... "* -alkyl radicals and organic radicals having 6 to 20 carbon atoms from the class of aromatic hydrocarbon radicals and halogenated derivatives thereof. 2. The method according to claim 1, characterized in that it is carried out at a reaction temperature between about 170 and 26O ⁰ C and a reaction pressure between about 14 and 35 bar (about 200 to 500 psi). 3. The method according to any one of the preceding claims, characterized in that the phthalic acid in an amount between about 2 and 20 moles of the anhydride per mole of aromatic bis (ether phthalimide) is present. 4. The method according to any one of the preceding claims, characterized in that a replacement catalyst Trialkylamine is used. 5. The method according to claim 4, characterized in that triethylamine is used as the exchange catalyst. 6. The method according to any one of claims 1 to 5, characterized in that that the catalyst in a molar ratio of about 1 to 3 moles of catalyst per mole of bis (imide) is used. 7. The method according to any one of the preceding claims, characterized in that, on a weight basis, water in an amount between about 0.01 and 100 parts per part Until (imid) is used. 8. The method according to any one of the preceding claims, characterized in that the organic solvent Toluene is used. 9. The method according to any one of the preceding claims, characterized in that on a weight basis the solvent is used in an amount between 0.01 and 100 parts per part of bis (imide). 10. The method according to any one of the preceding claims, characterized in that R is methyl. 11. The method according to any one of the preceding claims, characterized in that the aromatic bis (etherphthalic acid) Is 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane. 12. The method according to any one of the preceding claims, characterized in that the bis (ether-N-organosubstituted Phthalimide) 2,2-Bls [4- (3,4-dicarboxyphenoxy) phenyl] propane-bis-N-methylimide is. 13. Two-phase imide-anhydride exchange process for manufacture aromatic bis (etherphthalic acid) of the formula O-* -4- or their anhydride from aromatic bis (etherphthalimide), marked by A) Heating to a temperature of 170-260 ⁰ C at a pressure of 14-35 bar (200-500 psi) of a mixture with (i) aromatic bis (ether phthalimide) of the formula O — R— (ii) 2 to 20 moles of phthalic anhydride or phthalic acid per mole of (i), (iii) 1 'to 3 moles of a trialkylamine exchange catalyst per mole (i), (iv) 0.01 to 100 parts of water per part by weight (v) 0.01 to 100 parts of a water immiscible one organic solvent per part by weight of (i) to an equilibrated liquid two-phase reaction mixture with an aqueous phase, selectively dissolved therein the aromatic bis (etherphthalic acid) formed in the exchange reaction, the trialkylamine catalyst together with excess phthalic acid, and with an organic phase, in which N-organo-substituted phthalimide is selectively dissolved the formula which was also formed in the exchange reaction, together with unreacted aromatic Bis (etherphthalimide), B) separating the organic phase from the aqueous phase, * * ■ fl <# -5- C) Obtaining the aromatic bis (etherphthalic acid) from the aqueous phase, where R is a divalent aromatic radical with 6 to 30 carbon atoms and R is a monovalent organo radical from the class of C ... _o , - (i-oj Alkyl radicals and organic radicals having 6 to 20 carbon atoms is from the class of aromatic hydrocarbon radicals and halogenated derivatives thereof, where X is a radical from the class nitro, halogen, 1
Fluorine, bromine, etc., and R is as previously defined. 14. Two-phase amide-anhydride exchange process according to one of claims 1 to 13, characterized by a number of equal weight adjustment and phase separation steps. 15. The method according to claim 14, characterized in that the reaction components, catalysts and solvents are recycled and continuously obtained. 16. Two-phase imide-anhydride exchange process according to a of claims 1 to 13, characterized in that it is made continuous by adding the mixture (A) is passed through a hot coil reactor. 17. The method according to claim 16, characterized in that it is carried out at a reaction ^{temperature between about 170 and 260 0} C and at a reaction pressure between about 14 and 49 bar (about 200 and 700 psi). 18. Continuous, two-phase imide-anhydride exchange process according to claim 16 for the preparation of aromatic bis (etherphthalic acid) of the formula: O-R-0 or their anhydride from aromatic bis (etherphthalimide), marked by A) Passing a mixture with (i) aromatic bis (ether phthalimide) of the formula ο ο C C, O + o-R-o-f O (ii) 2 to 20 moles of phthalic anhydride or phthalic acid per mole of (i),
(iii) 1 to 3 moles of a trialkylamine exchange catalyst per mole of (i), (iv) 0.01 to 100 parts of water per part by weight of (i), (v) 0.01 to 100 parts of a water-immiscible organic solvent per part by weight of (i) through a tubular coil reactor at 170 to 260 ⁰ C and a pressure of 14 to 49 bar (200 to 700 psi) to an equilibrated, liquid, two-phase reaction mixture with an aqueous phase, the aromatic bis (ether phthalic acid formed in the exchange reaction) selectively dissolved therein ), the trialkylamine catalyst together with excess phthalic acid, and with an organic phase, selectively dissolved therein N-organo-substituted phthalimide of the formula 0
C. ,1 which was also formed in the exchange reaction, together with unreacted aromatic bis (etherphthalimide) , φ. 4t »ft M * Λ« · —7 - B) separating the organic phase from the aqueous phase and C) Obtaining the aromatic bis (etherphthalic acid) from the aqueous phase, where R is a divalent aromatic radical with 6 to 30 Carbon atoms, R is a monovalent organic radical from the class of C, .._ ".- alkyl radicals and organic Radicals with 6 to 20 carbon atoms from the class aro-. matic hydrocarbon residues and halogenated derivatives of these and X is a radical from the class of the nitro group and halogen. 19. The method according to claim 18, characterized in that the reaction components, catalysts and solvents are continuously recycled.