US3649496A

US3649496A - Process for the production of alkylaryl succinic anhydrides

Info

Publication number: US3649496A
Application number: US856180A
Authority: US
Inventors: Vsevolod Vladimiro Nesterovsky; Marfa Markovna Murashkina; Vladimir Ivanovich Karzhev; Ekaterina Ivanovna Silchenko; Nina Vasilievna Goncharova; Margarita Viktorovna Maikova; Julius Lazarevich Khmelnitsky; Valentina Petrovna Svirina
Original assignee: VSEVOLOD VLADIMIROVICH NESTERO
Current assignee: VSEVOLOD VLADIMIROVICH NESTERO
Priority date: 1969-09-08
Filing date: 1969-09-08
Publication date: 1972-03-14
Anticipated expiration: 1989-03-14

Abstract

A PROCESS FOR THE PRODUCTION OF ALKYLARYL SUCCINIC ANHYDRIDES COMPRISING THE CONDENSATION OF ALKYL DERIVATIVES OF BENZENE WITH ANHYDRIDES OF DIBASIC ALIPHATIC ACIDS. THE PROCESS INVOLVES HEATING THE MATERIALS UNDER PRESSURE UNDER THE ACTION OF IONIZING RADIATION. ADDITIONALLY, ORGANIC PEROXIDES MAY BE USED WITH THE RADIATION.

Description

United States Patent 50 l" 3,649,496 PROCESS FOR THE PRODUCTION OF ALKYLARYL SUCCINIC ANI-IYDRIDES sevolod Vladimirovich Nesterovsky, Ulitsa Pivchenkova *"5," kv: 28; Julius-Lazarevich Klimelnitsky, Semenovuskaya naberezhnaya 3/1, korpus 1, kv. 41; Vladimir lvanovich Karzhev and Ekaterina Ivanovna Silchenko, both of Zubovsky bulvar 31/ 33,'kv. 30; Nina Vasilievna Goncharova, Jurievsky pereulok 22, korpus 1, kv. 111; Valentina Petrovna Svirina, Shosse Entuziastov 146- 154, kv. 91; Margarita Viktorovna Maikova, Rublevskoeshosse 91, korpus 3,. kv. 43; and Marfa Markovna Mur'ashkina, 5 Parkovaya ulitsa 38/13, korpus 4, kv. 12, all oliMoscow,,U.S.S.R.vv No Drawing.,Filed Sept. 8, 1969, Ser. No. 856,180

,7 ..Int'. Cl. B01j N US. Cl. 204- 162 BE 17 Claims ABSTRACT OF THE DISCLOSURE A process for the production of alkylaryl succinic anhydridescomprising the condensation of alkyl derivatives ofbenzenewith anhydrides of dibasic aliphatic acids. The process involves heating the materials under pressure under the action of ionizing radiation. Additionally, organic peroxides maybe used with the radiation.

The present invention relates. to processes for the production of anhydrides of dibasic acids and, more particularly, to a process for the production of alkylaryl succinic anhydrides employed for the synthesis of dialkyl esters of saidacids. These esters can serve as ingredients oflubricants for modern machinery. -In apreviously known process for the production of alkylaryl. succinic'anhydrides, alkyl derivatives of benzeneare; condensed with anhydrides of dibasic aliphatic acids undera pressure of about 40 gauge atm. in the presence of iodine, bronze, finely divided quartz or a Friedel-Crafts catalyst or without a catalyst while heating above 300?v C. (cf. GeraPats. 607,380 and 623,338). Disadvantages of the above process employing a cata l'yst are the necessity of separating said catalyst from the reaction products, and regenerating said catalyst, as well asith'e low yield of final products-up to 42%. When condensation is carried out without a catalyst the yield is stilllov'verk It is .als'o known to initiate the condensation of alkyl derivatives of benzene with anhydrides of dibasic aliphatic acids by rn'eans of organic peroxides while heating to 155 C., cf. Pat. 2,692,270).

7 The disadva'ntage of this process is the impossibility 5f producing benzylsuccinic anhydride from toluene and maleic anhydride,

' 'Itis accordingly the object of the present invention to provide an improved process for the production of alkylaryl'succinic anhydrides employing a new initiator for the, condensation of alkyl derivatives of benzene with anhydrides of dibasic aliphatic acids.

This objecthas been accomplished by the provision of aprocess for the production of alkylaryl succinic anhydrides involving the condensation of alkyl derivatives of benzene with anhydrides of dibasic aliphatic acids by heating under pressure in the presence of an initiator, wherein, accordingv to the invention, condensation is carried. out under the action of ionizing radiationor under the action of ionizing radiation in the presence of an organc'peroxide.

' Toluene, ethylbenzene and m-xylene are preferably employed as alkyl derivatives of benzene.

Maleic or citraconic anhydride is advantageously employed as the {anhydride of a dibasic aliphatic acid.

'ice

The highest yield 'of final product per unit reaction volume is obtained when the molar ratio of alkyl derivatives of benzene to dibasic acid anhydrides'is in the range of 5:1 to 45:1 and the volume feed rate is 0.3-0.9

, Condensation 'is preferably carried out under'theaction of gamma radiation in a dose of 0.5 x 10 to 1.3 X10 rad at a rate of not less than 50 rad/sec. at a temperature of ZOO-350 C. and pressure of 6 to 70 gauge atm.

Condensation can also be carried out under the action of gamma radiation from co'balt in the presence of isopropylbenzene hydroperoxide or di-tert-butyl peroxide. Organic peroxides are preferably taken in an amount equal to 0.03 wt. percent of the raw material.

Condensation under the action of ionizing radiation in the presence of an organic peroxide is preferably carried out at a temperature of ZOO-265 C. and under a pressure of 6 to 20 gauge atm.

The process is carried out as disclosed below.

The mixture of reagents is fed under pressure into a preheated reactor situated in a field of ionizing radiation. After passing through the reactor the reaction products are separated from the unreacted material.

When both ionizing radiation and an organic peroxide are used simultaneously as initiators, the peroxide is added to the mixture of reagents and the process carried out as described above.

The process can be carried out either continuously or batchwise, preferably in the liquid phase.

The advantage of the present process when condensation is initiated by ionizing radiation is that no chemical initiator or catalyst is employed and consequently it is unnecessary to prepare said initiator or catalyst, separate the same from the reaction products and regenerate the same.

When an organic peroxide is used as an initiator in combination with ionizing radiation the stages of separation and regeneration are likewise unnecessary since the peroxides used decompose completely and do not contaminate the reaction products.

Combining an organic peroxide with ionizing radiation makes it possible to intensify the process or lower the temperature at which it is carried out.

The' process of this invention is illustrated in the following examples.

EXAMPLE I Production of benzylsuccinic anhydride An 0.8 l. autoclave is charged with 400 g. of toluene and 40 g. of maleic anhydride. The mixture is then irradiated with gamma radiation from a cobalt source for 3 hours at a temperature of 350 C. and pressure of 96 gauge atm. The radiation dose is 13x10 rad at a rate of 1200 rad/sec.

Benzylsuccinic anhydride is recovered from the reaction products in an amount equal to 108.2 wt. percent of the maleic anhydride taken; M.P. 92-96 C.

The white crystalline benzylsuccinic acid obtained by recrystallization from water has a melting point of 161 C. and acid number of 538, which corresponds to the calculated value.

Found (percent): C, 63.6; H, 6.05. Calculated (per cent): C, 63.4; H, 5.77.

EXAMPLE 2 Production of benzylsuccinic' anhydride An 0.8 l. autoclave is charged with 400 g. of toluene and 40 g. of maleic anhydride and the mixture irradiated with gamma radiation from a cobalt source for 3 hours at a temperature of 200 C. and pressure of 6 gauge atm. The radiation dose is 1.3 X101 rad at a rate of 1200 rad/sec.

Benzylsuccinic anhydride is obtained in ayieldequafto 55.7 wt. percent of the maleic anhydride taken; M.P. 92-95 C. p

Y EXAMPLE "3 Production of benzylSuccinic anhydride Production of benzylsuccinic anhydride Into an 0.8 1. reactor is passed a mixture of maleic anhydride and toluene in a molar ratio of 1:20 at a volume feed rate of 0.3 hr:- at a temperature of 265 C. and pressure of 70 gauge atm. while being irradiated with gamma radiation from a cobalt source in a dose of 7.1 10 rad at a rate of 800 rad/sec. Benzylsuccinic anhydride is obtained in a yield equal to 136 wt. percent of the maleic anhydride taken; M.P. 92-96 C.

EXAMPLE 5 Production of benzylsuccinic anhydride Into an 0.8 l. reactor is passed a mixture of maleic anhydride and toluene in a molar ratio of 1:45 at a volume feed rate of 0.9 hr.- at a temperature of 265 C. and pressure of 70 gauge atm., while being irradiated with gamma radiation from a cobalt source in a dose of 22.4X rad at a rate of 800 rad/sec. Benzylsuccinic anhydride is obtained in a yield equal to 147 wt. percent of the maleic anhydride taken; M.P. 92-95 C.

EXAMPLE 6 Production of benzylsuccinic anhydride An 0.8 l. autoclave is charged with toluene and maleic anhydride in a molar ratio of 5:1, and the mixture irradiated with gamma radiation from a cobalt source for 3 hours at a temperature of 350 C. and pressure of 16 gauge at-m. The radiation dose' is 1.3 10' rad at a rate of 1200 rad/sec. Benzylsuccinic anhydride is recovered from the reaction products in a yield equal to 43.5 Wt. percent of the maleic anhydride taken; M.P. 92-95 C.

EXAMPLE 7 Production of benzylsuccinic anhydride An 0.8 l. autoclave is charged with toluene and maleic anhydride in a molar ratio of :1, and the mixture irradiated with gamma radiation from a cobalt source "for 3 hours at a temperature of 265 C. and pressure of 16 gauge atm. The radiation dose is 0.5 X 10 rad at a rate of 50 rad/sec. Benzylsuccinic anhydride is recovered from the reaction products in an amount equal to 85 wt. percent of the maleic anhydride taken; M.P. 92-95 C.

EXAMPLE 8 Production of methylphenylmethylsuccinic anhydride An 0.8 l. autoclave is charged with 400 g. of ethylbenzene and 'g. *of maleic anhydride and themixture irradiated with gamma radiation from a cobalt source at a temperature of 265 C. and pressure of 10 gauge atm.

The radiation dose is 13x10" rad at a rate of 1200 rad/ sec. Methylphenylmethylsuccinic anhydride is recovered from the reaction products in an amount equal to 156 wt. percent of the maleic anhydride taken.

EXAMPLE 9 Production of m-methylbenzylsuccinic anhydride From a mixture of 400 g. ;of m-xylene and 35 g. of maleic anhydride there is obtainedin the conditiopsj'of Example 8, 137 wt. percent of m-methylbenzylsuccinic anhydride; M.P. 88-89" C.

The m-methylbenzylsuccinic acid obtained by recrystallization from water has a melting point of 127 Crand an acid number of 512 which is close to the calculated'ivalue Found (percent); C, 64.73; H, 6.48.

Calculated (percent): C, 64.6; H, 6,74,

Production of benzylmethylsuccinic anhydride- 'From a mixture of 400 g. of toluene and 39j g; of citraconic anhydride there is obtained, in the conditions of Example 8 benzylmethylsuccinic anhydride in an amount equal to 36 wt. percent of the citraconic anhydride taken; M.P. 8286 C.

EXAMPLE '11 Production of benzylsuccinic anhydride Production of ben zylsuccinic anhydride From a mixture of 400 g .of toluene, 40 g.of maleic anhydride and 0.12 g. of isopropylbenzene hydroperoxide there is obtained in the conditions of Example 11, benzylsuccinic anhydride in an amount equal to 57.3 wt. percent of the maleic anhydride taken; M.P. 92-95 C.

EXAMPLE 13 Production of benzylsuccinic anhydride The mixture specified in Example 1.1 is placedin an autoclave and irradiated with gamma radiationirom' a cobalt source at a temperature of 265 C. andpressure of 16 gauge atm. The radiation dose is 1.1x 10f at arate of 1000 rads/sec. Benzylsuccinic anhydride is recovered from the reaction products in an amount equal to 93.5 wt. percent of the maleic anhydride taken; M13. 92-95" C.-

EXAM-PLE 14 Production of benzylsuccinic anhydride The mixture specified in Example 12 is placed in an autoclave and irradiated with gamma radiation from-a cobalt source at a temperature of 265 C. and pressure of 16 gauge atm. The radiation dose is 1. 1X 10' rad ata rate of 1000 rad/sec. Benzylsuccinic anhydride is recovvered from the' reaction .products in a, yield equalto 54.2 wt. percent of the maleic anhydride taken; M.P. 92-959 0.

We claim: 1 v v 1. A process for theproduction of;.al'kylarylsuccinic anhydrides comprising condensing ,alkylbenzenes with maleic anhydride or derivatives thereofunder the effect of ionizing radiation at a temperature of from 200 to 350 C. and under a pressure of from .6 to 96 atm. ata radiation dose rate of from 50 to 1200 rad/ sec.

2. A process for the production of alkylarylsuccinic anhydrides comprising condensing alkylbenzenes with maleic anhydride or derivatives thereof under the combined effect of ionizing radiation and organic peroxides taken in an amount of 0.03% by weightbased on the feed stock, the process being conducted at a temperature of from 200 to 265 C. and under a pressure of from 16 to 70 atm. at a radiation dose rate of from 50 to 1200 rad/sec.

3. The process of claim 1 wherein the condensation is carried out under the effect of gamma radiation from a C source at a radiation dose of from 0.5 to 1.3 X 10' rad.

4. The process of claim 2 wherein the condensation is carried out under the efi'ect of gamma radiation from a C0 source at a radiation dose of from 0.5 X10 to 1.3 X 10 rad.

5. A process for the production of benzylsuccinic anhydride comprising condensing toluene with maleic anhydride under the effect of gamma radiation from a C0 source at a radiation dose of from 0.5 10 to 1.3 10' rad and a radiation dose rate of from 50 to 1,200 rad/sec., the process being conducted at a temperature of from 200 to 350 C., under a pressure of from 16 to 70 atm. and at a toluene-to-maleic anhydride molar ratio in the range of 5:1 to 45:1.

6. The process of claim 1 wherein the alkylbenzene is ethylbenzene.

7. The process of claim 2 wherein the alkylbenzene is ethylbenzene.

8. The process of claim 1 wherein the al'kylbenzene is m-xylene.

9. The process of claim 2 wherein the alkylbenzene is m-xylene.

10. The process of claim 1 wherein the maleic anhydride derivative is citraconic anhydride.

11. The process of claim 2 wherein the maleic anhydride derivative is citraconic anhydride.

12. The process of claim 1 wherein the alkylbenzeneto-anhydride molar ratio is in the range of 5 :1 to :1.

13. The process of claim 2 wherein alkylbenzenes and maleic anhydride or derivatives thereof are taken in a molar ratio of from 5 :1 to 45: 1.

14. A process for the production of alkylarylsuccinic anhydrides comprising condensing alkylbenzenes with maleic anhyride or derivatives thereof under the effect of gamma radiation from a C0 source and in the presence of isopropylbenzene hydroperoxide.

115. The process of claim 2 wherein the condensation is carried out under the elfect of gamma radiation from a C0 source and in the presence of di-tert-butyl peroxide.

16. The process of claim 1 wherein the space velocity of the feed stock is in the range of 0.3 to 0.9 hr.

17. The process of claim 2 wherein the space velocity of the feed stock is in the range of 0.3 to 0.9 hr.

References Cited UNITED STATES PATENTS 3,472,749 10/ 1969 Bradshaw 204162R BENJAMIN R. PADGETT, Primary Examiner US. Cl. X.R. 204158 HE