JPS5934189B2 - Method for producing diisobutenyl succinic anhydride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention produces diisobutenyl succinic anhydride (hereinafter abbreviated as "DIB・SA"), which is a species of alkenyl succinic anhydride, in a high yield by a thermal addition reaction of diisobutylene and maleic anhydride. It is about the method.

In general, alkenyl co-citric anhydride is used as an epoxy resin curing agent, polyester resin, alkyd resin, plasticizer, etc.
Used as a raw material for surfactants, etc.

The method for producing DIB-SA is described by Kurt Alder and Herbert Soll (A Blood, Vol. 565, No. 5).
7 (1949)) reported an example.
According to this method, 30 diisobutylene (2,4,4-trimethylpentene-1/2,4,4-trimethylpentene-2=approximately 4/1: weight ratio) (O,2
7 mol) [2,4,4-trimethylpentene-1 approx.
22 mol] and maleic anhydride 20y (O, 20 mol) were reacted at 190°C for 24 hours in 30ml of benzene, and then the reaction solution was distilled under reduced pressure to reduce the degree of vacuum to 12.
Fraction 26y at 172-174°C in mmHg (this fraction is D
IB/SA. ), and distillation residue 101
It was hot. The selectivity of DIB-SA at this time was 72.2
%. However, the selectivity was calculated as (weight of alkenyl succinic anhydride)/(total weight of alkenyl succinic anhydride and distillation residue) x 100%, and below:
The same is true. As a result of repeating the above experiment, we found that most of the distillation residue was heavy.

This shows that the ene addition reaction between maleic anhydride and olefin produces a large amount of heavy by-products in addition to the target alkenyl succinic anhydride. Unreacted olefins and unreacted maleic anhydride can be recovered and reused, so when producing alkaline succinic anhydride industrially, it is necessary to reduce the amount of heavy by-products. Unless the amount is decreased, the selectivity of alkenyl co-citric anhydride will not be improved, and therefore the yield will not be improved either. In order to solve these problems, we have attempted to reduce the amount of residue by subjecting α-olean to maleic anhydride to a thermal addition reaction in the presence of a hydroxyaromatic compound or an aminoaromatic compound, thereby reducing the amount of alkenyl A method for producing succinic anhydride with good selectivity (yield) has been reported (US Pat. No. 341,211).
1 specification).

This report mainly focuses on the reaction of dodecenyl anhydride as α-olefin with maleic anhydride in the presence of hydroquinone (a hydroxy aromatic compound) or phenothiazine (an amino aromatic compound). - It is stated that citric acid is produced with good selectivity. However, even if an olefin containing 2,4,4-trimethylbenzene-1 as a main component is reacted with maleic anhydride in the presence of the above compound, DIB-SA cannot be produced with good selectivity. The present invention solves these problems, has a small amount of residue, and can reduce the amount of DIB.
-Providing a method for producing SA with good selectivity.

That is, in the present invention, when producing diisobutenyl co-citric anhydride by reacting an olefin containing 2,4,4-trimethylbenzene-1 as a main component with maleic anhydride, N-N'-di-Sec. -Butyl-p-p/-diaminodiphenylmethane The present invention relates to a method for producing diisobutenyl co-citric anhydride, characterized in that the reaction is carried out in the presence of -butyl-p-p/-diaminodiphenylmethane.

Note that N-N'-di-Sec-butyl-p-p'-diaminodiphenylmethane is disclosed in the above-mentioned U.S. Patent No. 341211.
This is not stated in Specification No. 1.

Diisobutenyl succinic anhydride exists in various isomers, and the typical structure is shown by the following formula.

2,4,4-trimethylbenzene, the raw material of the present invention
An example of the olefin containing 1 as a main component is diisoptylene.

Diisobutylene is usually used industrially as Annalen No. 56.
As described in Vol. 5, page 57 (1949), it is an isomer mixture of 2,4,4-trimethylbenzene-1 and 2,4,4-trimethylbenzene-2, and the weight ratio is approximately 4. It is contained at a ratio of /1. However, the olefin used in the present invention is not limited thereto, and may include 2,4,4-trimethylbenzene-1 alone or 2,4,4-trimethylbenzene-1 as a main component, for example, 2,4,4-trimethylbenzene-1 as a main component. - An olefin mixture containing other olefins such as 4,4-trimethylbenzene-2 may also be used. In the olefin mixture, 2,4,4-trimethylbenzene-1
It is preferable that 50 mol% or more of is contained in order to improve the selectivity of DIB-SA.

α-olefin 2,4,4-trimethylbenzene-1 undergoes an ene addition reaction with maleic anhydride, resulting in DIB-S
Generate A. 2,4,4-trimethylbenzene-2 does not react directly with maleic anhydride, but it reacts with 2,4,4-trimethylbenzene-2 by heating.
・Isomerize to 4-trimethylbenzene-1, and then,
Since DIB-SA is produced by reacting with maleic anhydride, even if 2,4,4-trimethylbenzene-2 is contained in the olefin, there is no major disadvantage in the production of DIB-SA.

The amount of N-Nl-di-Sec-butyl-p-p'-diaminodiphenylmethane used is a particular feature of the present invention; A range of .01% by weight or more is preferred.

When the amount used is less than 0.01% by weight, the yield tends to decrease. Note that even if it is added in an amount exceeding 5% by weight, the selectivity does not decrease, but the selectivity does not improve in proportion to the amount added. From this point of view, the amount used is particularly preferably 0.05 to 1% by weight based on maleic anhydride. A suitable reaction temperature is 150-250°C. 150°C
If it is less than 250°C, the reaction will be too slow and it is not practical, and if it exceeds 250°C, the product will be undesirably colored.

In order to prevent DIB-SA from coloring, especially 180-220
A range of 0.degree. C. is preferred. The charging ratio of 2,4,4-trimethylbenzene-1 and maleic anhydride is not particularly limited. In order to produce DIB-SA with high selectivity, 1.7≦a
A range of /b is preferred.

When this molar ratio is less than 1.7, the selectivity decreases, and when it is less than 1, the product tends to be colored. There is no particular upper limit on the upper limit, but if the molar ratio exceeds 15, the amount of olefin recovered will increase, which tends to increase the capacity of reactors, distillation columns, etc., and increase utility costs. Also, from this perspective, a/b
is particularly preferably from 2 to 10. In addition, 2.4.4-
A polymer of trimethylbenzene-1 is not produced as a by-product. The appropriate reaction time is about 2 to 7 hours at about 200°C. Next, the present invention will be explained in detail with reference to examples, but the present invention is not limited by the following examples unless it exceeds the gist of the invention. The composition of diisobutylene is shown in Table 1.

Diisoptylene 2247 (200 mol) and maleic anhydride 65.47 (0.667 mol) were placed in a 500 ml autoclave, and further 0.297 ml of N-N'-di-Sec-butyl-p-p'-diaminodiphenylmethane was added. (
After adding 0.44% by weight based on maleic anhydride, the mixture was electrically heated with stirring and reacted at 200° C. for 2 hours.

Take the reaction solution (homogeneous solution) 2007 and distill it under reduced pressure in a flask equipped with a Claisen type connecting tube (oil bath temperature 10
0-150℃) and unreacted diisobutylene 121.07
, 16.57 unreacted maleic anhydride was recovered. The pressure was further reduced and distillation was carried out at a vacuum level of 3 ml/LHg until the boiling point was 1.
42-146°C fraction (DIB-SA fraction) 58.0f
was obtained, and the distillation residue had a weight of 2.9f. At this time, D
The selectivity of IB-SA was 95.2%, and the residue was also 4.8%. In addition, the shortage (loss) during distillation 1
．． 6t, which is considered to be diisobutylene.

Example 2 The reaction time of Example 1 was changed from 2 hours to 7 hours, and the reaction and distillation were carried out under exactly the same conditions.

The results are shown in Table 2. Comparative example 1 N-N-di-Sec-butyl p-P7 used in Example 1
The reaction and distillation were carried out under exactly the same conditions except that hydroquinone was used instead of -diaminodiphenylmethane.

The results are shown in Table 2. Comparative example 2N-Merge-Sec-
Table 2 shows the results when phenothiazine was used instead of butyl-p-pl-diaminodiphenylmethane.

Comparative Example 3 Under the conditions of Example 1, N-N'-di-Sec-butyl-p
An experiment was conducted in the case where -p'-diaminodiphenylmethane was not added.

The results are shown in Table 2. As is clear from the above, in the present invention, by using a compound of the general formula (in which R1 to R2 are C2 to C8 alkyl groups), significantly heavier by-products (residues) are produced compared to conventional methods. DIB-SA can be produced with high selectivity (and therefore high yield) by reducing the amount of produced.

Claims (1)

[Claims] 1 In producing diisobutenylsuccinic anhydride by reacting an olefin containing 2,4,4-trimethylpentene-1 as a main component with maleic anhydride, N.N'-di-sec-butyl - A method for producing diisobutenyl succinic anhydride, characterized in that the reaction is carried out in the presence of p.p'-diaminodiphenylmethane. 2. Diisobutenyl anhydride according to claim 1, wherein the amount of N.N'-di-sec-butyl-p.p'-diaminodiphenylmethane used is 0.01% by weight or more based on maleic anhydride. Method for producing succinic acid.