JPS61172866A - Production of alkenylsuccinic anhydride - Google Patents

Abstract

PURPOSE:To produce an alkenylsuccinic anhydride suitable as a sizing agent for paper-making, economically on an industrial scale, by isomerizing a straight- chain 1-olefin to obtain isomerized olefins at a specific ratio, and adding maleic anhydride thereto. CONSTITUTION:A 12-22C straight-chain 1-olefin (especially preferably a mixture of 14C, 16C and 18C 1-olefins or 16C 1-olefin) is subjected to the isomerization reaction in the presence of an isomerization catalyst to decrease the 1-olefin content to <=20mol% and the content of the olefin component having the double bond inside of the 6-carbon atom to <=40mol%. 1mol of the olefin is added with 0.5-1.5mol of maleic anhydride, and subjected to the addition reaction in the presence of the same isomerization catalyst at 150-240 deg.C to obtain the objective alkenylsuccinic anhydride. EFFECT:The reaction can be carried out using the same catalyst at a low temperature producing little by-products such as tar, sludge, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a method for producing alkenylsuccinic anhydride. More specifically, the present invention relates to an industrially advantageous method for producing alkenylsuccinic anhydride suitable for use as a paper sizing agent.

``Prior Art'' Conventionally, long-chain alkenylsuccinic anhydrides are known to be effective as sizing agents for 91 paper (for example, Japanese Patent Publication No. 53-28526, VT No. 57-15).
4495, JP-A-59-62580, etc.).

The technique described in Japanese Patent Publication No. S7-28526 is a technique in which an olefin having 12 to 24 carbon atoms is reacted with maleic anhydride as an active ingredient, but the olefin used here is It is a so-called internal olefin in which the double bond is located inside the molecular chain. Such internal olefins are, for example, octadecene-9, tetrazo7ane-7, hexadecene-8, etc.; According to , it was found that reaction products made from such internal olefins do not have sufficient sizing effects as paper sizing agents.

JP-A-57-154495 proposes a method that eliminates the drawbacks of the method described in the above publication. According to this method, an olefin having 8 to 18 carbon atoms is produced.

It is characterized by using as a raw material a linear internal olefin in which the bonding positions are almost evenly distributed at each position except for the α-position. However, according to experiments conducted by the present inventors, it has been found that reaction products made from such mixed olefins do not have sufficient sizing effects as paper sizing agents.

Furthermore, what is described in Japanese Patent Application Laid-Open No. 59-62580,
2. As an olefin. This is a method using a linear a-olefin having 13 to 16 carbon atoms and a subordinate internal olefin or branched olefin having 14 to 22 carbon atoms. According to this method, the raw material olefin can be obtained relatively inexpensively, but according to the experiments of the present inventors, the reaction product made from this raw material does not have sufficient sizing effect as a paper sizing agent. I found out.

``Problems that the invention seeks to solve'' The present invention uses readily available olefin as a raw material, has low solubility in water but has good dispersibility, has little performance deterioration due to hydrolysis during storage, and It is an object of the present invention to provide an industrially advantageous method for producing alkenylsuccinic II anhydride, which has a large amount of fixation on bulbs, exhibits excellent sizing effects, and is suitable for use as a paper sizing agent.

"Means for Solving the Problems" However, the gist of the present invention is that the number of carbon atoms is from 12 to
Up to 22 linear 1-olefins are subjected to an isomerization reaction using an isomerization catalyst to convert 1.1-olefin components into 2
0 mol% or less, the olefin component whose double bond is inside the 6th carbon position is 40 mol% or less, and maleic anhydride is 0.5 to 0.5% to 1 mole of this olefin.
Added in a range of 1.5 mol, in the presence of an isomerization catalyst, 15
Flukenylsuccine W! is characterized by carrying out an addition reaction in the temperature range of 0 to 240°C. It consists in a method of manufacturing an anhydride.

The present invention will be explained in detail below.

The olefin used in the present invention has 12 to 22 carbon atoms.
It is a straight chain olefin. If an olefin with less than 12 carbon atoms is used, the product obtained by addition reaction with maleic anhydride will be poorly soluble in water, and the amount fixed on the pulp during paper making will be small, so the final product Those having a carbon number greater than 22 are not preferred because the sizing of the paper is not improved, and those having a carbon number greater than 22 are not preferred because the product obtained by addition reaction with maleic anhydride is difficult to disperse in water during use.

Linear 1-olefins having 12 to 22 carbon atoms are olefins with an even number of carbon atoms obtained by low polymerization of ethylene, such as olefins with carbon atoms of 12, 14, 16, 18, 20, 22, etc.
olefins and mixtures thereof; internal olefins obtained by isomerizing 1-year-old fins that are easily available industrially; those obtained by decomposition of wax and dehydrochlorination of chlorinated paraffins; obtained by Fischer-Tropsch synthesis method Among the olefins with 12 to 22 carbon atoms, which refer to a wide range of linear olefin mixtures and those obtained by distillation thereof, mixtures of olefins with 14, 16 and 18 carbon atoms, or It is particularly preferable to use the number 16 because the reaction product has particularly good dispersibility in water and tends to form fine dispersed droplets of the sizing agent.

The olefin used in the method of the present invention has 12 to 12 carbon atoms.
In addition to the 22 atoms, as mentioned above, the 1-olefin component is 20 mol % or less, and the olefin component whose double bond is located inside the 6-position carbon is 40 mol % or less.

This means that for olefins whose double bond is at the 1st carbon position, the reaction product obtained by addition reaction with maleic anhydride is solid at room temperature except for olefins with 12 carbon atoms, and when used, it is Since it is difficult to disperse in the olefin and the size effect is extremely poor, the proportion of
The content shall be 0 mol% or less. Particularly preferably, the content of the 1-olefin is 5 mol % or less.The olefin used in the method of the present invention is also an olefin component in which the double bond is located internally from the 6th carbon position. be 40 mol% or less. When an olefin having such a composition is used, the reaction product obtained by the addition reaction with maleic anhydride is easily dispersed in water, and a large amount of it is fixed to the pulp during paper making, resulting in an excellent sizing effect.

In the method of the present invention, an olefin having the above requirements, 1-
It can be produced by subjecting an olefin to an isomerization reaction using an isomerization catalyst.

In the present invention, isomerization catalysts include silica/titania, silica/alumina, silica/titania/alumina, silica/titania/iron oxide, silica/alumina/iron oxide, alumina/iron oxide, and silica with various composition ratios. - Refers to iron oxide, silica/alumina/magnesia, silica/alumina/calcium oxide, silica/titania/magnesia, aluminosilicates of alkali metals or alkaline earth metals, etc.

The above isomerization catalysts can be used alone or in combination of two or more.

The above-mentioned isomerization catalyst can be produced by various conventionally known methods, such as a homogeneous precipitation method, an impregnation method, and a gas phase synthesis method. The "homogeneous precipitation method" is a method that complies with Weimarn III when producing a precipitate from a homogeneous solution. In the "impregnation method", a ready-made catalyst carrier such as commercially available silica, alumina, or silica/alumina is immersed in an aqueous solution of a salt containing a catalytically active component by a competitive adsorption method, and after drying, the salt is thermally decomposed. This is a method of activating. The "gas phase synthesis method" is a method of producing oxide fine powder through a gas phase reaction. In addition, there is also a method of simply mixing fine powder and press-molding it.

Furthermore, various catalysts proposed as 1-olefin isomerization catalysts, such as Japanese Patent Publication No. 44-13482,
Catalysts described in Japanese Patent Publication No. 45-15483 and the like can also be used.

The amount of the isomerization catalyst used is based on the 1-olefin.
It is best to choose between 0.0001 and 10% by weight. If the amount of catalyst used is less than 0.0001 to 10% by weight, the catalyst may be deactivated by coking during the isomerization reaction. , the reaction stops progressing midway, which is undesirable, and 1
If it is more than 0% by weight, it will be economically disadvantageous. Within the above range, a range of 0.05 to 1.0% by weight is particularly preferred.

To isomerize 1-olefin, in a sealed reaction vessel,
The raw material 1-olefin and the isomerization catalyst were charged, the atmosphere inside the reaction vessel was replaced with an inert gas, and the internal temperature was reduced to 160℃ under stirring.
The temperature is raised to ~220°C, maintained, and the position of the double bond of the olefin is confirmed by analysis, while the reaction is carried out until the composition essential for the present invention is achieved.

In addition, in order to prepare the olefin that satisfies the above-mentioned requirements used in the method of the present invention from industrially easily available 1-olefin, the following method may be used.

That is, first, a 1-olefin and an isomerization catalyst were charged into a sealed reaction vessel purged with nitrogen gas, and
In the temperature range of 20°C, while analyzing the double bond position of the olefin, the reaction can be carried out using insects that achieve a composition that satisfies the requirements essential to the present invention.The reaction time and reaction temperature are as follows: It varies depending on the type, type of isomerization catalyst, amount used, etc.

For example, when isomerizing a 1-year-old fin with 16 carbon atoms, sII was prepared by coprecipitation as a catalyst.
・ChiP Near Catalyst (S io2/T!Oi= 1
/ 1) When 0.2% by weight of olefin activated at 400°C is added, the temperature is 170°C.
4 to 6 hours at a temperature of 1.5 hours at a temperature of 200℃
In 2.5 hours, an olefin having a composition that satisfies the essential requirements of the present invention can be obtained. When 0.5% by weight was added to the olefin, it was added at a temperature of 170°C for 2 to 3 hours.
An olefin having a composition satisfying the essential requirements of the present invention can be obtained.

The position of the double bond in the olefin after the isomerization reaction can be confirmed by analysis during the olefin isomerization reaction. Type, amount added, reaction temperature,
It is also possible to confirm the opening during the reaction and the position of the double bond in the product, and then perform the isomerization reaction depending on the conditions after confirmation.

In the isomerization reaction that changes the position of the double bond in a 1-olefin, the double bond is isomerized sequentially to the 2nd, 3rd, and 4th positions. Isomerization Reaction - The lower the temperature, the lower the reaction rate, but an olefin having a composition that satisfies the essential requirements of the present invention can be easily obtained. If the isomerization reaction temperature is high, the position of the double bond tends to shift to the inner carbon of the molecular chain, resulting in an olefin having a composition that does not meet the essential requirements of the present invention, which is not preferable.

The position of the double bond in the isomerization reaction product is analyzed and confirmed by ozone-triphenyl 7-sphine 11-W chromatography.

The details of this method are as follows. That is, 0.1 part of the olefin to be analyzed is taken into a test tube using a volumetric pipette, and 1 part of ethyl acetate and 1 part of methyl alcohol are respectively added thereto to dissolve the olefin. While keeping the test tube below 0°C with ice water, oxygen containing ozone is blown into the test tube using a glass capillary, and gentle bubbling is continued for about 5 minutes. After 5 minutes, after confirming that ozone odor remains in the test WkW, stop blowing oxygen gas containing ozone, and instead blow nitrogen gas and perform gentle bubbling to drive out dissolved ozone and oxygen. Subsequently, 0.6 g of triphenyl heptasphine is added to this test tube, and the tube is allowed to stand at room temperature for 10 minutes or more. The fatty acid aldehyde, which is a decomposition product, is measured in the supernatant by chromatography using a programmable automatic heating system, and the position of the olefin double bond is confirmed.

〃The operating conditions for chromatography should be as follows.

Column conditions: 0V-17 (silicon 0V-173%
, Cromosorb 80 mesh) 3 Kasumi column detector: FID Benjexin 3 column temperature: 260℃ column temperature =
70°C for 5 minutes, heated to 260°C at a heating rate of 8°C/min and held at this temperature for 5 minutes Injection volume: 1 μm According to the present invention, the double bond position is changed to 1 by the isomerization reaction! ! From a segmented olefin and maleic anhydride,
For producing alkenyl succinic anhydride, it is preferable to use a sealed reaction vessel.

The ratio of the same raw materials when carrying out an addition reaction between olefin and maleic anhydride is preferably in the range of 1.5 mol of maleic anhydride aO9S to 1 mol of olefin.If this molar ratio becomes too large, This is not preferable because too much olefin is produced in the reaction, which increases the cost of recovering it, and conversely, the mole I+ is /1)s/n+W. increases, and the probability that two or more maleic anhydrides are added to one olefin molecule increases, which is undesirable as it causes the formation of sludge, tar-like substances, coloration of the reaction product, increase in viscosity, gelation, etc.

In the above range, the molar ratio of olefin to maleic anhydride is particularly preferably in the range of 0.7 to 1.2.

To obtain the desired product according to the method of the present invention, under an inert gas atmosphere, using a sealed reaction vessel in which 1-olefin isomerization reaction was carried out or a similar sealed reaction vessel of #1 structure. Carry out an addition reaction.

After the isomerization reaction is completed, the isomerization catalyst is not recovered or partially recovered from the reaction mixture, and a required amount of maleic anhydride is added thereto, and the reaction mixture is heated under an inert gas atmosphere for 150~
When maleic anhydride is added to the reaction system after the completion of the isomerization reaction in which the addition reaction is carried out in the temperature range of 240° C., the olefin isomerization reaction is stopped. Therefore, after the isomerization reaction is completed, the process of removing the isomerization catalyst, lowering the temperature of the reaction system, and increasing the temperature can be omitted. The addition reaction is preferable because the presence of the isomerization catalyst does not hinder the progress of the reaction and rather allows the addition reaction temperature to be lowered.

When the addition reaction is carried out in one step, the reaction temperature of the addition reaction can be reduced by allowing the reaction to occur in a temperature range of 170 to 220° C. for 2 to 10 hours to complete the addition reaction. When reacting in multiple stages, first react in a temperature range of 160 to 200°C for 2 to 5 hours, then slowly raise the temperature to 200 to 220°C, and react in this temperature range for 2 to 6 hours, the reaction rate will increase. 8
The target reaction product can be obtained by reaching 5% or more. The temperature of the addition reaction is within the temperature range of the isomerization reaction (16
It is particularly preferable that the temperature be the same as 0 to 220°C.

The reaction product that has completed the addition reaction in the above method is used as a sizing agent for paper manufacturing, either as it is or by recovering unreacted olefin under reduced pressure.

When the reaction product (alkenylsuccinic anhydride) obtained by the method of the present invention is used as a sizing agent for paper manufacturing, the alkenylsuccinic anhydride is mixed with cationized starch or a surfactant and stirred vigorously. This is dispersed in water to form a dispersion having an average particle size of 2 μm or less, and mixed with a pulp dispersion. At this time,
One or more of calcium carbonate, talc, and kaolin may be added as fillers, and one or more of cationic starch, cationic polyacrylamide, anionic polyacrylamide, amphoteric polyacrylamide, etc. may also be added. If these are added and mixed, paper is made, and then dried, sized paper can be obtained.

"Effects of the Invention" The present invention has the following particularly remarkable effects, and its industrial utility value is extremely large.

(1) According to the method of the present invention, the same isomerization catalyst is used in the isomerization reaction and the addition reaction, so these two reactions can be carried out at low temperatures, and the reaction time can be shortened.
The reaction rate and yield can be increased.

(2) When using the method of the present invention, a 1-olefin having 12 to 22 carbon atoms is used as a raw material, an isomerization reaction is performed to adjust the position of the double bond, and the process is directly transferred to an addition reaction. Therefore, the process is simple and industrially extremely easy.

(3) When using the method of the present invention, the two reactions of isomerization reaction and addition reaction can be carried out at low temperatures, and there is little by-product of tar and slazo, which prevents these from adhering to the walls of the reaction vessel and stirring tools. In addition, it is possible to obtain a product of excellent quality with little coloring.

(4) When using the method of the present invention, since an olefin having a specific composition as a main component is used as a raw material, the resulting alkenylsuccinic anhydride has low solubility in water but good dispersibility. There is little performance deterioration due to hydrolysis etc. during storage, and moreover, there is a large amount of fixation to the pulp during paper making.
Demonstrates excellent size effect.

“Examples” The present invention will be explained in detail based on Examples below.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 (Preparation of catalyst) Water glass and aqueous solution of aluminum sulfate were mixed with Si/AI=
Mix at a ratio of 1/1 (molar ratio), and add 1/1
0% aqueous ammonia was added to form a precipitate. After adding a sufficient amount of aqueous ammonia, the precipitate was filtered, washed with water, and centrifugally dehydrated to recover a dehydrated cake. To this dehydrated cake, a 20% iron chefate aqueous solution was added so that the iron element was Si/AI/Fe-1/I10.1, and after air drying, it was heated at 350°C for 3R and then at 450°C for 1
Calcinate for each time, transfer to a desiccator, slowly cool, and prepare a silica/alumina/iron oxide catalyst [SiOx/AI
zOs/CFezos·Felon)] was obtained.

(Isomerization reaction) A 1-olefin having 16 carbon atoms (manufactured by Mitsubishi Chemical Industries, Ltd., Guyalene A
10 g of the catalyst obtained by the above method was added to 5.4 kg of O-16), and the inside of the reaction vessel was purged with nitrogen gas. Under stirring,
When the temperature was raised to 170°C and held at this temperature for 4 hours and 10 minutes to carry out an isomerization reaction, the olefin produced was confirmed by ozone-triphenyl-7-osphine reduction chromatography, and the composition was as shown in Table 1. became.

(Addition reaction) Into the reaction vessel in which the above isomerization reaction was performed, maleic anhydride was charged to a concentration of 2.36%, and while stirring, the inside of the reaction vessel was replaced with nitrogen gas, and the temperature was raised to 170°C. Then, the internal temperature of this anti-TBgII vessel was raised to 220°C and kept at this temperature for 4 hours to continue the addition reaction.
After the reaction was completed, the internal temperature was rapidly cooled to 80° C., and the catalyst was recovered by a separate furnace method. Sludge and tar-like substances were not adhered to the inner wall or stirring blade of the reaction vessel.

Unreacted substances in the reaction product were collected under reduced pressure of 20+smHg to obtain a pale yellow and transparent alkenyl succinic aS hydrate (hereinafter referred to as rAsAJ) in 7.3.

(Evaluation of paper sizing degree) (1) Preparation of pulp After dissociating hardwood sal 7 ate pulp (LBKP) with water, using a TAPP I-type Naia Beater, the pulp concentration was 3%, and The pulp was beaten until the 7-leaness value measured with a Canadian purity tester reached a value of 400, and a pulp dispersion was prepared.

(2) Emulsification method of ASA The ASA obtained in the present invention and a 10 mole adduct of 7-nilftechnylethylene oxide were mixed at a weight ratio of 9:1. 2.23 g of this mixture was added to 400 ml of water and stirred vigorously for 1 minute using a homomixer to obtain an emulsion containing 0.5% by weight of ASA.

(3) Trial 1 [)lllt Add (2) to the pulp dispersion prepared by the method described in (1).
) A predetermined amount of the ASA emulsion prepared by the method described in section (
0.15, 0.20 and 0.25 weight 1 for pulp
%) and stirred for 5 minutes. Then, 1% by weight of cationized starch starch (CATO-F, manufactured by National Starch Co., Ltd., trade name) was added to the pulp, and the mixture was further stirred for 5 minutes. The dispersion thus obtained has a basis weight of 90 g/
The paper was made using a TAPP I-type round sheet machine so that the paper size was 1.

After papermaking, the test paper is sandwiched between NO, 3F paper and 3.5gk/
It was dehydrated by holding at c+m2 for 5 minutes, and then using a new filter paper and holding at 3.5 kg/am2 for 3 minutes for dehydration. Then, after air drying at room temperature, the humidity is 65% and the temperature is 25°C.
The humidity was adjusted for 4 hours and used as a test paper.

(4) Size test method Compliant with JIS P8122.

The measurement results are shown in Table 1.

Comparative example 1 (isomerization reaction) It was the same as described in Example 1.

(Addition reaction) After the isomerization reaction was completed, the internal temperature of the reaction vessel was lowered to 50° C. for 15 minutes, and the isomerization catalyst was removed by filtration. As in Example 1, the position of the double bond in the obtained olefin was confirmed by ozone-tri7-endyl-7-osphine reduction chromatography. The results are shown in Table 1.

The olefin from which the catalyst had been removed was placed in the same reaction vessel, and maleic anhydride was further charged to a concentration of 2.35%, and while stirring, the inside of the reaction vessel was replaced with nitrogen, heated to 170°C, and maintained at this temperature for 2 hours. Then, by raising the internal temperature to 220℃,
The addition reaction was continued by holding at this temperature for 4 hours.

The unreacted substances in the reaction product were collected under reduced pressure of 20 smHg, and 6.1 kg of ASA was obtained. A black tar-like substance was observed to be attached to the gas-liquid interface on the inner wall of the reaction vessel. ASA was dark brown in color.

(Evaluation of paper size degree) It was the same as described in Example 1.

Example 2 (Preparation of catalyst) Water glass and an aqueous solution of titanium sulfate were mixed so that the molar ratio of Si/Ti was 1/1, and aqueous ammonia was added thereto to form a precipitate. The rice precipitate was treated in a furnace, washed with water, and then centrifugally dehydrated to obtain a dehydrated cake. After air-drying this cake, it was baked at 350℃ for 4 hours and placed in a desiccator.
, slowly cooled, and transferred to a silica titania catalyst (SiO
i0z=1/1) was obtained.

(isomerization reaction) Volume 111? A mixture of 1-olefins having 16 and 18 carbon atoms at a weight ratio of 57:43 (manufactured by Mitsubishi Chemical Industries, Ltd., Gui'rkn A) was placed in a pressure-tight sealed container equipped with a stirrer.
2. O168) 500 kg L, the catalyst obtained by the above method.
Ok, it was added and the inside of the reaction vessel was replaced with nitrogen gas. While stirring, the temperature was raised to 170°C and maintained at this temperature for 9 hours to carry out an isomerization reaction to obtain an isomerized olefin. Regarding this olefin, as in Example 1, ozone
The position of the double bond was confirmed by phenyl 7t sphine reduction chromatography. The results are shown in Table 1.

The reaction mixture 1 after the above isomerization reaction was sampled from a sampling tube provided at the bottom of the reaction vessel, and the following tests were conducted.

The collected reaction mixture was separated into a catalyst, and the entire amount of the separated catalyst was immersed in maleic anhydride and left for a while. After standing, 3000 G″cR core separation was performed to obtain catalyst No. 10.

500 g of the isomerized olefin from which the catalyst was removed was placed in a reactor with a capacity of 11, 10 g of the catalyst treated by immersion in maleic anhydride was added thereto, and the inside of the reaction container was replaced with nitrogen gas while stirring. Then, the internal temperature was raised to 170°C and held at this temperature for 30 minutes.

Thereafter, the internal temperature was rapidly cooled, and the positions of double bonds in the contents of the reaction vessel were confirmed by ozone-triphenyl-7-osphine reduction chromatography.

The results were almost identical to the previous measurements.

This experimental result shows that the catalytic ability of the isomerization catalyst rapidly disappears by adding maleic anhydride.

(Addition reaction) Anhydrous maleic 112
05 was charged with +t, the inside of the reaction vessel was replaced with nitrogen gas under stirring, the temperature was raised to 170°C and held at this temperature for 2 hours, and then the internal temperature of this reaction vessel was raised to 220°C, The temperature was kept at this temperature for 4 hours and the addition reaction was continued. After the completion of the reaction, the internal temperature was rapidly cooled to 80°C and the catalyst was recovered by the transient method. Sludge and tar-like substances were found on the inner walls and stirring blades of the reaction vessel. Nothing was attached.

The unreacted reaction product was collected under reduced pressure of 20+mHH to obtain 669 kg of pale yellow and transparent ASA.

(Evaluation of paper size degree) It was the same as described in Example 1.

Comparative example 2 (isomerization reaction) Same as described in Example 2.

(Addition reaction) After the isomerization reaction was completed, the internal temperature of the reaction vessel was lowered to 80° C. in 30 minutes, and the isomerization catalyst was removed with F:AI to obtain 493 kg of isomerized olefin. The position of the double bond in the isomerized olefin was confirmed by ozone-tri-7-enyl-7-osphine reduction chromatography. The results are shown in Table 1.

The entire amount of the olefin from which the catalyst has been removed is placed in the same reaction vessel, and further added to maleic anhydride 203, and heated under stirring. ! 7 The inside of the vessel was replaced with nitrogen gas, held at 170℃ for 2 hours, then the internal temperature was raised to 220℃, and at this temperature
The addition reaction was continued for a period of time.

The unreacted substances in the reaction product were collected at 20 to 50 mmHg, and ASA of 578 was obtained.Black sludge and tar-like substances were attached to the gas-liquid interface on the inner wall of the reaction vessel. The color of the ASA was dark brown.

(Evaluation of paper size degree) It was the same as described in Example 1.

Example 3 (Catalyst Preparation) 100 g of the silica-titania catalyst obtained by the method described in Example 2 (Catalyst Preparation) was mixed with 100 g of a 20% iron oxalate aqueous solution. After soaking, take out and air dry, 400
It was calcined at ℃ for 3 hours and slowly cooled to obtain a silica/titania/iron oxide catalyst.

(Isomerization reaction) In a pressure-tight IT container equipped with a stirrer and having a volume of 4 1, 1.
1677) 1-2 fin Cr earlen AO-16
) 6 g of the catalyst obtained by the above method was added to 2, and the inside of the reaction vessel was purged with nitrogen gas. The isomerization reaction was carried out by maintaining the temperature at 190° C. for 2 hours while stirring.

In the obtained isomerized olefin, the position of the double bond was confirmed by the chromagography method described above. The results are shown in Table 1.

(Addition reaction) Maleic anhydride 87% was added to the reaction vessel in which the isomerization reaction was performed.
Add 5g of
After raising the temperature to ℃ and holding it at this temperature for 2 hours, the internal temperature was raised to 22℃.
The temperature was raised to 0°C and maintained at this temperature for 4 hours to carry out an addition reaction.

After the completion of the addition reaction, unreacted substances were removed at 20-50+*mHg, and the catalyst was separated into a furnace to obtain 2.76 kg of ASA.Sludge and tar-like substances were found on the inner walls and stirring blades of the reaction vessel. No adhesion was observed.

(Evaluation of paper size degree) The method described in Example 1 was followed.

Comparative Example 3 The same procedure as described in Example 3 was carried out except that the reaction time of (isomerization reaction) was changed to 8 hours.

Table 1 shows the results of confirming the position of the double bond of the olefin after the isomerization reaction and the evaluation results of the paper sizing degree of the obtained ASA.

Comparative Example 4 The same procedure as described in Example 1 was carried out except that the reaction time of (isomerization reaction) was changed to 1.5 hours. The results of confirming the position of the double bond in the olefin after the completion of the isomerization reaction and the results of evaluating the paper sizing degree of the obtained ASA are shown in the first column, respectively.

The following is clear from the first decay.

(1) When the method of the present invention is used, alkenylsuccinic anhydride of good quality can be obtained even though sludge and tar-like substances are produced as by-products.

(2) Alkenylsuccinic anhydride obtained from an olefin that satisfies the requirements specified in the claims of the present invention exhibits excellent sizing effects when used as a sizing agent (Examples 1 to 3) reference).

(3) On the other hand, alkenylsuccinic anhydride obtained from an olefin that does not meet the requirements specified in the claims of the present invention does not have a very good sizing effect when used as a sizing agent. No effect (Comparative example 3)
-4)).

(4) In addition, when no isomerization catalyst is present in the addition reaction system, sludge and tar-like substances are likely to be produced as by-products, and
The yield of the addition reaction decreases (see Comparative Examples 1 and 2).

Claims (3)

[Claims] (1) An isomerization reaction is performed on a linear 1-olefin having 12 to 22 carbon atoms using an isomerization catalyst, and the 1-olefin component is 20 mol% or less, and the double bond is at the 6-position. The olefin component located inside the carbon is 40 mol% or less, maleic anhydride is added in the range of 0.5 to 1.5 mol per 1 mol of this olefin, and in the presence of an isomerization catalyst, 150 mol% A method for producing alkenylsuccinic anhydride, characterized in that an addition reaction is carried out in a temperature range of -240°C. (2) Production of alkenylsuccinic anhydride according to claim (1), characterized in that a mixture of 1-olefins having 14, 16 and 18 carbon atoms is used as the olefin. Method. (3) Claim No. (3) characterized in that a 1-olefin having 16 carbon atoms is used as the olefin.
1) The method for producing alkenylsuccinic anhydride described in section 1).