JP2000273119A - Production of organic amine salt of aromatic polymer sulfonated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the production of a high quality organic amine salt of a sulfonated product in good efficiency without causing thermal deterioration. SOLUTION: Sufonation was carried out at a reaction temperature of 45 deg.C by using a polystyrene having an average molecular weight of about 5,000 dissolved in 1,2-dichloroethane at a concentration of 11% (by weight) as a raw material and liquid SO3 as a sulfonating agent at a molar ratio of the SO3 of 1.15 and then, 15 kg reaction product containing the solvent was introduced into a vibration drier from a feed port at its upper part, and the temperature of the drier was controlled to 90 deg.C and the drier was evacuated so as to have an absolute pressure of about 200 Torr. The solvent began to volatilize and distill out from an outlet at the upper part of the drier. Operation of vibrating the drier was performed and the powder of polystyrenesulfonic acid was collected at the bottom of the drier to obtain 2.84 kg powder. The yield was 99.5% (by weight) of the theoretical amount of the sulfonated product, and the remaining amount of the solvent was 0.5% (by weight) based on the solid product. The aromatic polymer material having an average molecular weight not smaller than about 5,000 can suitably be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the production of organic amine salts of aromatic sulfonated compounds, and more particularly to the production of organic amine salts of aromatic polymer sulfonated compounds.

[0002]

BACKGROUND ART An organic amine salt of an aromatic polymer sulfonated compound represented by polystyrene sulfonic acid is known as an antistatic agent for kneading-type plastic materials having excellent durability and washing resistance ( Japanese Patent Application No. 10-38925,
Japanese Patent Application No. 9-360691, Japanese Patent Application No. 9-32344, etc.) and industrially advantageous production methods thereof are required. Production methods of aromatic amine sulfonated organic amine salts are described in, for example, JP-A-57-73006, JP-A-8-104787,
It is disclosed in 10-101731. However, there is no disclosure of an operation for separating an organic solvent which is a mixture with a sulfonated organic amine salt. For evaporating the solvent of the polymer-containing solution using a drum dryer, for example,
JP-A-52-47082, JP-A-61-76508, JP-A-4-
No. 293919. Further, the evaporation of the solvent using another type of dryer may be performed, for example, as described in JP-A-7-24.
No. 7366.

[0003] These conventional methods disclose a method of controlling a dryer to a relatively high temperature to efficiently evaporate a solvent.

[0004]

When the solvent is removed by the conventional method, the dryer is controlled to a relatively high temperature. However, organic amine salts of sulfonated organic amines, for example, organic amine salts of aromatic high molecular sulfonated compounds represented by long-chain alkylamine ethylene oxide adduct salts of polystyrene sulfonic acid generally have a low glass transition point, and thus have an adhesive property due to heat. Due to the fact that they increase and adhere to the equipment during the process of removing the solvent and that the products are easily fused together by heat, they form a large mass due to the amine salt product, and the adhered matter traps the solvent inside In some cases, agglomeration occurs in this state, and in this case, there is a problem that the recovery rate of the solvent is reduced and that the quality of the sulfonated product is deteriorated.

Accordingly, an object of the present invention is to produce a sulfonated organic amine salt which can solve the above-mentioned problems. In other words, the present invention can efficiently dry the sulfonated organic amine salt while effectively preventing the attachment of the sulfonated organic amine salt to the dryer even if it is a thermoplastic sulfonated organic amine salt. Is efficiently separated from the sulfonated organic amine salt, a high-quality sulfonated organic amine salt can be obtained, and a method for producing a sulfonated organic amine salt capable of improving the solvent recovery rate is provided. The purpose is to: Furthermore, an object of the present invention is to improve the solvent recovery rate by effectively preventing the fixation of the sulfonated organic amine salt, and to produce a sulfonated organic amine salt of good quality. An object of the present invention is to provide a method for producing an amine salt.

Another aspect of the present invention is to provide a method for producing a sulfonated organic amine salt which can prevent the thermal deterioration of the sulfonated organic amine salt and can produce a good quality sulfonated organic amine salt. With the goal.

[0007]

FIG. 1 shows a schematic flow chart of a sulfonation step to which the present invention can be applied, a sulfonated product and a process for producing a sulfonated organic amine salt. Generally, it is difficult to cause a homogeneous reaction with a sulfonating agent of a polymer as a raw material for sulfonation, for example, polystyrene as it is. For this reason, at the time of sulfonation, the raw materials are dissolved in a solvent. Generally, a halogen-based organic solvent is used as this solvent (solvent 1). In the present invention, the liquid SO is used as the sulfonating agent.
Sulfonate with 3. In this case, a sulfonating agent, a liquid raw material in which a raw material polymer is dissolved in an organic solvent, and an additional solvent for properly maintaining the reaction rate are introduced into a sulfonation reaction apparatus (step S1), and a continuous reaction method is performed. To perform sulfonation (step S2). In this step, the polymer, for example, styrene, is sulfonated,
Produces a sulfonate, ie, a polymer (styrene) sulfonic acid. Next, the resulting mixture of the sulfonated product and the solvent is introduced into a dryer, and the sulfonated product is dried. That is, the sulfonated product and the organic solvent are separated (Step S3). The solvent is condensed and recovered, and is circulated and used as a sulfonated solvent (step S4).

After the sulfonate has been dried to a predetermined level, the sulfonate is neutralized (step S5). This neutralization is performed with an organic amine. In this case, another lower alcohol (such as butanol) solvent is used to dissolve the organic amine (solvent 2) (step S6). Neutralization of the sulfonated product with the organic amine produces a sulfonated organic amine salt. Next, the sulfonated organic amine salt and the solvent 2 are dried and separated (step S7).
The sulfonated organic amine salt can be obtained in pure form. Note that the solvent 2 is collected and recycled (Step S8). In addition, a halogen-based organic solvent that can be effectively used in the sulfonation reaction is used in an amine neutralization reaction. Before the sum reaction,
It is desirable to eliminate the halogen-based solvent to such an extent that neutralization and drying are not hindered.

It is desirable to use a lower alcohol solvent in the neutralization reaction due to the compatibility with the amine. According to one feature of the present invention, an aromatic polymer raw material is dissolved in an organic solvent, a sulfonating agent is added thereto, and sulfonated to form an aromatic sulfonated product, and the sulfonated product is dissolved in the organic solvent. A slurry which is substantially uniformly dispersed is formed, and the slurry comprising the sulfonated product and the organic solvent is introduced into a dryer which is set at a temperature of about 100 ° C. or lower and controlled in a predetermined vacuum state, and the sulfonated product is dried. Thereby separating the organic solvent and the sulfonate, dissolving the amine compound in a lower alcohol solvent, and reacting the sulfonate with the amine compound dissolved in the alcohol solvent to produce a sulfonate organic amine salt, The mixture of the sulfonated organic amine salt and the alcohol solvent is guided to a dryer controlled at a temperature of about 100 ° C. or less and a predetermined vacuum state. And the mixture was separated and the lower alcohol solvent and sulfonated organic amine salt by drying the containing sulfonated organic amine salt, and recovering the sulfonated organic amine salt.

In a preferred embodiment, the sulfonated organic amine salt may be supplied in the form of a thin film to a moving dry surface. For example, the drying surface can be a rotating drum having a circumferential surface or a screw-like form. When the surface of the rotating drum is used as the drying surface, the surface of the pair of rotating drums is used as the drying surface, and the sulfonated organic amine salt is supplied in a thin film form so as to be drawn between the pair of rotating drums. Is desirable. In one form of dryer that can be used in the present invention, a vacuum double drum dryer can be used. This type of dryer has two counter-rotating drums, between which a sulfonated organic amine salt and a lower alcohol solvent mixture are in thin film between the drums. It is supplied in a state of being caught in. At this time, the interior of the dryer is preferably kept in a predetermined vacuum state.
The mixture adheres to the drum surface in the form of a thin film. Thereafter, the solvent volatilizes and is separated from the drum surface. As a result, a solid substance of the sulfonated organic amine salt remains on the drum surface as a residue. By scraping the sulfonated organic amine salt, the sulfonated organic amine salt can be recovered.

The drying process is performed, for example, at about 400 To
By performing the reaction at a pressure of rr or less and within a time range of about 120 minutes or less, the sulfonated organic amine salt and the lower alcohol solvent can be separated. In addition, in order to prevent agglomeration of the products, iron balls or the like may be put in the space inside the dryer and stirred together. Examples of the aromatic sulfonated polymer include the following.
Sulfonates of polymers of aromatic hydrocarbon monomers such as styrene, α-methylstyrene, p-hydroxystyrene, vinyltoluene and vinylnaphthalene; aliphatic dienes such as butadiene, isoprene, pentadiene and cyclopentadiene; Sulfonated copolymer of hydrogen monomer, ethylene, propylene, butene, sulfonated copolymer of olefins such as isobutylene and the aromatic hydrocarbon monomer, acrylic acid, methacrylic acid, maleic acid, fumaric acid, Crotonic acid, itaconic acid, sulfonated copolymer of unsaturated carboxylic acid such as citraconic acid and the above aromatic hydrocarbon monomer, and others,
Two or more kinds of monomers that can be combined as a sulfonated product of a copolymer of the above-mentioned aromatic hydrocarbon monomer with acrylonitrile, divinylbenzene, or the like and a copolymer with an aromatic hydrocarbon monomer can be used.

On the other hand, the organic solvent is guided from the dryer to the outside, recovered through a predetermined recovery device, and then used again to dissolve the aromatic polymer material for sulfonation. . In addition, it is desirable to use a halogenated hydrocarbon inert to the sulfonating agent as the sulfonating raw material and the solvent for the sulfonated product. In particular, carbon number 1
Or 2 aliphatic halogenated hydrocarbons are preferable, specifically, methylene dichloride, 1,2-dichloroethane,
1,1-dichloroethane, ethyl chloride, carbon tetrachloride,
1,1,2,2-tetrachloroethane, chloroform,
Ethylene bromide or the like can be used. After the sulfonate has dried to a predetermined level, the sulfonate is neutralized, this neutralization being carried out with an organic amine.

Examples of the organic amine include butylamine, hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, monoethanolamine, coconut oil alkylamine, tallow alkylamine, hydrogenated tallow Primary amines such as alkylamines, and ethylene oxide adducts of these primary amines (average number of moles of ethylene oxide added: 2-100) dibutylamine, dihexylamine, dioctylamine, didecylamine, didodecylamine, ditetradecylamine, Hexadecylamine, dioctadecylamine, diethanolamine,
Secondary amines such as morpholine, tertiary amines such as tributylamine, trihexylamine, trioctylamine, tridecylamine, tridodecylamine, tritetradecylamine, trihexadecylamine and trioctadecylamine; Mixtures of more than one species may be used.

Among these, from the viewpoint of antistatic properties, primary amines such as dodecylamine, tetradecylamine, hexadecylamine, and octadecylamine; and primary amines such as dodecyldiethanolamine, tetradecyldiethanolamine, hexadecyldiethanolamine and octadecyldiethanolamine. Preferred are ethene oxide adducts of primary amines. Further, another lower alcohol (such as butanol) solvent is used to dissolve the organic amine. In this case, the lower alcohol is preferably an alcohol having 4 or less carbon atoms, for example, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, and branched isomers thereof. Among them, ethyl alcohol, propyl alcohol, butyl alcohol and isomers thereof are preferable because of easy separation from the polymerization solvent remaining in the sulfonated aromatic polymer.

Then, the sulfonated organic amine salt is produced by neutralization of the sulfonated product with the organic amine. The resulting sulfonated organic amine salt exhibits an antistatic effect by being kneaded with the resin, and thus is useful as an antistatic agent for resins. In order to obtain a highly pure sulfonated organic amine salt, it is necessary to efficiently separate the solvent. The solvent such as lower alcohol separated from the sulfonated organic amine salt is recovered and recycled.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Example 1 A mixture of a hardened tallow alkylamine ethylene oxide adduct (average number of moles added: 2) of polystyrene sulfonic acid (100% sulfonation ratio) having an average molecular weight of about 15,000 and ethanol (1/1) (1 wt ratio), the drum is heated to 90 ° C. and rotated (1.5 rpm) and the absolute pressure is set to 350 Torr.
r double vacuum drum dryer (drum surface area 0.
Separation of organic amine salt (hardened tallow alkylamine ethylene oxide adduct (average addition mole number: 2) salt) from ethanol using 69 m ² , drum diameter 300 mm, drum length 300 mm, manufactured by Nippon Refine Co., Ltd. The drying operation of the amine salt was performed.

Referring to FIG. 2, there is shown a sulfonated organic amine salt drying system 20 including a vacuum double drum dryer 21 used in the present example. The vacuum-type double-drum dryer 21 of this example includes a horizontal cylindrical tank main body 22, in which a pair of drums 23 and 24 are arranged in a horizontal direction. The rotation directions of the drums are such that the respective drums rotate inward when viewed from above. The raw material is supplied to the two drums 2 in the tank 22 from the upper raw material inlet 25 through a nozzle 26.
It is designed to be introduced near the middle contact point between 3, 24. Heat from the steam pipe 27 is supplied to the drum, so that the surface of the drum can be controlled to an appropriate temperature. Further, a vacuum pump is connected to the tank internal space so that the pressure can be reduced so as to achieve a predetermined degree of vacuum. The sulfonated organic amine salt dries and adheres to the drum surface. The sulfonated organic amine salt adhering to the drum surface is scraped off by the drum scrapers 28 and 29 and accumulates at the bottom of the tank.

The sulfonated organic amine salt that has accumulated at the bottom of the tank is then recovered from a recovery port 30 at the bottom. On the other hand, the solvent (ethanol) is vaporized in the dryer, gas-liquid separated in a separation tower 32 through a pipe from an upper outlet 31, cooled by a condenser 33, and collected in a condensed liquid receiving tank 34. . In this example, a mixture of a sulfonated organic amine salt and a solvent was placed in the above dryer for 1 hour.
Introduced at a feed rate of 50 kg / h for 2 hours, steam was introduced into the dryer to control the temperature of the drum surface to about 90 ° C., and the interior of the dryer was evacuated to an absolute pressure of about 300
Controlled to Torr. As a result, the solvent volatilized and began to distill from the outlet 31 above the dryer.

The residual amount of the solvent is 0.6% based on the solid components.
(Weight). No signs of heat denaturation were seen in the product. Example 2 Instead of the polystyrene sulfonic acid-cured tallow alkylamine ethylene oxide adduct salt of Example 1, styrene /
Maleic acid copolymer (copolymerization ratio 9/1, average molecular weight 5
The solvent was removed in the same manner as in Example 1 except that a cured alkylamine ethylene oxide adduct (average number of moles added: 2) having a molecular weight of 000 and a sulfonation ratio of 99% was used. Solvent residual amount is 0.7% (weight) based on solid components
Met. Example 3 A mixture of a polystyrene sulfonic acid-cured tallow alkylamine ethylene oxide adduct (average number of moles added: 2) salt of Example 1 and ethanol was heated to 90 ° C. and a dryer having a screw-type paddle (self-cleaning processor) ) (SCP-100, screw diameter 100 mm, screw length 900 mm, manufactured by Kurimoto Iron Works Co., Ltd.) to separate the sulfonated organic amine salt from the ethanol solvent. The operating condition was such that the rotation speed of the screw paddle was 20 rpm, and the operating pressure inside the dryer was controlled to 100 Torr as an absolute pressure.

FIG. 3 shows a schematic system diagram of the drying system used in this example. Referring to FIG. 3, the dryer 41 of the present example includes a horizontal cylindrical tank 42, and a biaxial screw that meshes with each other is disposed inside. The screw has a paddle arranged to form a gap of 1.5 mm. The dryer of the present example is provided with a heating device 47 for heating the inside. The raw material is introduced from the upper inlet port 43 at one end of the horizontal tank-shaped dryer, and the solvent-separated sulfonate is taken out from the lower recovery port 44 at the other end. Has become. On the other hand, the solvent is vaporized in the dryer, cooled by the condenser 46 through the pipe from the upper outlet 45, and collected in the condensate receiving tank.

In this example, a mixture of a sulfonated organic amine salt and an ethanol solvent was added to the above dryer at 50 kg / kg.
h and fed for 2 hours. In this case, the mixture was introduced between approximately 1.5 mm between the paddles of the intermeshing screws and between the screws in such a manner as to be wound by the screws. At this time, dryer 4
The temperature in 1 was controlled at about 90 ° C. The pressure in the tank was maintained at about 100 Torr. From one end side, dryer 41
Is introduced into the other end by rotation of the screw, and is guided to the recovery port side. During this time, the ethanol solvent volatilizes and is separated from the sulfonated organic amine salt. In the operation of this example, the mixture adheres to the surface of the screw in the form of a thin film, and the inside of the tank is maintained in a reduced pressure state, so that the solvent is efficiently separated.

As a result, a product was obtained in which the residual amount of the solvent was 0.5% (by weight) based on the solid components. Example 4 The solvent was removed under the same conditions as in Example 3 except that 1-butanol was used instead of ethanol in Example 3, and the residual amount of the solvent was 0.7% (weight) with respect to the solid component. A solid was obtained. Example 5 Example 3 was repeated except that didodecylamine was used instead of the cured tallow alkylamine ethyl alcohol oxide adduct (average number of moles added: 2) as the amine of the polystyrenesulfonic acid organic amine salt of Example 3. The solvent was removed under the same conditions, and the remaining amount of the solvent was 0.6% based on the solid component.
(Weight) solid was obtained. Comparative Example 1 The same raw material as in Example 1 was dried by using an organic solvent spray dryer in which the temperature of hot air was set to 120 ° C. The dried product is
All of the columns adhered to the inner wall and could not be discharged. In addition, a beard-like polymer grew with an atomizer that supplied the solution with the treatment time, and the dispersibility of the solution became poor. Furthermore, the dried matter attached to the inner wall changed from white to black due to thermal deterioration. Comparative Example 2 The same raw material as in Example 1 was supplied at normal pressure to a double drum dryer controlled at 160 ° C. to perform drying. The raw material immediately turned black on the drum surface and was thermally degraded. Also,
The dried product was entangled with the scraping blade and could not be peeled off from the drum satisfactorily.

[0023]

As described above, according to the present invention, a mixture of a sulfonated organic amine salt and a lower alcohol solvent is supplied to a dryer in the form of a thin film or the solvent is separated while applying vibration. Since the operation is performed so as not to generate a large fixed substance as much as possible, it is possible to efficiently separate the sulfonated organic amine salt from the lower alcohol solvent. In addition, in the present invention, the pressure in the drying apparatus is reduced and the temperature is controlled so as not to be as high as possible, so that the problem that the sulfonated organic amine salt undergoes thermal denaturation or the like and the quality is reduced can be solved. it can.

[Brief description of the drawings]

FIG. 1 is a flowchart of a sulfonation and sulfonate treatment step to which the present invention can be applied;

FIG. 2 is a schematic system diagram of a sulfonated organic amine salt drying system according to one embodiment of the present invention;

FIG. 3 is a schematic system diagram of a sulfonated organic amine salt drying system according to another embodiment of the present invention.

[Explanation of symbols]

 21 Double Drum Vacuum Dryer 28, 29 Scraper 30 Product Recovery Port 26 Raw Material Input Port 23, 24 Drum 27 Steam Pipe 31 Outlet 32 Condensate Receiving Tank 41 Dryer (Self Cleaning Processor).

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Sou Shigematsu 1-3-7 Honjo, Sumida-ku, Tokyo F-term in Lion Corporation (reference) 4J100 AA02Q AA03Q AA04Q AA05Q AB00P AB00Q AB02P AB03P AB04P AB07P AB07R AB16Q AJ01Q AJ02Q AJ08Q AJ09Q AM02Q AR17Q AS02Q AS03Q AS04Q BA56H BA56R CA01 CA04 CA05 CA31 GC04 GC26 GD03 HA31 HA61 HB52 HC43 HC44 HC45 HC47 HC63 HF00 JA15

Claims (3)

[Claims] 1. An aromatic polymer raw material is dissolved in an organic solvent, a sulfonating agent is added thereto, and sulfonated to form an aromatic sulfonate, and the sulfonate is substantially uniformly dispersed in the organic solvent. A slurry is formed.
C. or lower, and introduced into a dryer controlled at a predetermined vacuum state, and the organic solvent and the sulfonate were separated by drying the sulfonate, and the amine compound was dissolved in a lower alcohol solvent, Reacting the sulfonated product with an amine compound dissolved in the alcohol solvent to produce a sulfonated organic amine salt, and controlling the mixture of the sulfonated organic amine salt and the alcohol solvent to a temperature of about 100 ° C. or less; And, introduced into a dryer controlled to a predetermined vacuum state, the mixture containing the sulfonated organic amine salt is dried to separate the sulfonated organic amine salt from the lower alcohol solvent, and the sulfonated organic amine salt is removed. A method for producing an organic amine salt of an aromatic high molecular sulfonate, comprising recovering the organic amine salt. 2. The method of claim 1, wherein the sulfonated organic amine salt is provided in a thin film form on a moving dry surface. 3. The method according to claim 1, wherein the surfaces of the pair of rotary drums are dry surfaces, and the sulfonated organic amine salt is supplied in the form of a thin film so as to be drawn between the pair of rotary drums. A method characterized by the following.