KR20020024350A - Novel polybutadiene derivative and a method of preparation thereof - Google Patents

Abstract

PURPOSE: Provided is a novel polybutadiene derivative, which can eliminates odors from the industrial area and the surroundings by reacting with odor material, especially, which can eliminate toxic material exhausted to the atmosphere from the industrial area. CONSTITUTION: The polybutadiene derivative (formula I) with a molecular weight of 1000-6000 is produced by a process comprising the steps of: reacting hydroxy-substituted polybutadiene and alkyl amine; reacting the resultant with sulfuric acid; reacting the resultant with alkyl amine to alkylate the amine group of the polybutadiene additionally; neutralizing the obtained compound with hydroxide of an alkali metal or an alkali earth metal to convert a sulfonic acid group into a metal salt. In the formula, n is an integer, R1 and R2 are C1-C5 alkyl, and M is the alkali metal or the alkali earth metal.

Description

Novel Polybutadiene Derivatives and Manufacturing Method Thereof {NOVEL POLYBUTADIENE DERIVATIVE AND A METHOD OF PREPARATION THEREOF}

The present invention relates to a polybutadiene derivative containing an alkylamine group at one end and a sulfonate group at the other end, and a method for producing the same. More specifically, polybutadiene containing a hydroxyl group, an alkylamine, and concentrated sulfuric acid are reacted at room temperature, and then further reacted with diethylamine or dimethylamine, and then neutralized with a basic compound such as sodium hydroxide or potassium hydroxide. The present invention relates to a method for producing a polybutadiene derivative containing an alkylamine group at one end of a butadiene and a sulfonate group at the other end, a polybutadiene derivative obtained by the production method and a use thereof.

In everyday life, odors are detected when chemical compounds that bind to the olfactory organs chemically bind to olfactory epithelial cells, and when potential stimulation occurs due to chemical binding, the potential stimulus is transmitted to the brain through nerve cells.

In general, odor sources are chemical wastes generated from biological waste, decay, industrial wastewater, household sewage, and incinerators, and various volatile and nonvolatile substances generated during industrial activities. The lower surface is roughly classified into acidic and alkaline odors such as hydrogen sulfide, ammonia, mercaptans and amines.

The most widely used methods for removing such odorous substances include a washing method, an adsorption method, a combustion method, an ozone oxidation method, a concealment method, and the like, and various materials suitable for such a method have been developed.

The water washing method is to remove odor by dissolving odor causing substances in water. It is used to remove water-soluble odorous substances such as ammonia, amines, ketones, aldehydes and lower organic acids having hydrophilic polar groups. Although it is inexpensive and simple to operate, a large amount of water is required, and it is not suitable for removing non-aqueous odorous substances such as non-polarity. There is a problem that causes the problem is not recognized as a way to fundamentally remove the odor.

The adsorption method is a method in which a substance having adsorption characteristics, that is, an odor causing substance is adsorbed onto an adsorbent and deodorized. In the adsorption method, activated carbon is mainly used as an adsorbent, and has retaining properties for hydrophobic components having a high molecular weight because it has the property of adsorbing other components even in the presence of moisture. In general, it is widely used for the removal of low concentration mixed odor. On the other hand, gas containing soot or dust is required for pretreatment, and high concentrations of odorous substances cannot be adsorbed due to the limitation of adsorption capacity and are discharged as they are. There is a problem such as doing.

The combustion method is a method of rapidly oxidizing and decomposing odor-causing substances. There is a direct combustion method and a catalytic combustion method, and the deodorizing effect is excellent for flammable components, but it costs a lot for incineration facilities, and the fuel consumption is large, so it is economically adopted. It is difficult and there is a problem of secondary pollution such as dioxin emissions. In particular, since nitrogen or sulfur-containing materials generate toxic gases such as nitrogen oxides and sulfur oxides during combustion, measures for secondary pollution are necessary.

The ozone oxidation method is a method of oxidatively decomposing odorous substances by oxidizing ozone, which is a kind of oxidation method, and is relatively effective in removing odorous substances from sulfur compounds. The ozone oxidation method has the advantage that the odorous substance is not reduced again after being oxidized by a chemical reaction, but measures for secondary pollution by residual ozone after treatment are required.

The concealment method is a method of canceling and treating an odor by spraying a perfume material stronger than a malodorous substance or by mixing other odorous substances. The concealment method is used to deodorize a low concentration of odor and has a problem that the deodorizing effect is not great and the fundamental treatment is not made, and the concentration of the malodorous substance or the concentration of the treated substance requires attention.

As described above, the conventional technology is that each technology has specificity only for a particular odorous substance, the deodorizing effect varies depending on the operating conditions, the replacement time of the odorous substance is short, or it is vulnerable to a high concentration of odorous substance, or is operated. Each technology has different disadvantages such as high cost or secondary pollution problem.

MEANS TO SOLVE THE PROBLEM As a result of earnest research and research in order to solve the said problem, when a sulfonate group and an amine group or its derivative are combined and used for polybutadiene, the sulfonate group and the amine group of these compounds are sulfur compounds, ammonia, mercaptans, and amines. It has been found that the odor can be removed by acid alkali reactions of acidic and alkaline malodorous substances such as ketones, and the present invention has been completed.

That is, an object of the present invention is to provide a polybutadiene derivative containing an alkylamine group at one end and a sulfonate group at the other end.

Another object of the present invention is to provide a method for producing a polybutadiene derivative containing an alkylamine group at one end and a sulfonate group at the other end.

Generally, it can be easily reacted with an amine group and an acidic odor component to remove odors. The sulfonate group can be easily reacted with an alkaline odor component to remove odors, and the amine group (or sulfonate group) can be removed. When the sulfonate group (or the amine group) was attached again after the compound (carrier) was attached, it was not easy for the amine group and the sulfonate group to react and attach both groups to one compound at the same time.

Thus, polybutadiene was selected as a carrier, and in consideration of the reactivity of the polybutadiene, the end of the polybutadiene was substituted with various reactive groups, and then reacted with the amine group and the sulfonate group to attach to the polybutadiene. Substituted polybutadiene is too reactive to attach the following alkylamine and sulfonate to the same carrier, thereby replacing both ends of the polybutadiene with a hydroxy group to obtain hydroxybutadiene to obtain the target compound of the present invention. Could.

Hereinafter, the manufacturing method of the target compound of this invention is demonstrated.

Hydroxy substituted polybutadiene is reacted with alkylamine to attach an amine group. This reaction is preferably carried out in a solvent which does not adversely affect the room temperature and the reaction. Examples of the solvent include alcohols such as ethanol, ketones such as dimethyl ether, and aliphatic hydrocarbons such as hexane. Anhydrous sulfuric acid is gradually added to the resulting compound to replace the hydroxyl group at the other end of the polybutadiene with a sulfonate group. At this time, the desired molecular weight of the final target compound can be obtained by adjusting the reaction time. In other words, if the reaction time is about 30 minutes, the compound having a molecular weight of about 5000 to 6000 is obtained. However, if the reaction is about 50 to 70 minutes, the compound having a molecular weight of about 1500 to 2000 is obtained. Can be.

The reaction product is then reacted with a compound selected from the group consisting of dimethylamine, diethylamine, dipropylamine, dibutylamine and dipentylamine to alkylate the amine groups of polybutadiene. The compound thus obtained is neutralized with an aqueous solution of an alkali metal or alkaline earth metal hydroxide to convert the sulfonic acid group into a metal salt, thereby obtaining a polybutadiene derivative containing an alkylamine group at one end of the present invention and a sulfonate group at the other end thereof.

This can be expressed as a general formula:

(Wherein R ₁ and R ₂ represent a lower alkyl group having 1 to 5 carbon atoms and M represents an alkali metal or an alkaline earth metal)

It is preferable that the weight molecular weight is 1000-6000 among the compounds of the said general formula, 200-5000 are more preferable, It is the most preferable that it is 1500-2000. That is, the molecular weight of 1000 or less is not satisfactory deodorizing effect due to the number of double bonds, the compound of 6000 or more is inconvenient to use due to the high viscosity, the compound inside the product, unless the product is extremely thin form when the final product Silver is not preferable because it hinders the reaction and deteriorates the deodorizing effect.

In particular, polybutadiene derivatives having a molecular weight of 1500 to 2000 are chemically stable water-soluble substances at -20 to 200 ° C. Since the alkylamine group has such a molecular structure, the alkylamine group becomes a deodorant having specificity to the nonpolar malodorous substance, and the sulfonate group can be applied to a malodorous source in which various malodorous substances are mixed.

Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples. However, the scope of the present invention is not limited by these Examples.

Example 1

160 ml of n-hexane was placed in a five-necked reactor equipped with a stirrer (capacity 500 ml) on a water bath capable of temperature control at low temperature, and 100 g of polybutadiene containing hydroxyl group and 17 g of ethylamine were added to the sock end and mixed homogeneously. . The temperature was adjusted to 20 ± 1 ° C. and 18 g of anhydrous sulfuric acid was slowly added over 60 minutes, so that the reaction temperature did not exceed 25 ° C. After reacting again for 3 hours, 16 g of diethylamine was added and reacted for 2 hours. A polybutadiene derivative containing an alkylamine group at one end and a sulfonate group at the other end was prepared by reacting with a 30% (W / V) aqueous sodium hydroxide solution until reaching a neutralization point for 60 minutes. The molecular weight of this polybutadiene derivative was about 2000 when measured by gas chromatography (GPC, Shodex RI-71, Futecs F6110 pump, OHpak SB-802.5 HQ column).

In the above reaction, a polybutadiene derivative having a molecular weight of about 6000 was obtained in the same manner except that the reaction time was 30 minutes after anhydrous sulfuric acid was added.

Example 2

The same procedure as in Example 1 was carried out except that 30% (W / V) aqueous sodium hydroxide solution was reacted to 20% (W / V) aqueous potassium hydroxide solution to the neutralization point, and sulfonate at one end of the alkylamine group and the other end thereof. A polybutadiene derivative containing a group was prepared. The molecular weight of the polybutadiene derivative was about 2000 when measured by gas chromatography (GPC, Shodex RI-71, Futecs F6110 pump, OHpak SB-802.5 HQ column).

In the above reaction, a polybutadiene derivative having a molecular weight of about 6000 was obtained in the same manner except that the reaction time was 30 minutes after anhydrous sulfuric acid was added.

Example 3

Except for using 16g of dimethylamine instead of 16g of diethylamine was carried out in the same manner as in Example 1 to prepare a polybutadiene derivative containing an alkylamine group at one end and sulfonate group at the other end. The molecular weight of this polybutadiene derivative was about 2000 when measured by gas chromatography (GPC, Shodex RI-71, Futecs F6110 pump, OHpak SB-802.5 HQ column).

In the above reaction, a polybutadiene derivative having a molecular weight of about 6000 was obtained in the same manner except that the reaction time was 30 minutes after anhydrous sulfuric acid was added.

Example 4

A polybutadiene derivative containing an alkylamine group at one end and a sulfonate group at the other end was prepared in the same manner as in Example 1 except that 21g of dipropylamine was used instead of 16g of diethylamine. The molecular weight of this polybutadiene derivative was about 2000 when measured by gas chromatography (GPC, Shodex RI-71, Futecs F6110 pump, OHpak SB-802.5 HQ column).

In the above reaction, a polybutadiene derivative having a molecular weight of about 6000 was obtained in the same manner except that the reaction time was 30 minutes after anhydrous sulfuric acid was added.

Example 5

Except that 25g of dibutylamine instead of 16g of diethylamine was carried out in the same manner as in Example 1 to prepare a polybutadiene derivative containing an alkylamine group at one end and a sulfonate group at the other end. The molecular weight of this polybutadiene derivative was about 2000 when measured by gas chromatography (GPC, Shodex RI-71, Futecs F6110 pump, OHpak SB-802.5 HQ column).

In the above reaction, a polybutadiene derivative having a molecular weight of about 6000 was obtained in the same manner except that the reaction time was 30 minutes after anhydrous sulfuric acid was added.

Example 6

A polybutadiene derivative containing an alkylamine group at one end and a sulfonate group at the other end was prepared in the same manner as in Example 1 except that 27g of dipentylamine was used instead of 16g of diethylamine. The molecular weight of this polybutadiene derivative was about 2000 when measured by gas chromatography (GPC, Shodex RI-71, Futecs F6110 pump, OHpak SB-802.5 HQ column).

In the above reaction, a polybutadiene derivative having a molecular weight of about 6000 was obtained in the same manner except that the reaction time was 30 minutes after anhydrous sulfuric acid was added.

Test Example 1

1.Into each 500 ml flask, 1 ml of any one of 10% (W / V) ammonia, amines, methyl mercaptan, hydrogen sulfide, acetaldehyde, trimethylamine, benzene, and toluene is added and sealed, and the mixture is kept at room temperature for 30 minutes. It was left.

2. The concentration was measured using a detection tube.

3. A 100-fold dilution 0.5ml of a polybutadiene derivative containing an alkylamine group and a sulfonate group at one end synthesized in Examples 1 to 6 was injected and sealed through a nozzle equipped with a nozzle. It was left to stand at room temperature for 30 minutes.

4. The concentration was measured using a detection tube.

According to the test example, a polybutadiene derivative containing an alkylamine group at one end and a sulfonate group at the other end produced by the method of Examples 1 to 6 was ammonia, amines, methyl mercaptan, hydrogen sulfide, and acetaldehyde. The results of testing the deodorizing ability for, trimethylamine, benzene and toluene are shown in Table 1 below.

Unit: Detection concentration in ppm and removal rate in% division ammonia Amines Methyl mercaptan Hydrogen sulfide Acetaldehyde Trimethylamine benzene toluene Control Detection concentration 100 100 90 100 90 85 100 100 Removal rate 0 0 0 0 0 0 0 0 Example 1 Detection concentration 5 10 16 7 8 13 35 23 Removal rate 95 90 82.2 93 91.1 84.7 65 77 Example 2 Detection concentration 3 8 10 3 7 10 30 19 Removal rate 97 92 88.9 97 92.2 88.2 70 81 Example 3 Detection concentration 5 9 17 5 7 14 35 25 Removal rate 95 91 81.1 95 92.2 83.5 65 75 Example 4 Detection concentration 7 12 16 9 10 15 30 30 Removal rate 93 88 82.2 91 88.9 82.4 70 70 Example 5 Detection concentration 6 10 16 10 14 17 25 24 Removal rate 94 90 82.2 90 84.4 80 75 76 Example 6 Detection concentration 10 15 20 10 17 20 20 20 Removal rate 90 85 77.8 90 81.1 76.5 80 80 Remarks Urine Fish Kimchi, Protein Industrial site Tobacco, fungus Fish sanitary napkin Industrial site Industrial site

The polybutadiene derivatives prepared by the method of Examples 1 to 6, containing an alkylamine group at one end and a sulfonate group at the other end, have a removal rate of at least 65% to 97% with respect to various malodorous substances as shown in the above table. Has

Test Example 2

The polybutadiene derivative of the general formula (I) having a spraying amount of 2000 and the compound having a molecular weight of 6000 were tested for deodorizing power using the same detection tube method as in Test Example 1, and the results are shown in Table 2 below.

division ammonia Amines Methyl mercaptan Hydrogen sulfide A B A B A B A B Control Detection concentration 100 ppm 100 ppm 100 ppm 100 ppm 90 ppm 90 ppm 100 ppm 100 ppm Removal rate 0% 0% 0% 0% 0% 0% 0% 0% Example 1 Detection concentration 5 ppm 10 ppm 10 ppm 14 ppm 16 ppm 25 ppm 7 ppm 15 ppm Removal rate 95% 90% 90% 86% 82.2% 72.2% 93% 85% Example 2 Detection concentration 3 ppm 7 ppm 8 ppm 12 ppm 10 ppm 14 ppm 3 ppm 8 ppm Removal rate 97% 93% 92% 88% 86.9% 84.4% 97% 92% Example 3 Detection concentration 5 ppm 11 ppm 9 ppm 14 ppm 17 ppm 22 ppm 5 ppm 10 ppm Removal rate 95% 89% 91% 86% 81.1% 75.6% 95% 90% Example 4 Detection concentration 7 ppm 10 ppm 12 ppm 16 ppm 16 ppm 20 ppm 9 ppm 12 ppm Removal rate 93% 90% 88% 84% 82.2% 77.8% 91% 86% Example 5 Detection concentration 6 ppm 9 ppm 10 ppm 15 ppm 16 ppm 22 ppm 10 ppm 15 ppm Removal rate 94% 91% 90% 85% 82.2% 75.6% 90% 85% Example 6 Detection concentration 10 ppm 15 ppm 15 ppm 10 ppm 20 ppm 25 ppm 10 ppm 20 ppm Removal rate 90% 85% 85% 82% 77.8% 72.2% 90% 80% Remarks Urine Product Kimchi, Protein Industrial site

Acetaldehyde Trimethylamine benzene toluene A B A B A B A B Control Detection concentration 90 ppm 90 ppm 85 ppm 85 ppm 100 ppm 100 ppm 100 ppm 100 ppm Removal rate 0% 0% 0% 0% 0% 0% 0% 0% Example 1 Detection concentration 3 ppm 10 ppm 13 ppm 16 ppm 35 ppm 34 ppm 23 ppm 20 ppm Removal rate 91.1% 88.9% 84.7% 81.2% 65% 66% 77% 80% Example 2 Detection concentration 7 ppm 8 ppm 10 ppm 14 ppm 30 ppm 28 ppm 19 ppm 18 ppm Removal rate 92.2% 91.1% 88.2% 83.5% 70% 72% 81% 82% Example 3 Detection concentration 7 ppm 12 ppm 10 ppm 17 ppm 35 ppm 30 ppm 25 ppm 21 ppm Removal rate 92.2% 86.7% 88.2% 80% 85% 70% 75% 79% Example 4 Detection concentration 10 ppm 10 ppm 15 ppm 21 ppm 30 ppm 25 ppm 30 ppm 28 ppm Removal rate 88.9% 88.9% 82.4% 75.3% 70% 75% 70% 72% Example 5 Detection concentration 14 ppm 17 ppm 17 ppm 21 ppm 25 ppm 22 ppm 24 ppm 20 ppm Removal rate 84.4% 81.1% 80% 75.3% 75% 78% 76% 80% Example 6 Detection concentration 17 ppm 20 ppm 20 ppm 30 ppm 20 ppm 16 ppm 20 ppm 15 ppm Removal rate 81.1% 77.8% 76.5% 64.7% 80% 84% 80% 85% Bad smell Cigarette, fungus Fish sanitary napkin Industrial site Industrial site

Note: 1) In the table, the unit of detection concentration is ppm and the removal rate is%.

2) In the table, A is a case where the general formula (I) compound whose molecular weight (MW) is 2000 is used, and B is a case where the general formula (I) compound which has a molecular weight (MW) 6000 is used.

The polybutadiene derivative containing an alkylamine group at one end and a sulfonate group at the other end of the present invention can be stored for a long time when used with water-soluble polysaccharides (sodium alginate, sodium carboxymethylcellulose, hydroxyethyl cellulose), etc. In addition, when used in combination with the aromatic material can improve the deodorizing performance.

As described above, the compound (I) of the present invention is composed of a polybutadiene derivative or a salt thereof containing an alkylamine group at one end and a sulfonate group at the other end thereof, or a salt thereof, ammonia, mercaptans, amines, ketones, etc. Odor can be removed by reacting most of the odorous substances generated around the living, and in particular, it is possible to treat at low cost in the removal of toxic substances released into the air at industrial sites, and improve the working environment of workers and long-term The preventive effects on occupational diseases that can be caused by exposure can be obtained.

Claims (6)

Polybutadiene derivative of the following general formula (I) whose molecular weight is 1000-6000. [Wherein n is an integer, R ₁ and R ₂ represent an alkyl group having 1 to 5 carbon atoms, and M represents an alkali metal or an alkaline earth metal.] A polybutadiene substituted with hydroxy is reacted with an alkylamine, followed by sulfuric acid, followed by reaction with an alkylamine in the reaction product to further alkylate an amine group of the polybutadiene, and the obtained compound is reacted with an alkali metal or alkali metal hydroxide. A method for producing a polybutadiene derivative of the general formula (I), characterized by converting a sulfonic acid group into a metal salt by neutralization reaction. 3. The process according to claim 2, wherein the hydroxy substituted polybutadiene is reacted with an alkylamine in a solvent. The method according to claim 2 or 3, wherein the solvent is a lower alcohol having 1 to 5 carbon atoms, a ketone having 8 or less carbon atoms, or an alkane compound having 1 to 6 carbon atoms. The process according to claim 2 or 3, wherein the amine is a lower amine having 1 to 5 carbon atoms. The process according to claim 2 or 3, wherein the molecular weight of the compound of general formula (I) is produced at 1500 to 2000 with a time of reacting with sulfuric acid at about 50 to 60 minutes.