JPH09157328A - Gas collector - Google Patents

Abstract

PROBLEM TO BE SOLVED: To collect aliphatic aldehydes that are off-taste components and off- odor components resulting from decomposition of polyolefin resins by introducing highly reactive dinitrophenylhydrazine units to side chains of a linear polymer. SOLUTION: This gas collector is a compound which is a linear polymer whose main chain has repeat units represented by formulae I and II and whose side chains are represented by formulae III and IV. The gas collector is produced, for example, as follows; 6-chloro-3,5-dinitroaniline is reacted with a (meth)acrylic monomer (e.g. methacrylic anhydride) in a solvent (e.g. dehydrated tetrahydrofuran). The resulting compound is reacted with hydrazine in a solvent to give a (meth)acrylic acid type monomer. In the polymerization of the monomer, the reaction is carried out in a solvent in the presence or absence of a comonomer (e.g. a methacrylate) using a polymerization initiator (e.g. N,N'- azobisisobutyronitrile).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a gas trap. This gas trapping material traps aliphatic aldehydes, which are off-flavor and off-flavor components generated by decomposition of the polyolefin resin, for quantitative analysis.

BACKGROUND OF THE INVENTION Polyolefin resins such as polyethylene, when exposed to a high temperature environment, undergo oxidative decomposition to generate aliphatic aldehydes, which give off taste and odor. In order to analyze such trace substances in the environment, it is conventionally necessary to perform pretreatment such as concentrating the sampled sample or removing interfering substances. Liquid-liquid extraction operations by liquid chromatography, column chromatography, and the like are used for such treatment.

Further, as a simple method, there is a solid phase extraction method in which a compound in a liquid sample is adsorbed on a stationary phase and distributed and retained. In this analysis method, a stationary phase in which a carrier is coated with a substance that reacts with an extract or a material that partitions is used, which is derivatized and eluted by liquid chromatography for analysis. However, such a method limits the samples that can be processed to liquid samples.

Further, in the case of a gas sample, there is also used a method in which a porous polymer is adsorbed and then thermally desorbed for analysis. In these analysis methods, the target component is adsorbed,
After distribution, qualitative analysis and quantitative analysis are performed by separating and analyzing by liquid chromatography or gas chromatography. However, in such a method,
The substance adsorbed on the porous polymer is not desorbed unless heat treatment is performed, and there is no guarantee that desorption will be surely performed.

[0004]

OBJECT AND SUMMARY OF THE INVENTION An object of the present invention is to provide a gas scavenger capable of easily qualitatively and quantitatively analyzing an aliphatic aldehyde produced by oxidative decomposition of a polyolefin resin such as polyethylene under a high temperature environment. It is in.

The inventors of the present invention react (derivatize) regardless of whether the sampling sample is in a solution state (aqueous solution) or a gas state to capture an aliphatic aldehyde which is a target,
As a result, we have conducted intensive studies to obtain a substance that develops color and can be qualitatively analyzed. As a result, we found that a linear polymer copolymer or homopolymer in which highly reactive dinitrophenylhydrazine units were introduced into the side chain was useful as a simple gas scavenger for aliphatic aldehydes. The invention was completed.

That is, the present invention provides a gas scavenger containing a linear polymer as a main chain and a polymer compound having a side chain represented by the following formula (I).

[0007]

Embedded image (In the formula, -A- is a direct bond, -NH-CO- or -O.
Representing —CO—) One copolymer of the present invention is produced, for example, as follows. 6-chloro-3,5 in a solvent such as dehydrated THF
-Dinitroaniline (CDNA) with methacrylic anhydride,
A (meth) acrylic acid-based monomer such as methacrylic acid chloride, acrylic acid anhydride, or acrylic acid chloride is reacted. The obtained compound is reacted with hydrazine in a solvent,
A (meth) acrylic acid type monomer is obtained. When the above-mentioned monomer is polymerized, the reaction is carried out in a solvent in the presence or absence of a comonomer using a polymerization initiator such as N, N′-azobisisobutyronitrile. As the comonomer at the time of the polymerization, a methacrylic acid ester such as methyl methacrylate (MMA), or an acrylic acid ester,
In addition, α-olefins such as ethylene, propylene, vinyl acetate and styrene are used, and a gas scavenger excellent in physical properties such as heat resistance as compared with a homopolymer can be obtained.

The other copolymer of the present invention is produced by the following production method. 6-chloro-in a solvent such as dehydrated THF
3,5-Dinitrophenol (CDNP) is reacted with a (meth) acrylic acid-based monomer such as methacrylic acid chloride and acrylic acid chloride. The obtained compound is reacted with hydrazine in a solvent to obtain a (meth) acrylic acid type monomer. Upon polymerization, the reaction is carried out in a solvent in the presence or absence of a comonomer using a polymerization initiator such as N, N′-azobisisobutyronitrile. As the comonomer at the time of polymerization, the same monomer as described above such as methyl methacrylate (MMA) may be used, and a gas scavenger having excellent physical properties such as heat resistance as compared with a homopolymer can be obtained.

Still another polymer of the present invention is produced, for example, by the following reaction route. Using 6-chloro-3,5-dinitroaniline (CDNA) as a raw material, hydrogenolysis is carried out in a solvent in the presence of a catalyst, and then borofluoric acid is reacted. The solution obtained is reacted with ethylene in the presence of a catalyst.

Alternatively, the raw material 6-chloro-3,
Using 5-dinitroacetophenone (CDNA), sodium borate is reacted in a solvent. The obtained compound is dehydrated with p-toluenesulfonic acid or the like,
A compound similar to the above is obtained.

The styrene-type monomer is obtained by reacting the compounds obtained by the above-mentioned two kinds of production methods with hydrazine in the presence of a polymerization inhibitor in a solvent.

Polymerization of these monomers can be carried out in a solvent in the presence or absence of a comonomer using a polymerization initiator such as N, N'-azobisisobutyronitrile. As a comonomer, methyl methacrylate (MM
The same monomers as described above such as A) may be used, and a gas scavenger excellent in physical properties such as heat resistance as compared with a homopolymer can be obtained.

The average molecular weight of these copolymers is about 10,000 to 100,000.

In the present invention, the repeating unit is particularly represented by the following formula (VII
I) and the following formula (III)

Embedded image

Embedded image Is a polymer compound (copolymer A) or a repeating unit having the following formula (IX) and formula (III)

Embedded image

Embedded image Or a repeating unit of the following formula (X)

Embedded image The present invention provides a gas scavenger containing the polymer compound (polymer C).

Further, the present invention provides a gas detector filled with these gas collecting materials.

The copolymer of the present invention reacts with an aliphatic aldehyde which is a decomposition product of polyolefin as follows.

[0017]

Embedded image

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BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail based on specific examples.

[Experiment 1 (Copolymer A)] The above copolymer A is produced, for example, by the following reaction route.

[0019]

Embedded image 200 mL of dehydrated THF was placed in the flask, and 10.9 g of 6-chloro-3,5-dinitroaniline (CDNA) was dissolved at room temperature. After dissolution, hydroquinone 0.2 was added to the system.
Then, 7.7 g of methacrylic anhydride was added dropwise, and the reaction was carried out at room temperature under a nitrogen atmosphere for about 8 hours.
After completion of the reaction, the whole solution was concentrated under reduced pressure, methylene chloride was added to the residue to dissolve it, and the residue was washed with an aqueous hydrochloric acid solution. The methylene chloride layer was dried over Na ₂ SO ₄ and then concentrated under reduced pressure.
The residue was separated and purified by silica gel column chromatography having a coolable structure so as not to polymerize (yield: about 70%).

8.6 g of the obtained compound was added to ethanol 15
It was dissolved in 0 mL, 0.2 g of hydroquinone was added thereto, and the mixture was reacted with 1.0 g of hydrazine at 40 ° C. for about 4 hours in a nitrogen atmosphere. After completion of the reaction, the whole solution was concentrated under reduced pressure, methylene chloride was added to the residue to dissolve it, and the residue was washed with an aqueous hydrochloric acid solution. The methylene chloride layer was dried over Na ₂ SO ₄ , concentrated under reduced pressure, and the residue was separated and purified by silica gel column chromatography having a coolable structure so as not to polymerize to obtain a methacrylic acid type monomer (yield: about 55%).

Then, methyl methacrylate (MMA) dissolved in 50 mL of dehydrated and purified toluene in the polymerization tube 2.
After adding 5 g and 7.0 g of the previously obtained methacrylic monomer, and further adding 0.3 g of N, N'-azobisisobutyronitrile as a polymerization initiator, dissolved oxygen is generated in a state of being solidified with liquid nitrogen. The degassing was repeated until it stopped. After completion of the degassing operation, the mixture was heated to about 50 to 60 ° C. and the polymerization reaction was carried out for about 6 hours in a water bath. After completion of the reaction, the mixture was allowed to cool, the polymerization tube was broken, and the solution was poured into a large amount of ether for reprecipitation. The precipitate was repeatedly washed with ether and dried to obtain a copolymer. The molecular weight of the obtained copolymer was about 40,000, and it was confirmed from the results below that the target copolymer was obtained. ¹ H-NMRppm (CDCl ₃ ): δ 9.0-9.2 (aromati
c), 7.5-8.1 (aromatic), 7.1 (NH), 4.5-4.7 (NH-NH ₂ ),
3.8-4.0 (CH ₂ ), 2.4-2.5 (OCH ₃ ), 1.2-1.4 (CH ₃ ) [Experiment 2 (Copolymer B)] The copolymer B is produced, for example, by the following reaction route.

[0022]

Embedded image 200 mL of dehydrated THF was placed in the flask, and 10.9 g of 6-chloro-3,5-dinitrophenol (CDNP) was dissolved at room temperature. After dissolution, this was cooled, 1.0 g of triethylamine was added, 5.3 g of methacrylic acid chloride was slowly added dropwise at room temperature under a nitrogen atmosphere, and the mixture was allowed to react for 1 hour under cooling and returned to room temperature for about 2 hours.

After completion of the reaction, the whole solution was concentrated under reduced pressure, methylene chloride was added to the residue to dissolve it, and the residue was washed with an aqueous hydrochloric acid solution. The methylene chloride layer was dried over Na ₂ SO and then concentrated under reduced pressure, and the residue was separated and purified by silica gel column chromatography having a coolable structure so as not to polymerize (yield: about 60%).

8.6 g of the obtained compound was added to ethanol 15
Dissolve it in 0 mL, add 0.2 g of hydroquinone to it, and add 1.0 g of hydrazine and about 4 at 40 ° C under a nitrogen atmosphere.
Reacted for hours. After the reaction was completed, the whole solution was concentrated under reduced pressure,
Methylene chloride was added to the residue to dissolve it, and the residue was washed with an acidic aqueous solution of hydrochloric acid. The methylene chloride layer was dried over Na ₂ SO, concentrated under reduced pressure, and the residue was separated and purified by silica gel column chromatography having a coolable structure so as not to polymerize to obtain a methacrylic monomer (yield: about 45%. ). Next, 2.5 g of methyl methacrylate (MMA) dissolved in 50 mL of dehydrated and purified toluene and 7.0 g of the methacrylic monomer previously synthesized were added to the polymerization tube, and N, N ′ was further added.
-After adding 0.3 g of azobisisobutyronitrile,
Degassing was repeated until dissolved oxygen was not generated in the state of being solidified with liquid nitrogen. After degassing operation, about 50-60 ℃
The mixture was heated to 0 ° C. and polymerized in a water bath for about 6 hours.

After completion of the reaction, the solution was allowed to cool, the polymerization tube was broken, and the solution was poured into a large amount of ether for reprecipitation. The precipitate was repeatedly washed with ether and dried to obtain a copolymer. The molecular weight of the copolymer was about 35,000, and it was confirmed from the results below that the copolymer was the target. ¹ H-NMRppm (CDCl ₃ ): δ 9.0-9.2 (aromati
c), 7.5-8.1 (aromatic), 4.5-4.7 (NH-NH ₂ ), 3.8-4.0 (CH
_{2), 2.4-2.5 (OCH 3)} , 1.2-1.4 (CH 3) [ Experiment 3 and Experiment 4 (Polymer C)] The polymer C is
For example, it is produced by the following two types of reaction routes.

[0026]

Embedded image Experiment 3 (raw material: 6-chloro-3,5-dinitroaniline) 200 mL of dehydrated ethanol was placed in a pressure resistant tube, and 6-chloro-
10.9 g of 3,5-dinitroaniline (CDNA) was dissolved at room temperature. After dissolution, 0.2 g of platinum oxide was added thereto, and hydrogenolysis was performed at 5 kg / cm ² at room temperature for about 12 hours. After completion of the reaction, the catalyst was filtered off, and the filtrate was concentrated under a nitrogen atmosphere under reduced pressure. To the residue, 30% of 42% fluoroboric acid and 300 mL of water were added and stirred. This mixed solution was cooled to 0 ° C., and 150 mL of an aqueous solution in which 3.5 g of sodium nitrite was dissolved was slowly added dropwise. The obtained homogeneous solution was transferred to a pressure resistant tube again, 200 mL of acetonitrile was added, and then 20.6 g of sodium acetate and 6.0 g of bis (dibenzylideneacetone) palladium were successively added and dissolved. Then, the mixture was reacted under ethylene gas at 5 kg / cm ² at room temperature for 24 hours, and after completion of the reaction, diethyl ether was added for extraction. The organic layer was washed with an aqueous NaHCO ₃ solution and a saturated saline solution in this order, and then dried over anhydrous Na ₂ SO ₄ . After the desiccant was filtered off, 0.2 g of tert-butylcatechol was added to the filtrate and the mixture was concentrated under reduced pressure. The residue was separated and purified by silica gel column chromatography having a coolable structure so as not to polymerize (yield: about 45%).

Next, 8.6 g of the obtained compound was dissolved in 150 mL of ethanol, and 0.2 g of hydroquinone was added thereto.
Was added and reacted with 1.0 g of hydrazine in a nitrogen atmosphere at 40 ° C. for about 4 hours. After completion of the reaction, the whole solution was concentrated under reduced pressure, methylene chloride was added to the residue to dissolve it, and the residue was washed with an aqueous hydrochloric acid solution. The methylene chloride layer was dried with Na ₂ SO ₄ and then
Concentrate under reduced pressure, the residue is separated by alumina column chromatography having a structure that can be cooled so as not to polymerize,
A styrene type monomer was obtained by purification (yield: about 60%).

Then, 4.5 g of the styrene-type monomer dissolved in 50 mL of dehydrated and purified toluene in the polymerization tube.
Was added, and 0.3 g of N, N'-azobisisobutyronitrile was further added, and then degassing was repeated until dissolved oxygen was not generated in the state of being solidified with liquid nitrogen. After completion of the degassing operation, the mixture was heated to about 50 to 60 ° C. and a polymerization reaction was carried out for about 6 hours in a water bath. After completion of the reaction, the mixture was allowed to cool, the polymerization tube was broken, and the solution was poured into a large amount of methanol for reprecipitation. The precipitate was repeatedly washed with methanol and dried to obtain a polymer. The molecular weight of the polymer was about 25,000, and it was confirmed from the results below that the polymer was the target polymer. ¹ H-NMRppm (CDCl ₃ ): δ 8.8-8.9 (aromati
c), 7.6-8.3 (aromatic), 6.2-6.5 (CH), 5.3-5.4 5.6-5.
_{9 (CH 2), 4.7-4.8 (} NH-NH 2) Experiment 4 (material: 6-chloro-3,5-nitroacetophenone) was dissolved in anhydrous ethanol 300mL into the flask 6-chloro-3,5-nitroacetophenone (CDN
A) 10.9g was put, and sodium borate 2.8g was added at room temperature. After dissolution, react for 24 hours, then water 3
It was poured into 00 mL, neutralized, and extracted with methylene chloride. The organic layer was washed with water, dried over Na ₂ SO ₄ , and then concentrated under reduced pressure. The residue was separated and purified by silica gel column chromatography (yield: about 60%).

5.5 g of the obtained compound was added to benzene 200
Dissolve in mL, add 0.1 g of p-toluenesulfonic acid to this, and use a Dean-Stark trap to carry out dehydration reaction under reflux for 24 hours.
Time went. After completion of the reaction, the mixture was allowed to cool and benzene was distilled off under reduced pressure. The residue was separated and purified by alumina column chromatography having a coolable structure (yield: about 6
5%).

The obtained compound was prepared in the same manner as in Experiment 3.
Further, it was reacted with hydrazine to obtain a styrene-type monomer, which was polymerized to obtain a polymer C in the same manner as in Experiment 3.

(Adsorption test) Aliphatic aldehyde considered to be one of off-taste and off-odor in the decomposed product of polyethylene
Adsorption of the (co) polymers (A to C) obtained in Experiments 1 to 4 was evaluated for (R = C ₈ H ₁₇ , C ₉ H ₁₉ ). 1 polymer
Dry under reduced pressure at 00 ° C for 3 days, then use a glass tube (120 m long)
m × inner diameter 5 mmφ) was filled with 500 mg. A predetermined amount of C ₈ H ₁₇ CHO (nonanal) shown in Table 1 below is depressurized (10-
It was heated to 20 mmHg) to completely vaporize it, and passed through the glass tube inline for 10 minutes. The nonanal that did not react with the filled polymer and passed through was quantified by gas chromatography to calculate the adsorption amount (reaction amount) of the gas trapping material.

[Table 1] Note) All unreacted polymers are slightly yellowish white polymers.

[0032]

The gas trapping material of the present invention easily qualitatively and quantitatively analyzes an aliphatic aldehyde produced by oxidative decomposition of a polyolefin resin such as polyethylene under a high temperature environment.
This gas trapping material can be used by filling it in a gas detector.

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Claims (4)

[Claims] 1. Having a main chain of a linear polymer and having the following formula (I)
A gas scavenger containing a polymer compound having a side chain represented by. Embedded image (In the formula, -A- represents -NH-CO-, -O-CO- or a direct bond.) 2. The main chain linear polymer is represented by the following formulas (II) and (III): Embedded image Having a repeating unit represented by the following formula (IV) or side chain (V): Embedded image The gas collecting material according to claim 1, represented by: 3. The linear polymer has the following formula (VI): Having a repeating unit represented by the following formula (VII): The gas collecting material according to claim 1, represented by: 4. A gas detector tube filled with the gas trapping material according to claim 1.