JP2833407B2 - New oil adsorbent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a waste oil, a drain oil, a leak oil,
More specifically, the present invention relates to an oil adsorbent having excellent long-term storage stability by adding a specific antioxidant compound to a norbornene-based polymer.

[0002]

2. Description of the Related Art Hitherto, norbornene-based polymers have shown excellent oil adsorbing properties and are known as treatment materials for waste oils and waste oils (JP-A-59-82991). It is also known to add a metal stearate to prevent coagulation (Japanese Patent Laid-Open No. 4-501132). However, they have the drawback that, after long-term storage, the polymer is degraded, the oil absorbency is significantly reduced, and furthermore it becomes unusable due to coagulation.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an oil adsorbent excellent in long-term storage stability.

[0004]

Thus, according to the present invention, by adding a cresol-based and / or phosphite-based antioxidant compound to a norbornene-based polymer, an oil adsorbent excellent in long-term storage stability can be obtained. Provided. The norbornene-based polymer used in the present invention easily absorbs a large amount of solvents (toluene, benzene, xylene, etc.) and various oils (AC heavy oil, spindle oil, machine oil, light oil, kerosene, gasoline, etc.) even at room temperature. Bicyclo (2,2,1) heptene having the property of becoming agar-like (gelling)
2 or a ring-opening polymer or copolymer of this derivative, for example, a polymer obtained by polymerization according to the method described in JP-B-47-35800. The monomers used include bicyclo (2,2,1) heptene-2 and methyl-5-bicyclo (2,2,1) heptene-
2, ethyl-5-bicyclo (2,2,1) heptene-
2, alkyl or alkylidene-5-bicyclo (2,2,1) heptene-2 monomer such as ethylidene-5-bicyclo (2,2,1) heptene-2, methoxy-5-
Bicyclo (2,2,1) heptene-2, ethoxy-5
Alkoxy-5-bicyclo (2,2,1) heptene-2 based monomers such as bicyclo (2,2,1) heptene-2,
Cyano-5-bicyclo (2,2,1) heptene-2, ester monomer of bicyclo (2,2,1) heptene-2-5-carboxylic acid, bicyclo (2,2,1) heptene-2
And diester monomers of -5 and 6 dicarboxylic acids and mixtures thereof. A typical polymer includes polynorbornene, which is a ring-opened polymer of bicyclo (2,2,1) heptene-2.

[0005] The compound used as an anti-aging agent in the present invention is a cresol compound or a phosphite compound. Specific examples of cresol compounds include 2,6
Monophenolic compounds such as -di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-α-dimethylamino-p-cresol, 2,4-bis [(alkylthio) methyl] 2-methylphenol (the alkyl group is C ₅ -C _12), 4,4'-thiobis - (6-tert - butyl -o- cresol), 4,4'-butylidenebis - (3-methyl-6- Tert-butylphenol),
Thiobisphenol compounds such as 2,2-thiobis (4-methyl-6-tert-butylphenol), and triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] Phenolic compounds such as 2,2'-methylene-bis-
(4-methyl-6-tert-butylphenol), 2,
Bisphenol compounds such as 2′-methylene-bis- (4-methyl-6-cyclohexylphenol); and those having a melting point of 100 ° C. or less, for example, 2,4-bis [(octylthio) methyl 2-methylphenol, 2,6-di-tert-butyl-α-dimethylamino-p-cresol, 2,6-di-tert-butyl-4-methylphenol, triethylene glycol-
Bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and the like are preferable, and 2,4-bis [(octylthio) methyl] -6 is particularly preferable.
Methylphenol and 2,6-di-tert-butyl-4-methylphenol are more preferred.

Specific examples of the phosphite compound include tris (noryl phenyl) phosphite, tris (mixed mono- and di-nonylphenyl) phosphite, phenyl-diisodecyl phosphite, and diphenyl mono (2-ethylhexyl). ) Phosphite, diphenyl monotridecyl phosphite, diphenyl isodecyl phosphite, diphenyl isooctyl phosphite, diphenyl nonyl phenyl phosphite,
Triphenyl phosphite, tris (tridecyl) phosphite, triisodecyl phosphite, tris (2-
Ethylhexyl) phosphite, tris (2,4-di.
Tert-butylphenyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite, 4 , 4'-butylidenebis (3-methyl-6-tert-butyl-di-tridecylphosphite), 2,2'-ethylidenebis (4,6-tert-butylphenol) fluorophosphite, 4,4'-isopropyl isopropylidene - diphenol alkyl (C ₁₂ ~C ₁₅₎
Phosphite, cyclic neopentanetetraylbis (2,
4-di-tert-butylphenylphosphite), cyclic neopentanetetraylbis (2,6-di-tert-butyl-4)
-Methylphenyl phosphite), cyclic neopentanetetraylbis (nonylphenyl phosphite), bis (nonylphenyl) pentaerythritol diphosphite, dibutyl hydrogen phosphite, distearyl pentaerythritol diphosphite, hydrogenated bisphenol A penta And erythritol phosphite polymers. Of these compounds, those having a melting point of 100 ° C. or less, tris (norylphenyl) phosphite, and tris (mixed mono- and di-nonylphenyl) phosphites are preferable. In particular, tris (noryl phenyl) phosphite is more preferable.

[0007] These antioxidants may be used alone or as a mixture of two or more compounds. The addition amount of the antioxidant is not particularly limited, but is preferably 0.1 part or more and 20 parts or less based on 100 parts by weight (hereinafter, simply referred to as part) of the norbornene-based polymer. When 4-bis [(octylthio) methyl] -O-cresol is used, it is preferably used in an amount of 0.2 to 20 parts, more preferably 1.0 to 10 parts.

If the amount of the antioxidant is too small, a sufficient stabilizing effect cannot always be obtained, and if the amount is too large, an increase in cost cannot be expected.

In addition to these compounds, a necessary amount of soap powder, calcium carbonate, talc, etc. is added as an anti-clot agent, and if necessary, oils, other polymers, coloring agents, lubricants, etc. are added. You may.

[0010]

As described above, according to the present invention, it is possible to obtain a treated material for waste oil, drained oil, leaked oil, and spilled oil which has excellent long-term storage stability as compared with the prior art. In other words, when an oil spills due to an unexpected accident, it rushes to the site and when processing is started, the processing material is agglomerated and cannot be sprayed on the spilled oil, or the oil absorption decreases. As a result, it is possible to avoid a situation where prompt processing cannot be performed and a disaster is spread.

[0011]

The present invention will be described more specifically with reference to the following examples. Parts and% in Examples, Comparative Examples and Reference Examples are based on weight unless otherwise specified.

(Examples 1 to 3) A norbornene-based polymer and an antioxidant were charged into a mixer at the ratio shown in Table 1, stirred and mixed, heated to 100 ° C., cooled to 40 ° C., and coagulated at the ratio shown in Table 1. The lump inhibitor was added, mixed for 2 minutes with stirring and discharged, and cooled to room temperature to obtain a powder mixture. In addition, (1) Norbornene-based polymer powder "Nosorex (registered trademark)" manufactured by Atochem of France, having a particle size of 0.01 to 1 mm (hereinafter referred to as NSX); Nocrack 200 (compound name:
2,6-di-tert-butyl-4-methylphenol) or "Irganox 152" manufactured by Swiss Ciba Geigy.
0 "(compound name: 2,4 bis [(octyl) methyl] orthocresol); (3) As a phosphite-based compound," Nocrack TNP "(compound name: tris (nonylphenyl) phosphite manufactured by Ouchi Shinko Co., Ltd.) )It was used.

(Comparative Examples 1 to 3) Instead of a cresol compound or a phosphite compound as an antioxidant, p
-Phenylenediamine compounds (Nocrack 810NA)
(Ouchi Shinko Chemical Co., Ltd.)), a quinoline compound (Nocrack 224 (Ouchi Shinko Chemical Co., Ltd.)) and a hydroquinone derivative (Nocrack NS-7 (Ouchi Shinko Chemical Co., Ltd.)). To obtain a powder mixture.

(Test Example 1) Long-term storage method The powder mixtures prepared in the above Examples and Comparative Examples were put into a vat to a thickness of about 5 mm and placed in a hot air circulation oven (gear oven) controlled at 40 ° C. Were exposed for 6 months and 1 year.

(Test Example 2) Oil Adsorption Test The test was carried out in a room controlled at 23 ° C. according to the following test procedure. Fill the beaker with Fuel Oil A. The sample heat-treated in Test Example 1 was taken out of the gear oven, and about 1 g of the powder mixture was accurately measured.
It was left at 48 ° C. for 48 hours. This is put into a 100-mesh stainless steel wire basket, and the weight is accurately measured again. The basket containing the powder mixture is immersed in heavy oil A in a beaker. After one hour, the basket is taken out and left for one hour, and excess oil (adhered oil) is dropped and removed. Accurately weighed, adsorption oil amount (g / g) = (W 2 -
W ₀ ) / W ₁ (where W ₀ is the weight (g) of the stainless steel wire mesh, W ₁ is the weight (g) of the initial powder mixture, and W ₂ is the weight (g) after oil adsorption). The test results are shown in Table 1. The oil absorption retention rate (%) in the table is calculated by the oil absorption change rate after heat treatment when the oil absorption amount before untreatment is set to 100%.も の
The solidified agglomerate was represented by x.

[0016]

[Table 1]

From these results, it was found that the cresol-based compound or the phosphite-based compound exhibited a high amount of adsorbed oil over a long period of time.

(Examples 4 and 5) The amount of Irganox 1520 used as an anti-aging agent was 1.0% and 0.5%
The same test as in Example 2 was performed except that the test was changed to. As a result, the A heavy oil retention after one year was 94% and 7%, respectively.
9%, an effect of NSX alone or more was observed.

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Claims (1)

(57) [Claims] An oil adsorbent composition comprising a norbornene-based polymer and a cresol-based and / or phosphite-based antioxidant compound as an antioxidant.