JP6471288B2 - Fullerene composition, resin additive and resin composition - Google Patents

Description

  The present invention relates to a fullerene composition, a resin additive, and a resin composition.

Patent Document 1 describes that fullerene C ₆₀ is dissolved in salmon oil to 0.05% by mass. This is said to be related to the specific π-π interaction between phosphoglyceride lecithin and fullerene.

  In Non-Patent Document 1, data on the solubility of 200 or more solvents is arranged for the solvent that dissolves fullerene. It is described that it dissolves in pyridine or piperidine.

International Publication WO2007 / 001188

Karl M.M. Kadish, FULLLEENES Chemistry, Physics, and Technology, P53-90

  Fullerene is the only allotrope of carbon and can be dissolved in a solvent. However, the solvent capable of preferably dissolving fullerene is limited to some solvents having a benzene ring such as toluene, xylene, and trimethylbenzene, and the solubility is extremely low in other soluble solvents.

  The subject of this invention is providing the solvent which can melt | dissolve more than a fixed fullerene other than an aromatic compound.

  In addition, fullerene has an effect of scavenging radicals and is promising as an additive for resins. However, fullerenes are generally fine particles, and it is difficult to dissolve them even if the fine particles are added as they are. Even if a fullerene is dissolved in a solution such as toluene known as a solvent capable of dissolving fullerene and mixed with a resin having a polar group, the resin having a polar group does not dissolve in toluene, so the solvent is separated and mixed well. It was difficult.

  Accordingly, an object of the present invention is to provide a composition that dissolves fullerene and has excellent mixing properties with a resin having a polar group.

  As a result of intensive studies on the above problems, the present inventors have completed the present invention including the following aspects.

(1) the nitrogen-containing heterocyclic N- oxide compounds are dissolved fullerenes, the density before notated fullerene, the composition is 0.01 to 4 mass%.
(2) The composition according to item ( 1 ) , wherein the fullerene is fullerene C ₆₀ or fullerene C ₇₀ .
(3) the nitrogen-containing heterocyclic A composition according to item (1) or (2) a 4-7 membered ring.
(4) the nitrogen-containing heterocyclic A composition according to item (3) is a pyridine ring or a piperidine ring.
(5) A resin additive comprising the composition according to any one of ( 1 ) to ( 4 ) above.
(6) A resin composition obtained by mixing a resin having a polar group and the resin additive described in ( 5 ) above and removing the nitrogen-containing heterocyclic N-oxide compound.
(7) concentration of the pre-notated fullerene is, the resin composition according to item (6) is 0.0001 to 2 mass%.

  The composition of the present invention provides a resin composition having improved durability by being added as a resin additive to a resin having a polar group.

  The composition of the present invention comprises a nitrogen-containing heterocyclic N-oxide compound in which fullerene is dissolved.

Examples of the fullerene used in the present invention include C ₆₀ , C ₇₀ , C ₈₄ , higher order fullerene, and a mixture thereof. From the viewpoint of availability, it is preferable to use C ₆₀ or C ₇₀ or a mixture thereof.

  The concentration of fullerene in the composition of the present invention is preferably 0.01 to 4% by mass, more preferably 0.01 to 3% by mass, and still more preferably 0.03 to 2% by mass. If the fullerene concentration is in the above range, it is expected to dissolve at the molecular level, and a clear effect by addition of fullerene can be expected. When the fullerene concentration is 4% by mass or more, fullerenes that do not dissolve are present as aggregated particles, which adversely affects mechanical properties.

The heterocyclic ring of the nitrogen-containing heterocyclic N-oxide compound used in the present invention includes, for example, a 6-membered piperidine ring and a pyridine ring; a 5-membered pyrrolidine ring and a pyrrole ring; a 4-membered azetidine ring and an azeto ring; Preferred examples include a membered azepane ring and azepine ring. Among these, since it is stable, those having the 5-membered ring and the 6-membered ring are more preferable, and those having the 6-membered ring are more preferable.
The nitrogen-containing heterocyclic N-oxide compound may have a substituent, and examples thereof include a methyl group, an ethyl group, a hydroxyl group, and a carboxyl group. The substituent may be a condensed ring. It is preferable to have a phenyl group as a substituent because the solubility of fullerene is improved.

  Specific examples of the nitrogen-containing heterocyclic N-oxide compound used in the present invention include 2,2,6,6-tetramethylpiperidine-oxyl radical, pyridine oxide, benzo-2,2,6,6-tetramethylpiperidine- Examples include oxyl radical and benzopyridine oxide.

  As a method for producing the composition of the present invention, fullerene is dissolved using a nitrogen-containing heterocyclic N-oxide compound as a solvent. If the solvent is solid at room temperature, the fullerene should be dissolved at a temperature equal to or higher than the melting point. When the fullerene is dissolved in the nitrogen-containing heterocyclic N-oxide compound, an ultrasonic disperser, an ultradisperser, or the like can be used. At this time, a planetary mixer or the like can be used for a solvent having a high viscosity. When fine pulverization is performed by a medium type pulverizer such as a bead mill, fullerene has a high cohesive force, and thus the particle size may be increased.

  The resin additive of the present invention contains the composition of the present invention. Since the resin additive of the present invention contains fullerene, it can be used as a radical scavenger. In particular, the resin additive of the present invention can be suitably used for a resin having a polar group. As resins having polar groups, polyacrylamide, polyacrylic acid, polyimide, polyallylsulfonic acid (salt), nylon 6, nylon 66, cellulose, cellulose ester, polyphthalamide, polyethylene terephthalate, polyethylene oxide, polylactic acid, polyanhydride Maleic acid, polymethacrylic acid, polypyromellitimide, polytetrafluoroethylene, urea resin, polyurethane, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinylidene chloride, polyvinylidene fluoride, fluorine-containing elastomer, chlorine-containing elastomer Is mentioned.

  The content of the composition of the present invention in the resin additive of the present invention and the amount of the resin additive of the present invention added to the resin are preferably 0 when the resin additive is added to the resin. It is adjusted to contain 0.0001 to 2% by mass, more preferably 0.0002 to 1% by mass, and even more preferably 0.0002 to 0.5% by mass. If the fullerene content is in the above range, it is expected that fullerene will be dissolved in the resin at the molecular level, and no aggregation of fullerene will occur even after heating and cooling processes, and the above-mentioned effects are expected as a resin additive. it can.

  A general method can be used when the resin additive of the present invention is mixed with the resin, but melt kneading is suitable as a simple method.

  The nitrogen-containing heterocyclic N-oxide compound is a kind of heterocyclic compound that is very widely used in industrial products, medical and agrochemical intermediates, foods, cosmetics and the like. On the other hand, fullerene exhibits very excellent characteristics as an electron acceptor, has a remarkable function as a radical trap, and has been confirmed to have an additive effect in a wide range of applications.

  For this reason, the composition of the present invention in which fullerene is dissolved in a nitrogen-containing heterocyclic N-oxide compound has an effect of preventing deterioration and alteration by being used as an additive such as a pharmaceutical or agricultural intermediate or a resin. In particular, if it is used as an additive for a resin, it is expected to suppress the cleavage of the main chain, and effects such as improved heat resistance and durability of mechanical properties are expected.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited only to a following example.

<Example 1>
300 g of commercially available 2,2,6,6-tetramethylpiperidineoxyl radical is heated to 50 ° C. and 6 g of fullerene mixture (mixture containing C ₆₀ and C ₇₀ , nanomix ST, manufactured by Frontier Carbon Co.) is added with stirring. Then, it was treated with an ultrasonic disperser for 3 minutes to obtain a solution. The solution was cooled to room temperature and then pulverized in a mortar to obtain a powdery composition containing 1.96% by mass of fullerene.

<Example 2>
300 g of pyridine N-oxide was heated to 70 ° C., 6 g of a fullerene mixture (nanom mixST, manufactured by Frontier Carbon Co.) was added with stirring, and a solution was obtained in the same manner as in Example 1. This solution was cooled to room temperature to obtain a powdery composition containing 1.96% by mass of fullerene.

<Reference example>
A fullerene-containing toluene composition was obtained in the same manner as in Example 1 except that 0.1% by mass of the fullerene mixture of Example 1 was added to toluene.

  When the ultraviolet-visible light spectral curve of 300 nm to 900 nm of the fullerene compositions of Examples 1 and 2 was compared with the same spectral curve of a toluene solution containing 0.1% by mass of the fullerene mixture of the reference example, each peak wavelength ( (About 335 nm) was confirmed to be almost the same. In the measurement of the fullerene-containing compositions of Examples 1 and 2, an ultraviolet-visible light spectroscopic curve at a just dissolved temperature was obtained using a cold / hot cell holder. Conventionally, it has been known that fullerene dissolves in an amount of 0.1% by mass or more with respect to toluene, and if fullerene does not dissolve and forms aggregated particles, a spectroscopic analysis cannot provide a clear peak. It can be determined that the compositions of Examples 1 and 2 were dissolved fullerene.

<Comparative Example 1>
A fullerene-containing solution was obtained in the same manner as in Example 1 except that the addition amount of the fullerene mixture of Example 1 was 15 g. In this solution, a part of fullerene was precipitated without dissolving, but it was cooled without being filtered, and a powdery composition containing 4.76% by mass of fullerene was obtained.

<Comparative example 2>
A fullerene-containing solution was obtained in the same manner as in Example 2 except that the addition amount of the fullerene mixture in Example 2 was changed to 15 g. In this solution, a part of fullerene was precipitated without dissolving, but it was cooled without being filtered, and a powdery composition containing 4.76% by mass of fullerene was obtained.

<Examples 3-4, Comparative Examples 3-8>
The powder obtained in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 was used as a resin additive. These resin additives were kneaded into nylon 6 under the following conditions so as to have the blending amounts shown in Table 1 below. The kneading was performed under reduced pressure. During the kneading process, the nitrogen-containing heterocyclic N-oxide compound and toluene are evaporated and distilled off, and substantially only fullerene remains in nylon 6.
Kneading equipment; Labo Plast Mill (registered trademark) (Toyo Seiki)
Kneading temperature: 230 ° C
Kneading time: 5 minutes

Thereafter, a flat plate was formed with a press, and a dumbbell for tensile fatigue test (ASTMI dumbbell tensile test piece) was punched out. The tensile fatigue test was performed under the conditions of a single vibration, 5 Hz, a stress of 5.5 kg / mm ² , a stress ratio = 0, and room temperature, and the number of repetitions until breakage was measured. The measurement results of the tensile fatigue test are shown as relative values with the result of the additive-free product of the heterocyclic compound composition (Comparative Example 5 before deterioration) taken as 1.

  In Examples 3 and 4, as compared with Comparative Example 5, the number of times until breakage was improved. On the other hand, Comparative Examples 3 and 4 in which the amount of fullerene added was large, fractured less times than the additive-free product, and the deterioration was promoted. Since the amount of the fullerene contained is larger than those in Examples 1 and 2, it is assumed that the cause is that the fullerene is aggregated. Comparative Example 6 is a resin composition containing no fullerene as compared with Example 3. It turns out that there is no effect of durability improvement only by the heterocyclic compound. Further, Comparative Example 7 in which fullerene was added alone without using a heterocyclic compound was broken earlier than Example 4. In Comparative Example 7, it can be inferred that fullerene cannot be finely dispersed and aggregates are present. In Comparative Example 8 using the toluene composition, the deterioration was very rapid. It is inferred that the fullerene was unevenly distributed because the toluene composition was not mixed with nylon.

  The composition of the present invention can be added to a resin having a polar group, for example, by adding an additive such as a natural resin, a synthetic resin, an industrial article, a pharmaceutical / agrochemical intermediate, a food, a cosmetic, a lubricant, and the like It is effective in the field of oils and fats.

Claims (7)

Fullerenes are dissolved in nitrogen-containing heterocyclic N- oxide compounds,
Concentration before notated fullerene is, the composition is 0.01 to 4 mass%. The composition according to claim 1, wherein the fullerene is fullerene C ₆₀ or fullerene C ₇₀ . The nitrogen-containing heterocyclic A composition according to claim 1 or 2 is a 4-7 membered ring. The nitrogen-containing heterocyclic A composition according to claim 3 is a pyridine ring or a piperidine ring.   The resin additive containing the composition in any one of Claims 1-4. A resin composition obtained by mixing a resin having a polar group and the resin additive according to claim 5 and removing the nitrogen-containing heterocyclic N-oxide compound. Concentration before notated fullerene is, the resin composition according to claim 6 which is 0.0001 wt%.