JP3221888B2 - Inorganic-organic composite - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a crystalline interlayer inorganic was intercalated aliphatic primary amines having 4 or more carbon atoms of the layered phosphate - an organic complex.

[0002]

BACKGROUND ART Crystalline layered phosphate is catalyzed, ion exchange action, gas adsorption, but has excellent properties such as rust effect, all of which are hydrophilic substances.

[0003] Therefore, for example, when trying to prepare to paint and mixing them crystalline layered phosphate to the synthetic resin, cause the hydrophilicity possessed by them reduce the dispersibility in the synthetic resin .

[0004] In general, a coating method has been adopted as a method for making an inorganic compound hydrophobic. For example, a method of hydrophobizing an inorganic compound by coating the surface of the inorganic compound with a wax, a metallic soap, or a silane coupling agent or the like has been proposed (for coating with a metallic soap, for example, Yoshida et al., “ Properties and Applications of Metallic Soap "
Koshobo (1988), coating with a silane coupling agent is described in, for example, Shin-Etsu Chemical's catalog “silane coupling agent”.

[0005] However, with respect to the crystalline layered phosphate salt,
No studies have attempted to convert it to hydrophobic.

[0006]

As described above [0005], crystalline layered phosphate is hydrophilic, poor dispersibility into a resin, therefore, it was to cause the application range is limited .

Accordingly, the present invention is by converting the crystalline layered phosphate <br/> hydrophobic, to solve the problems based on the hydrophilic, aimed at widening the range of applications.

[0008]

Means for Solving the Problems The present inventor has conducted various studies to achieve the above object, and as a result, has found that the general formula M (HPO
₄ ) ₂ · XH ₂ O (where M is Ti or Ce;
X is between layers <br/> crystalline layered phosphate represented by a is) 0-2, by intercalating a number 4 or more aliphatic primary amines carbon, crystalline layered phosphate Have been found to be hydrophobic, and have completed the present invention.

Further, as described above, the number of carbon atoms between layers is 4 or less.
When hydrophobic crystalline layered phosphate by intercalating the aliphatic primary amine above, also have a hydrophobic at high temperatures of 200 to 300 degree ℃ such as those employed during the dispersion of the resin Not only is the method different from the conventional coating method, but the effect is also excellent.

That is, in the coating method which has been conventionally employed for making a general inorganic compound hydrophobic, a coating method of 20
At a high temperature of about 0 to 300 ° C., a coating agent such as a wax, a metal soap, or a silane coupling agent coated on the surface of the particles volatilizes due to heat or undergoes thermal degradation, resulting in a loss of hydrophobicity. but, according to the present invention, in relation to the number 4 or more <br/> aliphatic primary amines carbon to impart hydrophobicity is intercalated between layers of crystalline layered phosphate, the aliphatic 1 amine is less affected by heat, 200-300 ° C
It can have hydrophobicity even at such a high temperature.

Further, since the thermal stability of the crystalline layered aliphatic primary amines having 4 or more carbon atoms was intercalated between the layers of phosphate is improved, the present invention is the thermal stability of the aliphatic primary amine It can also be applied as a means for improving

The crystalline layered phosphate represented by the general formula M (HPO ₄ ) ₂ .XH ₂ O can be obtained, for example, by a reflux method in concentrated phosphoric acid (JP-A-62-226807), an autoclave method. (Japanese Unexamined Patent Publication No. 1-119507), a fluoro complex method [G. Alberti; Inorg. Nu
cl. Chem. , 30 , 317 (1968)].

[0018] In the present invention, the aliphatic primary amines having 4 or more carbon atoms capable of intercalated between the layers of the crystalline layered phosphate, for example, blanking ethylamine, hexylamine, octylamine, decylamine, 4 carbon atoms such as tetradecylamine and cetylamine
-16 aliphatic primary amines, the hydrocarbon moieties of which are within the category of aliphatic primary amines.
As long as it is not limited to the linear one as exemplified above, it may be any of branched, saturated and unsaturated.

In the present invention, a layer of a crystalline layered phosphate is used.
Carbon number of aliphatic primary amine intercalated between
Is limited to 4 or more in Tables 4 and 5 below.
As shown, almost hydrophobicity not expressed when is intercalated methylamine between layers of crystalline layered phosphate, clear when butylamine was intercalated crystalline layered phosphate since the hydrophobicity expression, inorganic having hydrophobic - to obtain an organic complex, requires that the number of carbon is intercalated four or more aliphatic primary amine between layers of crystalline layered phosphate To be
Is based on

[0020] 4 or more carbon atoms between layers of crystalline layered phosphate
The aliphatic primary amine as a method of the intercalated crystalline layered phosphate to the aqueous solution or organic solvent solution of the aliphatic primary amine added, by stirring,
Intercalating aliphatic primary amines having 4 or more carbon atoms into the interlayer of crystalline layered phosphate is carried out.

The above stirring may be carried out for about 1 hour, but a stable intercalating compound, that is, a stable inorganic compound
In order to obtain an organic composite, it is usually preferable to stir for about 5 hours with an ultrasonic disperser.

[0022] Incidentally, when intercalated into layers of crystalline layered phosphate of the aliphatic primary amine, carbon
Since the number 4 or more aliphatic primary amine emissions is small solubility in water, preferably dissolved the aliphatic primary amine in an organic solvent such as benzene.

Since the inorganic-organic composite of the present invention has hydrophobicity, when it is blended with a resin, fiber, paper, or the like, it has good compatibility with them and improved dispersibility, so that a high concentration can be obtained. filling becomes possible and significant reduction in the dispersion cost, improvement of the dispersion uniformity can be achieved to improve the physical properties, catalysis, ion exchange action of the crystalline layered phosphate,
Gas separation and rust prevention can be more effectively utilized.

Further, the inorganic-organic composite of the present invention may be a resin,
When blended in fibers, paper, and the like, the inorganic-organic composite of the present invention can also be used as a functional filler, for example, because of its hydrophobicity, it can help prevent water leakage and contamination.

[0025] In addition, inorganic of the present invention - organic complexes, charcoal
Since the intercalation of an aliphatic primary amine having a prime number of 4 or more has high lipophilicity, it can be applied to separation and recovery agents of spilled oil.

Further, the number of carbon atoms between layers of crystalline layered phosphate
The 4 or more aliphatic primary amines be intercalated, it is possible to improve the thermal stability of the aliphatic primary amine, the various reactants, catalysts, modifiers of polymer compounds, curing No. 1 aliphatic used in cosmetics
The amine can be subjected to higher temperature use.

That is, an aliphatic primary amine which could not be used at a high temperature because it conventionally evaporates and decomposes at a low temperature can be used at a high temperature by improving the thermal stability as described above. The range of application of the aliphatic primary amine is widened, for example, it can be used as a raw material for a reaction below or as a catalyst.

[0028] Particularly evaporation at low temperatures, decomposition ease Iabura aliphatic first
Amines have a large effect of improving the thermal stability as described above.

[0029]

EXAMPLES Next, reference examples will be described examples cited by the present invention in more detail, the present invention is not limited only to these examples it. All quantities in Reference Examples and Examples are based on weight unless otherwise specified.

Reference Example 1 Synthesis of ethylamine intercalate compound To 3.22 g of a 70% aqueous solution of ethylamine, benzene was added to make 500 ml to prepare a 0.1N ethylamine solution, and two 50 ml samples of this 0.1N ethylamine solution were prepared. .

A crystalline layered cerium phosphate [Ce (HPO ₄ ) _2.
2H ₂ O] and crystalline layered titanium phosphate [Ti (HP
O _{4) 2} · 2H ₂ O] was 5g each added separately,
And then stirred for 5 hours with an ultrasonic dispersing machine, ethylamine each crystalline layered phosphate <br/> interlayer is intercalated, then filtered, further washed with benzene and air dried at room temperature.

[0032] The resulting reaction product, from the result of an increase in the interlayer distance by the X-ray diffraction and differential thermal / thermal balance simultaneous measurement, in compounds ethylamine between layers of the crystalline layered phosphate intercalated It was confirmed that there was.

Table 1 shows the change in the peak value (2θ) of the X-ray diffraction profile before and after the intercalation of ethylamine (boiling point: 16.6 ° C.) and the change in the exothermic peak in the simultaneous measurement by differential heat / thermal balance.

[0034]

[Table 1]

Example 1 Synthesis of butylamine intercalate compound In the same manner as in Reference Example 1 except that 3.657 g of butylamine was used instead of ethylamine, butylamine was treated in the same manner as in crystalline layered cerium phosphate and crystalline layered layer. each phosphate <br/> titanium emission is intercalated to obtain two kinds of reaction products.

The obtained reaction product was a compound in which butylamine was intercalated between the layers of each crystalline layered phosphoric acid compound, based on the results of an increase in the interlayer distance by X-ray diffraction and the result of simultaneous measurement by differential heat / thermal balance. It was confirmed that there was.

Table 2 shows the change in the peak value (2θ) of the X-ray diffraction profile before and after the intercalation of butylamine (boiling point: 78.0 ° C.) and the change in the exothermic peak in the simultaneous measurement by differential heat / thermal balance.

[0044]

[Table 2]

Example 2 Synthesis of octylamine intercalated compound 6.463 g of octylamine was used in place of ethylamine, and otherwise the same treatment as in Reference Example 1 was performed to convert octylamine into crystalline layered cerium phosphate and each crystalline layered phosphate titanium emission is intercalated to obtain two kinds of reaction products.

[0046] The resulting reaction product was, from the result of an increase in the interlayer distance by the X-ray diffraction and differential thermal / thermal balance simultaneous measurement, in compounds octylamine between the layers of each crystal layered phosphate intercalated It was confirmed that there was.

Table 3 shows the change in the peak value (2θ) of the X-ray diffraction profile before and after the intercalation of octylamine (boiling point: 177.0 ° C.) and the change in the exothermic peak in the simultaneous measurement by differential heat / thermal balance.

[0048]

[Table 3]

Next, the above-mentioned Reference Example 1 and Examples 1-2.
By the same treatment as above, methylamine, propylamine,
Hexylamine, heptylamine, decylamine, tetra-decylamine, to synthesize a compound of the cetylamine was intercalated between the layers of the crystalline layered phosphate.

These intercalating compounds and reference
A hydrophobicity test was performed on the intercalate compounds obtained in Example 1 and Examples 1 and 2 . The test method and test results are as follows.

Hydrophobicity test A 50 ml sample bottle was charged with 5 m each of solvent and water.
l each, 20 mg of each of the above intercalating compounds was separately added thereto, and the mixture was vigorously shaken up and down for 2 minutes. After shaking, the mixture was allowed to stand at room temperature for 5 minutes, the state was observed, and the hydrophilicity and the hydrophobicity were determined based on which phase the intercalating compound was present.

Table 4 shows the test results when the solvent was chloroform. Table 5 shows the test results when the solvent was benzene.

[0053] For comparison, nothing was subjected to the same test on the crystallinity of the layered phosphate that has not been intercalated between the layers. The results are shown in Tables 4 and 5 as blanks.

[0054] Further, a similar test was carried out also for the crystalline layered phosphate with ammonia in the interlayer is intercalated. The results are also shown in Tables 4 and 5.

[0055] Incidentally, in Table 4 and Table 5, respectively of a crystalline layered phosphate in the following abbreviations.

CeP: crystalline layered cerium phosphate TiP: crystalline layered titanium phosphate

The symbols “W” and “O” in Tables 4 and 5 have the following meanings, respectively. W: hydrophilic O: hydrophobic

[0058]

[Table 4]

[0059]

[Table 5]

Next, an ammonia gas adsorption test was performed on the compound obtained by intercalating butylamine between the layers of the crystalline layered titanium phosphate obtained in Example 1 and ordinary crystalline layered titanium phosphate. The test method and results are as follows.

In a odor bag having a capacity of 3 liters of ammonia gas adsorption test , a compound in which butylamine was intercalated between the layers of the crystalline layered titanium phosphate obtained in Example 1 and an ordinary crystalline layered titanium phosphate were added in an amount of 0, respectively. 0.5g each, put 1040
3 liters of each ppm ammonia standard gas (N ₂ base, manufactured by Iron and Steel Chemical Co., Ltd.) was added. This was left at room temperature, and the ammonia concentration in the odor bag was measured over time with a gas detector tube, and the adsorption rate was determined from the measured concentration. Table 6 shows the results.

[0062]

[Table 6]

As shown in Table 6, the compound in which butylamine was intercalated between the layers of the crystalline layered titanium phosphate also had a slight delay in the adsorption rate, but the ordinary crystal in which butylamine was not intercalated was used. As in the case of the layered titanium phosphate, it had an adsorption performance for ammonia gas.

As described above, even when butylamine is intercalated between the layers of the crystalline layered titanium phosphate, there is no significant decrease in the adsorption performance to ammonia gas. By taking advantage of the above, a compound in which butylamine is intercalated between the layers of the crystalline layered titanium phosphate is kneaded with a resin, for example, to form a sheet, whereby a sheet-shaped adsorbent can be easily obtained.

[0065]

The inorganic-organic composite of the present invention has 4 carbon atoms.
Based on the above intercalation of the aliphatic primary amine,
It has hydrophobicity.

[0066] Thus, inorganic invention - organic complexes, dispersibility of the poor does not occur based on the obtained such a hydrophilic seen when dispersing the crystalline layered phosphate such as a resin,
Good dispersibility in resin and the like.

[0067] Moreover, inorganic invention - organic complexes, catalysis, ion exchange action based on crystalline layered phosphate,
Since it has a gas adsorption function, a rust prevention effect, etc., the inorganic-organic composite of the present invention is dispersed in resin, fiber, paper, etc. to form a catalyst, ion exchanger, gas adsorption in a molded state It can be used as an agent, and a rust preventive paint or the like can be easily prepared.

Further, since the inorganic-organic composite of the present invention has hydrophobicity, it can be used to prevent water leakage and contamination by filling it with resin, fiber, etc., so that it has a functional property. It can also be used as a filler.

[0069] In addition, inorganic invention - organic complexes, so improving the thermal stability of the layers of the crystalline layered phosphate was intercalated aliphatic primary amine, conventionally, used only at low temperatures It is also possible to use aliphatic primary amines that could not be used at high temperatures.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C01B 25/26 CA (STN)

Claims (1)

(57) [Claims] 1. A general formula _{M (HPO 4) 2 · XH} 2 O ( wherein, M is T i or Ce, X is a is 0 to 2) between layers of the crystalline layered phosphate represented by An inorganic-organic composite, wherein an aliphatic primary amine having 4 or more carbon atoms is intercalated.