JP3364147B2 - Fluoroalkylsilylated complexes of layered silicates - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel magadiite in which crystal surfaces between layers are fluoroalkylsilylated, and a method for producing the same.
The novel magadiite having a fluoroalkylsilylated crystal surface of the present invention has excellent water repellency and oil repellency on its surface, and its dispersibility.
It is useful as a new inorganic or organic nanocomposite (granular) as a water-repellent material or oil-repellent material, or as a filler for organic polymer resin or rubber.

[0002]

BACKGROUND OF THE INVENTION Magadiite
Is a crystalline compound that is a crystalline layered silicate consisting of only a SiO ₂ component having a layered structure (Kosuge Katsunori et al.
"Journal of the Ceramic Society of Japan, Volume 100, 326
P., 1992). Since the interlayer distance is about 1 nm, and silanol groups are regularly present between the layers, the layers are reactive and the inorganic-organic nanocomposite can be synthesized by immobilizing the organic group in the silylation reaction. It is known.

Heretofore, we have reported that by using a quaternary alkylammonium-magadiite intercalation compound as an intermediate, a sterically bulky organic group can be immobilized between the layers by silylation (T. Yanag
isawa, Etal. , Bull. Chem. So
c. Jan. , 61, 3743, 1988). Based on this report, it is considered that various organic groups can be immobilized between the magadiite layers.

[0004]

On the other hand, the original magadiite, which is not surface-treated, has a hydrophilic surface and does not have sufficient affinity for organic polymers, so that its filling properties, such as strength, are limited. was there. The surface-treated magadiite whose surface was treated with a quaternary alkylammonium also did not have sufficient properties. Further, a fluoroalkyl group is known to have properties different from those of an alkyl group due to properties such as high electron withdrawing property, stability, and weak intermolecular force. Therefore, in recent years, much attention has been paid to the field of functional materials such as liquid crystals, water and oil repellents, and electronics.

As described above, a magadiite derivative having excellent affinity with organic polymer materials, good dispersibility, and markedly improved strength is desired as a novel material particularly in the field of eroticism. It was rare. The present inventors have investigated various complexes of magadiite and have been developing new magadiite that can satisfy the above-mentioned various properties. It was found that a new complex having a fluoroalkylsilylated crystal surface was obtained. The new composite of the present invention has excellent water and oil repellency on the surface, and a new inorganic
As an organic nanocomposite (granular), it can be expected to be applied to a water-repellent material, an oil-repellent material, an organic polymer resin or a rubber filler, and the like.

[0006]

SUMMARY OF THE INVENTION The present invention provides novel conjugates of magadiite in which fluoroalkyl groups are regularly chemically bound to the surface. Since the fluoroalkyl groups are regularly chemically bonded to the surface of the new composite of the present invention, it has excellent affinity with organic polymers and good dispersibility, so that it can be blended in a large amount, so that the strength and the like are significantly improved. Improve to.

The novel magadiite complex of the present invention is a fluoroalkylsilylated silanol group between layers of magadiite. Examples of the fluoroalkylsilyl group for fluoroalkylsilylation of the present invention include tri (fluoroalkyl) silyl group, di (fluoroalkyl) alkylsilyl group, (fluoroalkyl)
Examples thereof include dialkylsilyl groups. The fluoroalkyl group of these fluoroalkylsilyl groups is a linear or branched fluoroalkyl group having 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and is a perfluoroalkyl group. However, 30% of the hydrogen atoms of these original alkyl groups, preferably 5
It is preferable that 0, more preferably 70% or more, is substituted with a fluorine atom. These fluoroalkyl groups preferably have no substituent other than a fluorine atom, but may have other substituents as long as they do not impair the properties of the magadiite complex of the present invention. Examples of such a substituent include an alkoxy group and a halogen atom.

Examples of preferred fluoroalkyl groups of the present invention include (perfluorobutyl) -methyl group,
(Perfluoropentyl) -methyl group, (perfluorohexyl) -methyl group, (perfluoroheptyl) -methyl group, (perfluorooctyl) -methyl group, 2-
(Perfluorobutyl) -ethyl group, 2- (perfluoropentyl) -ethyl group, 2- (perfluorohexyl) -ethyl group, 2- (n-perfluoroheptyl)-
Ethyl group, 2- (perfluorooctyl) -ethyl group,
3- (perfluorobutyl) -propyl group, 3- (perfluoropentyl) -propyl group, 3- (perfluorohexyl) -propyl group, 3- (perfluoroheptyl) -propyl group, 3- (perfluorooctyl) ) -Propyl group and the like.

As the alkyl group bonded to the silyl group,
A straight chain or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms can be mentioned. For example, methyl group, ethyl group, n-propyl group,
Examples thereof include an iso-pyropyr group and an n-butyl group.

Examples of the fluoroalkylsilyl group for fluoroalkylsilylation of the present invention include:
[(Perfluorobutyl) -methyl] dimethylsilyl group, bis [(perfluorobutyl) -methyl] methylsilyl group, tris [(perfluorobutyl) -methyl] silyl group, [(perfluoropentyl) -methyl] dimethylsilyl group Group, bis [(perfluoropentyl) -methyl] methylsilyl group, tris [(perfluoropentyl) -methyl] silyl group, [(perfluorohexyl)
-Methyl] dimethylsilyl group, bis [(perfluorohexyl) -methyl] methylsilyl group, tris [(perfluorohexyl) -methyl] silyl group, [(perfluoroheptyl) -methyl] dimethylsilyl group, bis [(per Fluoroheptyl) -methyl] methylsilyl group, tris [(perfluoroheptyl) -methyl] silyl group,
[(Perfluorooctyl) -methyl] dimethylsilyl group, bis [(perfluorooctyl) -methyl] methylsilyl group, tris [(perfluorooctyl) -methyl] silyl group,

[2- (perfluorobutyl) -ethyl]
Dimethylsilyl group, bis [2- (perfluorobutyl)
-Ethyl] methylsilyl group, tris [2- (perfluorobutyl) -ethyl] silyl group, [2- (perfluoropentyl) -ethyl] dimethylsilyl group, bis [2-
(Perfluoropentyl) -ethyl] methylsilyl group,
Tris [2- (perfluoropentyl) -ethyl] silyl group, [2- (perfluorohexyl) -ethyl] dimethylsilyl group, bis [2- (perfluorohexyl)-
Ethyl] methylsilyl group, tris [2- (perfluorohexyl) -ethyl] silyl group, [2- (perfluoroheptyl) -ethyl] dimethylsilyl group, bis [2-
(Perfluoroheptyl) -ethyl] methylsilyl group,
Tris [2- (perfluoroheptyl) -ethyl] silyl group, [2- (perfluorooctyl) -ethyl] dimethylsilyl group, bis [2- (perfluorooctyl)-
Ethyl] methylsilyl group, tris [2- (perfluorooctyl) -ethyl] silyl group,

[3- (perfluorobutyl) -propyl] dimethylsilyl group, bis [3- (perfluorobutyl) -propyl] methylsilyl group, tris [3- (perfluorobutyl) -propyl] silyl group, [3 -(Perfluoropentyl) -propyl] dimethylsilyl group, bis [3- (perfluoropentyl) -propyl] methylsilyl group, tris [3- (perfluoropentyl) -propyl] silyl group, [3- (perfluorohexyl) ) −
Propyl] dimethylsilyl group, bis [3- (perfluorohexyl) -propyl] methylsilyl group, tris [3
-(Perfluorohexyl) -propyl] silyl group,
[3- (perfluoroheptyl) -propyl] dimethylsilyl group, bis [3- (perfluoroheptyl) -propyl] methylsilyl group, tris [3- (perfluoroheptyl) -propyl] silyl group, [3- (per Fluorooctyl) -propyl] dimethylsilyl group, bis [3-
(Perfluorooctyl) -propyl] methylsilyl group, tris [3- (perfluorooctyl) -propyl] silyl group,

[(Perfluorobutyl) -methyl] diethylsilyl group, bis [(perfluorobutyl) -methyl] ethylsilyl group, [(perfluoropentyl) -methyl] diethylsilyl group, bis [(perfluoropentyl)- Methyl] ethylsilyl group, [(perfluorohexyl) -methyl] diethylsilyl group, bis [(perfluorohexyl) -methyl] ethylsilyl group, [(perfluoroheptyl) -methyl] diethylsilyl group, bis [(perfluoroheptyl) ) -Methyl] ethylsilyl group, [(perfluorooctyl) -methyl] diethylsilyl group, bis [(perfluorooctyl) -methyl] ethylsilyl group,

[2- (perfluorobutyl) -ethyl]
Diethylsilyl group, bis [2- (perfluorobutyl)
-Ethyl] ethylsilyl group, [2- (perfluoropentyl) -ethyl] diethylsilyl group, bis [2- (perfluoropentyl) -ethyl] ethylsilyl group, [2-
(Perfluorohexyl) -ethyl] diethylsilyl group, bis [2- (perfluorohexyl) -ethyl] ethylsilyl group, [2- (perfluoroheptyl) -ethyl] diethylsilyl group, bis [2- (perfluoroheptyl) ) -Ethyl] ethylsilyl group, [2- (perfluorooctyl) -ethyl] diethylsilyl group, bis [2-
(Perfluorooctyl) -ethyl] ethylsilyl group,

[3- (perfluorobutyl) -propyl] diethylsilyl group, bis [3- (perfluorobutyl) -propyl] ethylsilyl group, [3- (perfluoropentyl) -propyl] diethylsilyl group, bis [ Three
-(Perfluoropentyl) -propyl] ethylsilyl group, [3- (perfluorohexyl) -propyl] diethylsilyl group, bis [3- (perfluorohexyl)-
Propyl] ethylsilyl group, [3- (perfluoroheptyl) -propyl] diethylsilyl group, bis [3- (perfluoroheptyl) -propyl] ethylsilyl group,
[3- (perfluorooctyl) -propyl] diethylsilyl group, bis [3- (perfluorooctyl) -propyl] ethylsilyl group,

[(Perfluorobutyl) -methyl] dipropylsilyl group, bis [(perfluorobutyl) -methyl] propylsilyl group, tris [(perfluorobutyl) -methyl] silyl group, [(perfluoropentyl)
-Methyl] dipropylsilyl group, bis [(perfluoropentyl) -methyl] propylsilyl group, [(perfluorohexyl) -methyl] dipropylsilyl group, bis [(perfluorohexyl) -methyl] propylsilyl group, [(Perfluoroheptyl) -methyl] dipropylsilyl group, bis [(perfluoroheptyl) -methyl]
Propylsilyl group, [(perfluorooctyl) -methyl] dipropylsilyl group, bis [(perfluorooctyl) -methyl] propylsilyl group,

[2- (perfluorobutyl) -ethyl]
Dipropylsilyl group, bis [2- (perfluorobutyl) -ethyl] propylsilyl group, [2- (perfluoropentyl) -ethyl] dipropylsilyl group, bis [2
-(Perfluoropentyl) -ethyl] propylsilyl group, [2- (perfluorohexyl) -ethyl] dipropylsilyl group, bis [2- (perfluorohexyl)-
Ethyl] propylsilyl group, [2- (perfluoroheptyl) -ethyl] dipropylsilyl group, bis [2- (perfluoroheptyl) -ethyl] propylsilyl group,
[2- (perfluorooctyl) -ethyl] dipropylsilyl group, bis [2- (perfluorooctyl) -ethyl] propylsilyl group,

[3- (perfluorobutyl) -propyl] dipropylsilyl group, bis [3- (perfluorobutyl) -propyl] propylsilyl group, [3- (perfluoropentyl) -propyl] dipropylsilyl group , A bis [3- (perfluoropentyl) -propyl] propylsilyl group, a [3- (perfluorohexyl) -propyl] dipropylsilyl group, a bis [3- (perfluorohexyl) -propyl] propylsilyl group, [ 3- (perfluoroheptyl) -propyl] dipropylsilyl group,
A bis [3- (perfluoroheptyl) -propyl] propylsilyl group, a [3- (perfluorooctyl) -propyl] dipropylsilyl group, a bis [3- (perfluorooctyl) -propyl] propylsilyl group, and the like. Can be mentioned.

The magadiite composite obtained by fluoroalkylsilylating silanol groups between the layers of magadiite of the present invention can be produced by fluoroalkylsilylating silanol groups between the layers of magadiite. Accordingly, the present invention also provides a method for producing a complex of magadiite in which fluoroalkyl groups are regularly chemically bonded to the surface. The fluoroalkylsilylating agent used when producing a magadiite complex obtained by fluoroalkylsilylating silanol groups between the layers of magadiite of the present invention is a reactive silyl compound having a fluoroalkylsilyl group as described above. Derivatives can be used. The reactive derivative of the silyl compound is not particularly limited as long as it is a silyl compound having a leaving group, but a silyl halide or a chlorosilane derivative is preferable.

For the fluoroalkylsilylation between layers of magadiite, the magadiite can be directly fluoroalkylsilylated with the above-mentioned fluoroalkylsilylating agent. However, the magadiite is first converted into a tetraalkylammonium with a tetraalkylammonium compound. After that, a method of substituting the produced tetraalkylammonium group with a fluoroalkylsilylating agent is preferable. Examples of the alkyl group of the tetraalkylammonium group used in this case include a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 8 to 15 carbon atoms, and four alkyl groups are the same. May be different from each other, and one of the alkyl groups preferably has a relatively long carbon chain. Examples of preferable tetraalkylammonium group include a dodecyltrimethylammonium group.

The tetraalkylammonium-forming reaction can be carried out by a conventional method in the presence of water or a polar solvent such as ethanol or methanol at room temperature or under heating. The fluoroalkyl silylation reaction is carried out in the presence of a fluoroalkyl silylating agent in a molar ratio of 1 mol or more, preferably 5 mol or more, and more preferably 10 mol or more with respect to magadiite or tetraalkylammonium magadiite. It can be performed at room temperature or by heating. As the solvent, benzene, toluene, dioxane or the like can be used, and toluene is preferable. Further, the reaction is preferably carried out in a nitrogen atmosphere in order to suppress side reactions.

More specifically, the method for producing a magadiite complex of the present invention will be described. To manufacture. Due to this reaction, the basic spacing of magadiite is 1.56 nm.
To 2.81 nm, confirming the synthesis of the DTMA-magadiite intercalation compound (see Figure 1). Then
The obtained DTMA-magadiite and [2- (perfluorohexyl) ethyl] dimethylchlorosilane in a molar ratio of 10 mol or more were mixed in toluene under a nitrogen atmosphere at 1 mol.
By reacting at 10 ° C., magadiite (FHES-magadiite) having a [2- (perfluorohexyl) ethyl] dimethylsilyl group can be obtained. 2.83 nm in the XRD pattern of the sample after silylation
A diffraction peak and a peak due to its higher-order reflection were observed (see FIG. 1).

FIG. 1 shows the XRD patterns of the sodium salt of magadiite ((a) in FIG. 1), DTMA-magadiite ((b) in FIG. 1) and FHES-magadiite ((c) in FIG. 1). Show.

From the IR spectrum of FHES-magadiite, the appearance of an absorption band of ν (CF) and a large decrease of ν (CH) were observed. Furthermore, C
From the HN elemental analysis, the synthesis of FHES-magadiite was confirmed since the sample contained almost no nitrogen. FHES-Magadiite's ²⁹ SiCP /
In the MAS NMR spectrum, a signal was observed around 22.8 ppm (see FIG. 2). This signal is M
Is attributed to the Si atom of ^one unit (R ₃ Si -OSi),
It was shown that silylation had occurred. Figure 2 is FHES
-Shows the ²⁹ SiCP / MAS NMR spectrum of magadiite.

On the other hand, FHES-TG of Magadiite-
From DTA analysis, a weight loss of about 41 wt% was observed from around 35 ° C. to around 600 ° C. due to the combustion of organic species accompanied by an exothermic peak. Octyldimethylsilylated derivative magadiite (hereinafter referred to as ODMS-magadiite)
Considering that the combustion of the organic group at about 230 ° C starts, the organic group of FHES-magadiite has excellent thermal stability, which is considered to be due to the high thermal stability of the perfluoroalkyl group. Was given.

FHES-magadiite and ODMS-magadiite were compressed into pellets and the contact angle with water on the pellets was measured. The contact angles of ODMS-magadiite and FHES-magadiite are
It was 137 ° and 139 °, and the FHES-magadiite of the present invention showed higher water repellency.

Further, the dispersibility of FHES-magadiite in an organic solvent was examined. FHES-magadiite was stirred in octanol and ultrasonically dispersed samples were centrifuged at 4000 rpm for 5 minutes, and almost all the samples were precipitated. On the other hand, the sample stirred and ultrasonically dispersed in a 2- (perfluorohexyl) ethanol solvent was hardly precipitated after centrifugation, and the supernatant liquid was white and turbid. The XRD pattern of the film obtained by casting this supernatant liquid and drying it under reduced pressure showed that bottom reflection and its higher-order reflection were largely observed, and that the SEM (Scannin)
From the observation of electron micrographs (see FIG. 3), it was confirmed that the plate-like particles were laminated in a substrate shape, and it was confirmed that an oriented film of FHES-magadiite was obtained. In the SEM observation of FHES-magadiite powder, it was observed that the plate-like particles were aggregated. Therefore, FHES-magadiite was stirred in 2- (perfluorohexyl) ethanol solvent, and the particles were partially dispersed by ultrasonic dispersion. It was found that, after being dispersed and cast, the plate-like particles were laminated on the substrate. These phenomena were not observed in the ODMS-magadiite / octanol system, and were considered to be due to the affinity between the perfluoroalkyl chains that both the sample and the solvent had.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0029]

Example 1 1 g of magadiite was stirred in 50 ml of 0.1 mol / 1 dodecyltrimethylammonium chloride (DTMA ⁺ Cl ⁻ ) aqueous solution for 4 days to synthesize a DTMA-magadiite intercalation compound. The obtained DTMA-magadiite was added to the silylating agent [2- (perfluorohexyl)
Ethyl] dimethylchlorosilane was added to the DTMA-magadiite in a molar ratio of about 10 times or more, and the mixture was refluxed in a toluene solvent in a nitrogen atmosphere at 110 ° C. for 48 hours for silylation. After refluxing, the precipitate was washed several times with toluene and then with methanol, and then dried to obtain a powder sample, FHES-magadiite. All solid phases can be recovered (yield almost quantitative). The composition of the product was (silyl group) _1.7 {Si ₁₄ O ₂₉ }. In addition, {Si ₁₄ O
₂₉ } indicates the unit cell of magadiite.

[0030]

INDUSTRIAL APPLICABILITY The fluoroalkylsilylated magadiite of the present invention has excellent water repellency and oil repellency on its surface, and its dispersibility, as a new inorganic / organic nanocomposite (particulate). It is useful as an oil repellent material and as a filler for organic polymer resins and rubbers. Also,
It also provides substances useful as functional materials such as liquid crystals, water and oil repellents, and electronics.

[Brief description of drawings]

FIG. 1 shows the sodium salt of magadiite (FIG.
(A)), DTMA-magadiite (FIG. 1 (b)) and FHES-magadiite of the present invention (FIG. 1).
3C shows an XRD pattern of FIG.

FIG. 2 shows FHES-magadiite of the present invention.
²⁹ shows a ²⁹ SiCP / MAS NMR spectrum.

FIG. 3 shows SEM (Scanning electron mi) of FHES-magadiite of the present invention dispersed in 2- (perfluorohexyl) ethanol.
(a) in the figure is FH.
ES-Magadiite's, (b) in the figure is F
It is a cast film of HES-Magadiite.

─────────────────────────────────────────────────── ─── Continued Front Page (56) References Bull. Chem. Soc. Jpn. , 1988, Vol. 61, No. 10, p. 3743-p. 3745 (58) Fields investigated (Int.Cl. ⁷ , DB name) C07F 7/12 C01B 33/38

Claims (5)

(57) [Claims] 1. Magadiite in which the crystal surface between layers is fluoroalkylsilylated with a fluoroalkylsilyl group. 2. A fluoroalkylsilyl group is represented by [2-
The fluoroalkylsilylated magadiite according to claim 1, which is a (perfluorohexyl) ethyl] dimethylsilyl group. 3. A fluoroalkylsilylated magadiite characterized by fluoroalkylsilylating silanol groups existing between layers of magadiite or a derivative thereof with a silyl derivative having a fluoroalkylsilyl group. Production method. 4. The method for producing a fluoroalkylsilylated magadiite according to claim 3, wherein the derivative of magadiite is tetraalkylammonium-magadiite. 5. A silyl derivative having a fluoroalkylsilyl group is [2- (perfluorohexyl) ethyl].
The method for producing the looloalkylsilylated magadiite according to claim 3 or 4, which is dimethylchlorosilane.