JP2003095640A - Clay organic composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a clay organic composite which is highly heat-resistant and is evenly dispersed in a polymer. SOLUTION: A swelling layer-state silicate such as montmorillonite is treated with an nitrogen-containing aromatic ion such as 1-methyl-3-butyl benzimidazole chloride. Thereby, the clay organic composite containing an organic onium ion such as the above ion between the layers of the silicate is formed.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a clay organic composite, more specifically, a clay organic composite which contains nitrogen-containing aromatic ions between layers of a layered silicate, has high heat resistance and is uniformly dispersed in a polymer. Regarding the body

[0002]

2. Description of the Related Art Since thermoplastic polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polybutylene terephthalate (PBT) have excellent heat resistance, mechanical properties and chemical resistance, Widely used as fibers, films, resins, etc. Further, when the mechanical properties and heat resistance of the polymer alone are insufficient, attempts have been made to improve it by using an inorganic filler as a reinforcing agent (for example, JP-A-51-24653).
Issue). However, in order to sufficiently satisfy the mechanical properties and heat resistance, it is necessary to add a large amount of a reinforcing agent. In this case, although strength and heat resistance are improved, toughness and surface properties are greatly reduced, and further, specific gravity is increased. There's a problem. Possible causes for this are poor dispersion of the inorganic filler and size of dispersed particles. Therefore, recently, research has been actively conducted to improve high toughness, strength, gas barrier property, thermal stability and flame retardancy with a very small content by dispersing inorganic filler at the molecular level. Has been done in. Furthermore, very recently, very interesting reports such as improvement of biodegradability have been made. In the case of polyester, this technique is expected to improve mechanical strength, heat resistance and gas barrier property without losing transparency, and therefore, it may be used for a gas barrier film or a bottle. Further, if the biodegradability is improved, it may be used for agricultural materials. As the inorganic filler, there is a swellable layered silicate. The swelling layered silicate has several hundred unit layers each having a thickness of 1 nm, and it has been impossible to disperse it at a molecular level even if it is uniformly dispersed in a polymer. However, it was reported in JP-A-62-74957 that it is possible to disperse a swellable layered silicate treated with a quaternary ammonium salt in a polyamide at a molecular level, and then a polyimide (JP-A-4-33955). JP, JP 9-194723, JP 9-208822), an epoxy compound (Chem. Mater.,
5,1064 (1994)), polystyrene (J.Am.Chem.Soc., 121,161)
5 (1999)), polypropylene (J.Appl.Polym.Sci., 63,137
(1997)), a similar report has been made. Regarding polyester, JP-A-3-62846 and JP-A-7-16603
No. 6 and WO99 / 03914 disclose methods for uniform dispersion.

In the above invention, in order to uniformly disperse the swelling silicate, it is necessary to treat the interlayer with a quaternary ammonium salt. However, since the thermal decomposition temperature of quaternary ammonium salts is as low as 200 ° C or lower, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN)
When dispersed in a high melting point polymer, the ammonium salt causes thermal decomposition, leading to thermal deterioration of the polymer. Therefore, studies have been conducted on phosphonium salts having a thermal decomposition temperature of 300 ° C. or higher, but the use of phosphonium salts has a problem that the uniform dispersion of the swelling silicate is hindered.

[0004]

An object of the present invention is to provide a clay organic composite which has high heat resistance and can be uniformly dispersed in a polymer.

[0005]

The present inventors have found a clay organic composite which can suppress thermal deterioration of a polymer and can be uniformly dispersed in the polymer, and have completed the present invention.

That is, the present invention is as follows. 1. A clay-organic composite having organic onium ions between swelling layered silicate layers. 2. The clay-organic composite according to the above 1, wherein the organic onium ion is a nitrogen-containing aromatic ion. 3. 3. The clay-organic composite according to the above 2, wherein the nitrogen-containing aromatic ion is any one of the ions represented by the following formula (1).

[0007]

[Chemical 2]

(In each formula (1), R1 and R2 are each independently an alkyl group having 1 to 30 carbon atoms.) 4. 4. The clay organic composite according to any one of 1 to 3 above, wherein the swelling layered silicate comprises a smectite clay mineral or a swelling mica. 5. The clay organic composite as described in any one of 1 to 4 above, which has a thermal decomposition temperature of 300 ° C. or higher.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The swellable layered silicate used in the present invention is a layered silicate having a cation exchange ability and having a property of taking in water between layers and swelling. Examples thereof include smectite-based clay minerals and mica-based clay minerals.
Examples of the smectite clay minerals include hectorite, saponite, stevensite, beidellite, montmorillonite, natural or chemically synthesized products thereof, and substitution products, derivatives, or mixtures thereof. Examples of mica-based clay minerals include synthetic swelling mica having, for example, Li and Na ions between chemically synthesized layers, or substitution products, derivatives or mixtures thereof.

The clay organic composite of the present invention can be obtained by treating the swellable layered silicate with an organic onium ion. By such treatment, organic onium ions are inserted between the layers (faces) of the swellable layered silicate, and the distance between the layers is increased. As a method for confirming that this organic treatment has been performed, it is possible to obtain the interplanar spacing value from the diffraction peak derived from the bottom surface reflection of the (001) plane of the swelling layered silicate by wide-angle X-ray analysis. Also,
It is also possible to obtain the organic content by measuring the thermogravimetric change.

As the organic onium ion used in the present invention, a nitrogen-containing aromatic ion is preferable, and among them,
Each formula below (1)

[0012]

[Chemical 3]

A nitrogen-containing aromatic ion having a structure of (in each formula (1), R1 and R2 are each independently an alkyl group having 1 to 30 carbon atoms) is particularly preferable. Here, the alkyl group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 18 carbon atoms.

The nitrogen-containing aromatic ion represented by the above formula (1) is an onium ion derived from a corresponding nitrogen-containing aromatic compound. Specific examples of the nitrogen-containing aromatic compound include 1-methyl-3-methylimidazole, 1-methyl-3-ethylimidazole, 1-methyl-3-butylimidazole, 1-methyl-3-octylimidazole. , 1-methyl-3-decylimidazole,
1-methyl-3-dodecylimidazole, 1-methyl-
3-tetradecylimidazole, 1-methyl-3-hexadecylimidazole, 1-methyl-3-octadecylimidazole, 1-methyl-3-oleylimidazole, 1-methylpyrazole, 1-ethylpyrazole, 1
-Butylpyrazole, 1-octylpyrazole, 1-decylpyrazole, 1-dodecylpyrazole, 1-tetradecylpyrazole, 1-hexadecylpyrazole, 1-
Octadecylpyrazole, 1-oleylpyrazole, 1
-Methylpyridazine, 1-ethylpyridazine, 1-butylpyridazine, 1-octylpyridazine, 1-decylpyridazine, 1-dodecylpyridazine, 1-tetradecylpyridazine, 1-hexadecylpyridazine, 1-octadecylpyridazine, 1-oleylpyridazine , 1-methylpyrimidine, 1-ethylpyrimidine, 1-butylpyrimidine, 1-octylpyrimidine, 1-decylpyrimidine, 1-dodecylpyrimidine, 1-tetradecylpyrimidine, 1-hexadecylpyrimidine, 1-octadecylpyrimidine, 1- Oleylpyrimidine, 1-methyltriazine, 1-ethyltriazine, 1-butyltriazine, 1-octyltriazine, 1-decyltriazine,
1-dodecyltriazine, 1-tetradecyltriazine, 1-hexadecyltriazine, 1-octadecyltriazine, 1-oleyltriazine, 1-methylindole, 1-ethylindole, 1-butylindole,
1-octyl indole, 1-decyl indole, 1-
Dodecyl indole, 1-tetradecyl indole, 1
-Hexadecylindole, 1-octadecylindole, 1-oleylindole, 1-methyl-3-methylbenzimidazole, 1-methyl-3-ethylbenzimidazole, 1-methyl-3-butylbenzimidazole, 1-methyl-3 -Octylbenzimidazole, 1
-Methyl-3-decylbenzimidazole, 1-methyl-3-dodecylbenzimidazole, 1-methyl-3-
Tetradecylbenzimidazole, 1-methyl-3-hexadecylbenzimidazole, 1-methyl-3-octadecylbenzimidazole, 1-methyl-3-oleylbenzimidazole, 1-methylquinoline, 1-ethylquinoline, 1-butylquinoline , 1-octylquinoline, 1-decylquinoline, 1-dodecylquinoline, 1-
Tetradecylquinoline, 1-hexadecylquinoline, 1
-Octadecylquinoline, 1-oleylquinoline, 1-
Methyl-4-methylquinoxaline, 1-methyl-4-ethylquinoxaline, 1-methyl-4-butylquinoxaline, 1-methyl-4-octylquinoxaline, 1-methyl-4-decylquinoxaline, 1-methyl-4-dodecyl Quinoxaline, 1-methyl-4-tetradecylquinoxaline, 1-methyl-4-hexadecylquinoxaline,
1-methyl-4-octadecyl quinoxaline and 1-methyl-4-oleyl quinoxaline are mentioned.

The method for treating the swellable layered silicate with an organic onium ion is usually as follows: 1 part by weight of the swellable layered silicate and 1 to 10 parts by weight of the organic onium ion are mixed in water,
dry. The amount of water is 1 to 100 times that of the swellable layered silicate. The temperature for mixing is preferably 30 to 70 ° C, and the mixing time is preferably 0.5 to 2 hours. Drying conditions are preferably atmospheric pressure drying at 70 to 100 ° C. for 3 days and vacuum drying for 2 days.

The thus obtained organic onium ion-treated swellable layered silicate, that is, a clay-organic composite, is filled with a polymer, particularly a thermoplastic polyester, and does not cause its thermal deterioration so that it has heat resistance. It needs to be excellent. The heat resistance is determined from the thermal decomposition starting temperature obtained by thermogravimetric change measurement, and in the present invention, the thermal decomposition starting temperature is preferably 300 ° C. or higher.

The thermal deterioration of the polymer is obtained from the solution viscosity of the polymer after the swellable layered silicate is dispersed. Solution viscosity is measured by dissolving the polymer in a solvent of phenol / 1,1 ', 2,2'-tetrachloroethane = 60/40 (weight ratio) and measuring at 35 ° C.

The swelling layered silicate treated with the organic onium ion thus obtained has a weight ratio of the organic onium ion to the swelling layered silicate of 10:90.
Those having a ratio of ˜40: 60 have good dispersibility in the polyester.

The proportion (content) of the clay organic composite in the present invention in the polyester is 0.5 to 10% by weight.
Is more preferable, and if it is 1 to 5% by weight, higher dispersibility can be obtained.

As a method for dispersing the clay organic composite of the present invention in polyester, for example, the clay organic composite is
It is possible to employ a method in which the polyester is added at the time of polymerization and uniformly dispersed, or the polyester and the clay organic complex are dispersed by melt kneading or solution dispersion using a solvent.

Whether or not these clay-organic composites are uniformly dispersed is determined by swelling layered silicate (0
It is judged from the fact that the diffraction peak derived from the bottom reflection of the (01) surface shifts to a low angle of incidence, and the diffraction peak based on the interplanar spacing virtually disappears, that is, the interplanar distance is increased. . It is preferable for the clay-organic composite of the present invention that such a state can occur in the polymer.

[0022]

The clay-organic composite having nitrogen-containing aromatic ions between the layers of the swellable layered silicate of the present invention can suppress thermal deterioration of the polymer and can be uniformly dispersed in the polymer. It is extremely useful as a filler.

[0023]

The details of the present invention will be described in more detail with reference to the following examples.

The swellable layered silicate (montmorillonite) used in this example is Kunipia F, manufactured by Kunimine Industries Co., Ltd.
Dihydroxypolyoxyethylene oleyl methyl ammonium chloride is Takemoto Yushi Co., Ltd., trimethylbenzyl ammonium chloride is NOF Corporation, 1-methyl-quinoline, 1-methylbenzimidazole, 1-chlorobutane, toluene, phenol, 1,1 '. Kanto Chemical Co., Ltd. was used for 2,2,2'-tetrachloroethane, and Teijin Ltd. was used for PET (FK-OM). Of 1-methyl-3-butylbenzimidazole chloride
Synthetic 1-methylbenzimidazole 50g (0.37mo
l), 34.2 g (0.37 mol) of 1-chlorobutane,
It was dissolved in 50 ml of toluene and refluxed and stirred for 24 hours. After refluxing, reprecipitation with acetone was performed, and the target product was obtained by filtration and vacuum drying. Yield 18.2 g (yield 22%). Synthesis of 1 -butyl-quinoline chloride It was synthesized in the same manner as above except that quinoline was used instead of 1-methylbenzimidazole. Measurement of interlayer distance (spacing) of swelling layered silicate The interlayer distance (spacing) of the swelling layered silicate was measured using a wide-angle X-ray analyzer (Rigaku Denki Co., Ltd. CN2155). It was determined from the diffraction peak derived from the bottom reflection of the (001) plane. Thermogravimetric analysis and thermal decomposition evaluation The weight change before and after the introduction of the organic onium ion and the thermal decomposition evaluation after the introduction are performed by Rigaku Denki Co., Ltd. Thermo plus TG 8120.
Was calculated from the change in weight and the temperature at which pyrolysis started when the temperature was raised from room temperature to 600 ° C at 10 ° C / min in a nitrogen atmosphere. Polyester consisting of aromatic dicarboxylic acid having sulfonic acid group
Synthesis of stell copolymer dimethyl terephthalate 190.3 g (0.98 mol), 5-sodium sulfodimethylisophthalate 59.2 g (0.02 mol),
Ethylene glycol 99.3 g (1.6 mol), diethylene glycol 42.4 g (0.4 mol), tetrabutyl titanate 0.17
Charge g (0.05 mol%) into a 1 L three-necked flask and
Transesterification was carried out at ℃ for 4 hours. Further, polymerization was carried out at 250 ° C for 4 hours. The solution viscosity of the obtained polymer was 0.82. The porosity of swellable layered silicate treated with nitrogen-containing aromatic ions
Dispersion Method in Reester Polyester 870 g, polyester copolymer 100
g, Kunipia F (nitrogen-containing aromatic ion treatment) was weighed 3% by weight with respect to polyester, and melt-kneaded at 270 ° C. using a ruder (PCM-30, Ikegai Iron Works Co., Ltd.),
Kunipia F was dispersed in polyester. Solution Viscosity Measurement Polyester with swellable layered silicate dispersed in phenol
/ 1,1 ', 2,2'-Tetrachloroethane = 60/40 (weight ratio) It was dissolved in a solvent and measured at 35 ° C.

[Example 1] 1 g of Kunipia F and 1 g of 1-methyl-3-butylbenzimidazole chloride were added to 10 g of water.
Dissolve in 0 ml and stir at room temperature for 4 hours. After stirring, filtration and washing with water were repeated 3 times, followed by hot-air drying at 100 ° C. for 2 days and vacuum drying for 1 day. After drying, the interplanar spacing of the swellable layered silicate, the content of organic substances, and the thermal decomposition temperature were measured by the above methods. The results are shown in Table 1.

Next, 870 g of polyester, 100 g of polyester copolymer, Kunipia F37.
5 g was melted and kneaded at 270 ° C. by a ruder, and after kneading,
Solution viscosity measurement and surface spacing measurement were performed. The results are shown in Table 1.

[Example 2] The same as Example 1 except that 1-methyl-3-quinoline was used instead of 1-methyl-3-butylbenzimidazole chloride. The results are shown in Table 1.

Comparative Example 1 Same as Example 1 except that dihydroxypolyoxyethylene oleylmethylammonium was used in place of 1-methyl-3-butylbenzimidazole chloride. The results are also shown in Table 1.

Comparative Example 2 Same as Example 1 except that trimethylbenzylammonium was used in place of 1-methyl-3-butylbenzimidazole chloride. The results are also shown in Table 1.

[0030]

[Table 1]

From the above results, the number of nitrogen-containing aromatic ions was 4
The thermal decomposition initiation temperature is higher than that of primary ammonium salts, so it is extremely effective against the thermal deterioration of polyester, and the interplanar peaks of the layered silicate in the polyester have disappeared. You can see that they are dispersed in.

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Claims (5)

[Claims] 1. A clay-organic composite having organic onium ions between layers of a swellable layered silicate. 2. The clay-organic composite according to claim 1, wherein the organic onium ion is a nitrogen-containing aromatic ion. 3. A nitrogen-containing aromatic ion represented by the following formula (1):
The clay-organic composite according to claim 2, which is any one of the ions represented by [Chemical 1] (In each formula (1), R1 and R2 are each independently an alkyl group having 1 to 30 carbon atoms.) 4. The clay-organic composite according to claim 1, wherein the swelling layered silicate comprises a smectite clay mineral or a swelling mica. 5. The clay organic composite according to claim 1, which has a thermal decomposition initiation temperature of 300 ° C. or higher.