KR100583952B1 - Catalyst-substituted lamellar organic clay and PET-organic clay composite using the same - Google Patents

Abstract

The present invention relates to a PET-organoclay composite in which layered organic clay is completely peeled as a basic unit on a nano-scale sheet, and more particularly, in the method of preparing a PET-organic clay composite, in which clay is organicized using an organic agent. Instead of the conventional method, the present invention relates to a PET-organoclay composite in which the layered organic clay is completely separated into basic units on a nanoscale sheet by replacing the catalyst on the clay sheet.

PET, organoclay, catalyst, polyester, nanocomposite

Description

Catalytic-substituted lamellar organic clay and PET-organic clay composite using the same

The present invention relates to a PET-organoclay composite in which layered organic clay is completely peeled as a basic unit on a nano-scale sheet, and more particularly, in the method of preparing a PET-organic clay composite, in which clay is organicized using an organic agent. Instead of the conventional method, the present invention relates to a PET-organoclay composite in which the layered organic clay is completely separated into basic units on a nanoscale sheet by replacing the catalyst on the clay sheet.

Recently, many attempts have been made to add nano-particles as a method for improving the physical properties of polymer resins, and a lot of layered clays have been applied as additives.

The core technology of the polymer nanocomposite is how to change the layered clay so that the target polymer resin can be easily intercalated. Most of the clay is a layered silicate, which is polar hydrophilic, and cannot be easily inserted into most lipophilic polymer resins. Therefore, it is an organic layered silicate that modified so that various polymer resins could be easily inserted in each polarity according to the characteristic of this polar silicate.

Three methods for preparing clay dispersed nanocomposites are well known, such as a solution method, a polymerization method, and a compounding method. Among them, the polymerization method is known to be the best method for producing nanocomposites having excellent physical properties.

In order to facilitate uniform dispersion of the layered inorganic material to the polymer resin, U.S. Pat. No. 4,889,885 or the like discloses sodium or potassium ions which exist in a natural state between the unit layers of the multilayered particulate layered material such as inorganic silicate. After replacement by (alkylammonium ions or functionalized organosilanes), a technique is disclosed for mixing such layered materials with monomers or oligomers of the polymer. However, the layered organic clay disclosed in the patent has a low thermal stability at a level of 100 to 110 ° C., when the polymer resin-organic clay composite is prepared, there is a problem that the physical properties of the composite are degraded due to thermal decomposition of the organic clay.

In addition, US Pat. No. 6,057,035 discloses a method of organizing clay into a phosphorus compound and using silicon as an organic agent to improve the thermal stability of the organic clay. However, although the method of the patent can improve the thermal stability of the organic clay to 200 ° C. level, it is difficult to apply to composites of polyester and polypropylene due to low dispersibility and compatibility with the polymer resin.

In addition, Korean Patent Laid-Open Publication No. 2002-7583 discloses (i) a layered organic clay organicized with an organizing agent in which a functional group of a modified polypropylene and an amine-based non-halogen flame retardant are chemically bonded, (ii) modified propylene and (iii) polypropylene. Although a polypropylene-organic clay composite composed of a resin (matrix) is disclosed, the layered organic clay used in the patent has only a problem of improving compatibility with polypropylene and not having compatibility with other polymer resins. .

 Currently, in the art, polyamide-based nanocomposites have commercialized products having excellent physical properties prepared by polymerization. However, in the case of polyester-based nanocomposites, composites prepared by polymerization using organic clay have not yet been commercialized. Its physical properties have not reached the stage of superiority, and deterioration of organic agent decomposing in the manufacturing process due to high polymerization temperature remains a big problem.

Accordingly, the present inventors have replaced the catalyst required for PET polymerization to the layered clay by completely separating the organic clay in the composite, which could not be achieved by organicizing the layered clay with the organic agent in the conventional PET-organic clay nanocomposite production. It has been found that the organic clay can be completely exfoliated by allowing the polymerization of PET on a sheet of organoclay, thereby completing the present invention.

Therefore, the present invention is to solve the problems of the prior art as described above, the object of the present invention, instead of the conventional method of organicizing the clay using an organic agent in the method of producing a PET-organic clay composite, clay sheet Substituting the catalyst in the phase is to provide a PET-organoclay composite in which the layered organic clay is completely separated into basic units on a nanoscale sheet.

The layered organic clay of the present invention is characterized in that the alkali metal ions of the layered clay are substituted with a catalyst represented by the following general formula (I).

Wherein X is a halogen atom of F, Cl, Br, I.

The present invention relates to a layered organic clay in which the catalyst represented by the general formula (I) is substituted on a sheet of layered clay, which is generally substituted by replacing the catalyst represented by the general formula (I) with the layered clay being used. It is made by giving.

Layered clays with alkali metals present between layers are swellable by water, but are not known to penetrate other organic polymers. This is because the interlayer distance of the layered clay is only about 0.24 nm. In order to facilitate the penetration of the organic polymer into the clay, the organic agent composed of the head group of the cation and the lipophilic tail group It is necessary to increase the lipophilic properties of clay. At this time, the head group of the cation exchanges alkali metal ions on the clay surface, and the lipophilic tail group increases the interaction with the organic polymer and increases the interlayer distance of the clay to facilitate the interpenetration of the organic polymer. Play a role. However, in the present invention, since the organic use of the organizing clay cannot completely separate the clay in the organic polymer, in the present invention, the invention of the layered organic clay substituted with the catalyst by replacing the alkali metal ions of the layered clay with the catalyst To complete.

The catalyst may be selected and used according to the type of alkali metal present between the clay layers to be used, but it is preferable to use chlorotitanium triisopropoxide.

As the clay of the present invention, montmorillonite, saponite, hectorite, betelite, bentonite, nontronite or mica may be used, but generally montmorillonite using high swelling ability is used. It is preferable.

In addition, the PET-organic clay composite of the present invention is a PET-organic clay composite composed of PET and layered organic clay dispersed in PET, wherein the alkali metal ion of the layered clay is a catalyst represented by the following general formula (I). Characterized in that substituted.

Wherein X is a halogen atom of F, Cl, Br, I.

The content of the layered organic clay in the PET-organic clay composite of the present invention is preferably 0.1 to 10% by weight. If the content of the organic clay is less than 0.1% by weight, the effect of peeling the layered organic clay into the basic unit on the sheet of the nano-scale is insufficient, not fully peeled off, if it exceeds 10% by weight is not preferable because the manufacturing cost increases.

In the present invention, the basic principle is that the halogen atom of the catalyst represented by the general formula (I) causes a substitution reaction with the alkali metal ions of the layered clay so that the catalyst is bonded to the clay. First, the clay is swollen with a polar solvent, and then the halogen atoms of the catalyst are ion-bonded with the alkali metal ions of the clay, so that the layers between the organic clays are opened and the catalyst is present in the clay. Next, PET polymerization is performed by a catalyst between the layers of the organic clay in the polymerization process, and the PET chains are grown to obtain a state in which the clay is completely separated from the PET.

In the present invention, the method of substituting the catalyst on the clay sheet can be performed simply without any special apparatus in the following order.

First, the clay to replace the catalyst is vacuum dried at 150 ° C. for 24 hours before use. 100 g of anhydrous tetrahydrofuran (THF) was added to 10 g of vacuum dried clay in a glow box, followed by stirring at room temperature for 2 hours. 2 g of the catalyst was added to the suspension thus obtained and reacted at room temperature with stirring. After 24 hours, the clay was filtered and washed several times with filtered anhydrous THF to remove the catalyst which remained unsubstituted, thereby obtaining a layered organic clay in which the catalyst was substituted. Thus prepared layered organic clay can be determined by the replacement of the catalyst in the organic clay by measuring the EDX.

When PET-organic clay composite is prepared from the layered organic clay substituted with the catalyst of the present invention, since the catalyst is present on the sheet of the organic clay and polymerization occurs therein, the organic clay is separated from the PET-organoclay composite. The state can be obtained, which can be seen as a TEM picture.

Hereinafter, the present invention will be described in more detail with reference to the following examples. The following examples are merely examples for illustrating the present invention, and do not limit the protection scope of the present invention.

In the embodiment, there is no limitation on the type of alkali metal present between the layers of layered clay, but since it is generally used clay Na +, Southern Clay Cloisite product, a type of clay Na +, was used as clay.

(Example 1)

After vacuum drying the clay at 150 ° C. for 24 hours, 100 g of dry THF was added to 10 g of vacuum dried clay in a glow box, followed by stirring at room temperature for 2 hours. 2 g of chlorotitanium triisopropoxide was added to the suspension thus obtained as a catalyst and reacted at room temperature with stirring. After 24 hours, the clay was filtered and washed several times with filtered anhydrous THF to remove the catalyst remaining unsubstituted to obtain a layered organic clay substituted with a catalyst.

(Example 2)

After vacuum drying the clay at 150 ° C. for 24 hours, 100 mL of anhydrous dimethylformamide (DMF) was added to 10 g of vacuum dried clay in a glow box, followed by stirring at room temperature for 2 hours. 2 g of chlorotitanium triisopropoxide was added to the suspension thus obtained as a catalyst and reacted at room temperature with stirring. After 24 hours, the clay was filtered and washed several times with filtered anhydrous THF to remove the catalyst remaining unsubstituted to obtain an organic clay substituted with a catalyst.

(Example 3)

1% by weight of the layered organic clay (based on the total weight of dimethylene terephthalate and ethylene glycol) substituted with dimethylene terephthalate, ethylene glycol and the catalyst obtained in Example 1, at 230 ° C. under nitrogen atmosphere in a small polymerization apparatus for 1 hour, 230 After transesterification for 2 hours at ℃, 280 ℃, a condensation reaction in a vacuum of 0.1torr for 1 hour to prepare a PET-organic clay composite.

(Example 4)

2% by weight of layered organic clay (based on the total weight of dimethylene terephthalate and ethylene glycol) substituted with dimethylene terephthalate, ethylene glycol and the catalyst obtained in Example 1, at 230 ° C. under nitrogen atmosphere for 1 hour, 230 After transesterification for 2 hours at ℃, 280 ℃, a condensation reaction in a vacuum of 0.1torr for 1 hour to prepare a PET-organic clay composite.

(Example 5)

5% by weight of layered organic clay (based on the total weight of dimethylene terephthalate and ethylene glycol) substituted with dimethylene terephthalate, ethylene glycol and the catalyst obtained in Example 1, at 230 ° C. under nitrogen atmosphere in a small polymerization apparatus for 1 hour, 230 After 2 hours of ester exchange reaction at ℃, and 280 ℃, condensation reaction in a vacuum of 0.1torr for 1 hour to prepare a PET-organic clay composite.

(Comparative Example 1)

500 ppm of titanium isopropoxide was used as the dimethylene terephthalate (DMT), ethylene glycol, and catalyst based on DMT, and then 1% by weight of Cloisite 10A with an organizing agent (based on the total weight of dimethylene terephthalate and ethylene glycol) Was subjected to transesterification for 1 hour at 190 ° C. and 2 hours at 230 ° C. under a nitrogen atmosphere in a small polymerization apparatus, and a PET-organic clay composite was prepared through a condensation reaction at 280 ° C. in a vacuum of 0.1 torr for 1 hour.

(Comparative Example 2)

500 ppm of titanium isopropoxide was used as the dimethylene terephthalate, ethylene glycol, and catalyst based on DMT, and then 2% by weight of Cloisite 10A (organic weight of dimethylene terephthalate and ethylene glycol) with an organizing agent was compactly polymerized. The PET-organic clay composite was prepared by transesterification for 1 hour at 190 ° C. and 2 hours at 230 ° C. under a nitrogen atmosphere in the apparatus, and then for 1 hour at 280 ° C. under a vacuum of 0.1 torr.

(Comparative Example 3)

500 ppm of titanium isopropoxide was used as the dimethylene terephthalate, ethylene glycol, and catalyst based on DMT, and then 3% by weight of Cloisite 10A (organic weight of dimethylene terephthalate and ethylene glycol) with an organizing agent was compactly polymerized. The PET-organic clay composite was prepared by transesterification for 1 hour at 190 ° C. and 2 hours at 230 ° C. under a nitrogen atmosphere in the apparatus, and then for 1 hour at 280 ° C. under a vacuum of 0.1 torr.

(Comparative Example 4)

500 ppm of titanium isopropoxide was used as the dimethylene terephthalate, ethylene glycol, and catalyst based on DMT, and then 5% by weight of Cloisite 10A (organic weight of dimethylene terephthalate and ethylene glycol) with an organizing agent was compactly polymerized. The PET-organic clay composite was prepared by transesterification for 1 hour at 190 ° C. and 2 hours at 230 ° C. under a nitrogen atmosphere in the apparatus, and then for 1 hour at 280 ° C. under a vacuum of 0.1 torr.

The polymerization of the PET-organic clay composites obtained in Examples 3 to 5 and Comparative Examples 1 to 4 (○: polymerization was good, △: polymerization but foaming, ×: polymerization) and the relative viscosity was measured It is shown in Table 1 below.

TABLE 1

Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Polymerization ○ ○ ○ △ △ × × Relative viscosity 0.64 0.70 0.69 0.73 0.71

As can be seen in Table 1, in Comparative Examples 1 and 2 in which PET-organic clay composites were prepared from clay organicized with an organic agent as in the prior art, polymerization was performed, but difficulty in removing bubbles generated during polymerization was observed. There was this. In addition, in the case of Comparative Examples 3 and 4 in which PET-organic clay composites were prepared from clay organicized with an organic agent as in the prior art, the amount of bubbles generated was too high as the content of the organic clay was increased so that polymerization was not performed. In contrast, when the PET-organic clay composite was prepared from the layered organic clay substituted with the catalyst of the present invention obtained in Example 1 (Examples 3, 4 and 5), foaming occurred during polymerization compared to the conventional method. It could not be easily produced PET-organic clay composite.

As can be seen from the above, when the PET-organic clay composite is prepared from the layered organic clay substituted with the catalyst of the present invention, the PET-organoclay composite in which the organic clay is completely separated in PET can be prepared. In addition, foaming does not occur during polymerization, there is an advantage that can be easily produced PET-organic clay composite.

Claims (4)

 Alkali metal ions of the layered clay comprising one type selected from the group consisting of montmorillonite, saponite, hectorite, betelite, bentonite, nontronite and mica are chlorotitanium triiso of formula (I) Layered organic clay, characterized in that substituted by propoxide catalyst.

Wherein X is a halogen atom of F, Cl, Br or I. delete In the polyethylene terephthalate-organic clay composite comprising a layered organic clay dispersed in polyethylene terephthalate and polyethylene terephthalate, The layered organic clay is polyethylene terephthalate-organic clay composite, characterized in that the layered organic clay according to claim 1 of 0.1 to 10% by weight of the total composite weight. delete