KR20030068492A - A layered organic clay containing amineoxide ion, and a composites comprising the clay - Google Patents

Abstract

PURPOSE: A layered organic clay demineralized with an onium ion is provided. A polymer resin-layered organic clay complex having improved strength, elasticity, heat resistance and gas permeability is also provided. CONSTITUTION: The organic clay has a layered structure by demineralizing with an onium ion. The layered organic clay is characterized by comprising at least one amineoxide ions of the formula I as the onium ion, wherein each of R1, R2 and R3 is hydrogen, a C1-C30 alkyl group, a hydroxyalkyl, a polyethylene oxide compound, a polypropylene oxide compound, a C1-C30 aliphatic compound, a C1-C30 alicyclic compound or a C1-C30 aromatic compound.

Description

A layered organic clay containing amineoxide ion, and a composites comprising the clay}

The present invention relates to an amine oxide ion-containing layered organic clay and a polymer resin-organic clay composite (hereinafter referred to as "composite") containing the same. More specifically, the present invention relates to a layered organic clay and a composite comprising the same, wherein the inorganic ions present between the clay layers are substituted with amine oxides which are organic ions and have excellent dispersibility and heat resistance with the polymer.

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.

However, in the case of clay is hydrophilic, it is well dispersed in water, but there is a disadvantage that it is not dispersed in a lipophilic solvent or in a molten resin. As a result, polymer resin and layered clay are incompatible, and clay is not well dispersed in polymer resin during composite manufacturing, so improvement of the physical properties of the composite cannot be expected, and polymer resin penetrates well between layers of clay due to the narrow interval of layered clay. There were problems that were not.

In order to facilitate uniform dispersion of the layered inorganic material to the polymer resin, U.S. Patent 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 material such as inorganic silicates. (E.g., alkylammonium ions or functionalized organosilanes), followed by mixing of these layered materials with monomers or oligomers of the polymer. This cation exchange can render the existing hydrophilic silicates lipophilic and extend the interlayer distance of the layered material, thereby improving dispersibility to the resin.

Specifically, US Pat. No. 6,203,901 discloses a method of preparing fibers by dispersing a layered organic clay organicized with organic onium in a polyurethane urea resin. In the patent, examples of the organotium ions include 1-4 ammonium ions, pyridinium ions, imidazolinium ions, phosphonium ions, and sulfonium ions.

In addition, U.S. Pat. In order to provide a layered organic clay applicable to an ink, a paint, and the like.

In addition, Journal of Appl.Polym.Scien., Vol.55, pp. 119-123 (1995) used polysilicate stripped composites using inorganic silicates treated with 12-aminolauric acid. The technique to say is reported.

On the other hand, Japanese Patent Application Laid-Open No. Hei 10-182892 intercalates a polyolefin oligomer containing a functional group in an organic layered clay mineral to extend the interlaminar distance of the clay mineral to some extent, and then mix this composite material with an olefin resin. A method is described in which a layered clay mineral is dispersed in a matrix of an olefinic resin.

An object of the present invention is to produce a layered organic clay having low cost and excellent physical properties by using an organic agent which has not been conventionally used.

It is another object of the present invention to provide a polymer resin-organic clay composite having excellent compatibility and dispersibility with various polymer resins by containing the organic clay, thereby improving the mechanical properties of the composite as well as heat resistance and gas permeability. It is to.

The present invention is to a variety of polymer resins by organicizing sodium or calcium ions, etc. present in the natural state between each layer of the layered clay to the amine oxide (Amineoxide) ions of the general formula (I) instead of the conventionally known onium ions To provide a layered organic clay having excellent dispersibility and compatibility.

Wherein R _1, R ₂ and R ₃ each represent hydrogen, an alkyl group having 1-30 carbon atoms or a hydroxyalkyl, polyethylene oxide, polypropylene oxide compound, an aliphatic compound having 1-30 carbon atoms, or an alicyclic compound having 1-30 carbon atoms. Or an aromatic compound having 1 to 30 carbon atoms.

As such, the present invention is characterized in that the clay is organicized with a compound of the form of a new onium ion which is not conventionally applied, that is, the amine oxide onium ion of the general formula (I). In addition, the present invention is to provide a polymer resin-organic clay composite with improved physical properties by containing the layered organic clay of the present invention.

In order to achieve these problems, the layered organic clay of the present invention is in the form of an amineoxide onium ion of at least one of sodium or calcium ions present in each unit layer of the layered clay. It is characterized by being organic.

Wherein R _1, R ₂ and R ₃ each represent hydrogen, an alkyl group having 1-30 carbon atoms or a hydroxyalkyl, polyethylene oxide, polypropylene oxide compound, an aliphatic compound having 1-30 carbon atoms, or an alicyclic compound having 1-30 carbon atoms. Or an aromatic compound having 1 to 30 carbon atoms.

In other words, the layered organic clay of the present invention is characterized by containing (including) one or more amineoxide ions of the general formula (I) as onium ions. More specifically, the layered organic clay of the present invention may contain only one or more types of amine oxide ions of the general formula (I) as onium ions, and other types of sludge together with the amine oxide of the general formula (I). It may contain simultaneously ions.

In addition, the polymer resin-organic clay composite of the present invention is characterized in that the layered organic clay organicized with the amine oxide (amineoxide) ion of the general formula (I) is dispersed in the polymer resin.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The organic clay of the present invention can be prepared through the following processes.

First, an organic agent capable of forming an amine oxide ion of Formula (I) is reacted with an acid to prepare an organic agent in the form of onium salt, and then an aqueous solution and an organic solvent in which clay is dispersed. Or after reacting with a mixture of these at room temperature or heating, filtered and washed to remove the residual amount of the reaction by-product sodium chloride and the unreacted organic agent, dried and powdered to prepare the organic clay of the present invention,

The organic agent of the amine oxide compound of formula (I) is first reacted with an aqueous solution, an organic solvent or a mixture thereof in which clay is dispersed at room temperature or while heating, and then for removal of Na + ions. Acid, such as hydrochloric acid, is added to neutralize, precipitate, filter, and washed to remove the residual amount of the reaction by-product sodium chloride and the unreacted organic agent, and dried and powdered to prepare the organic clay of the present invention.

At this time, as the organic agent of the amine oxide of the general formula (I), such as lauryl dimethylamine oxide, cocoamido propyl amineoxide, etc. use.

A hydroxyl group (-OH), an acid group (-COOH), or an epoxy group (at the side or terminal of each of R _1, R _2, and R _{3 in} the amine oxide compound of Formula (I) It may have a reactor such as) or may include a linking group of ester, amide or ether in the molecular chain.

In the preparation of a composite with a water-soluble polymer, in order to improve the dispersion and interaction with the polymer resin, an organic clay which is organically treated with only the amine oxide compound of the general formula (I) may be used without using an acid.

The clay may be montmorillonite, saponite, hectorite, laponite, battellite, bentonite, nontronite, vermiculite, illite, muscobite, pyrophyllite or mica. .

In the present invention, other types of compounds capable of forming onium ions together with the amine oxide compound of the general formula (I) may be used simultaneously as the organic agent. In this case, in the layered organic clay of the present invention, (i) one or more amine oxide ions, (ii) one or more primary-quaternary ammonium ions, imidazolium ions, phosphonium ions, Sulfonium ions, imidazolinium ions, pyridinium ions or triazinium ions are optionally contained.

The layered organic clay described above may be mixed and polymerized together with the monomer from the initial stage of polymerization of the polymer resin to prepare the polymer resin-organic clay composite of the present invention.

In addition, the polymer resin may be melt compounded with organic clay, or the polymer resin-organic clay composite may be prepared by dispersing, coating and drying the polymer resin and the organic clay in a solvent.

In the present invention, it does not specifically limit the manufacturing method of the polymer resin-organic clay composite.

The polymer resin-organic clay composite of the present invention prepared as described above is (1) a polymer resin and (ii) dispersed in the polymer resin, and one amine oxide (amine oxide) ion of the general formula (I) It consists of the layered organic clay containing above.

Wherein R _1, R ₂ and R ₃ each represent hydrogen, an alkyl group having 1-30 carbon atoms or a hydroxyalkyl, polyethylene oxide, polypropylene oxide compound, an aliphatic compound having 1-30 carbon atoms, or an alicyclic compound having 1-30 carbon atoms. Or an aromatic compound having 1 to 30 carbon atoms, and a hydroxy group (-OH) or an acid group (-COOH) at the side or terminal of each of R _1, R ₂ and R _{3 in} the amine oxide compound of Formula (I) Epoxy group It may have a reactor such as) or may include a linking group of ester, amide or ether in the molecular chain.

The content of the layered organic clay in the polymer resin is preferably 0.1-15% by weight. If it is less than 0.1% by weight, the effect of improving the physical properties of the composite is insufficient, and if it exceeds 15% by weight, the dispersibility is lowered and the manufacturing cost is increased.

As the polymer resin, polyester resin, polyamide resin, epoxy resin, polyurethane resin, polyurethane urea resin, polyimide resin, polysiloxane resin, ABS resin or polyolefin resin can be used.

The layered organic clay of the present invention described above is excellent in compatibility and dispersibility with various resins, and the composite containing the layered organic clay of the present invention exhibits a property of greatly improving physical properties such as strength.

In the present invention, the physical properties of each of the layered organic clay and the composite were evaluated as follows.

Heat resistance (initial decomposition temperature, ℃)

TGA was heated at a rate of 20 ° C./min, and the temperature at the time of initial 5 wt% decomposition and reduction after water removal was measured to be heat resistant.

Interlayer distance of layered organic clay

It is measured by X-ray diffraction. Specifically, RIG-2000 Co., Ltd., Japan, was used, and coca (CoKa, α = 0.15 nanometer) light was used for observation.

Dispersibility of layered organic clay

It measures by the said X-ray diffraction method. Here, the observation And evaluated by dividing by △ and ×, The good dispersibility means that there is no specific peak of organic clay at 2θ = 10 ° or less as the result of X-ray diffraction of the organic clay mineral and the polymer resin composite. do. In addition, Δ is a dispersibility, which means that a specific peak of the organic clay appears at 2θ = 10 ° or less as a result of X-ray diffraction, and that dispersibility is normal when the interlayer distance of the organic clay is extended to 50 Å or more. In addition, X is a poor dispersibility, a specific peak of organic clay appears at 2θ = 10 ° or less as a result of X-ray diffraction.

Tensile Strength / Elongation / Tensile Modulus of Elastic Fiber

It was measured by ASTM D 2731-722 method.

Tensile strength / elongation / tensile modulus of composite (plastic specimen)

It was measured by ASTM D-638 method.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited only to the following examples.

Example 1

288 g of lauryl dimethylamine oxide (Miwon Corporation Co., Ltd.-Organics) was added to 7000 g of water, such as 10% aqueous hydrochloric acid solution 503 g, and stirred for 1 hour at room temperature to completely dissolve the lauryl dimethylamine oxide compound. Manufacture. On the other hand, 1000g of Na ⁺ -montmorillonite manufactured by SPC, USA, having an ion exchange capacity of 92.6 meq / 100g, was sufficiently dispersed in 50 L of 70 ° C. deionized water for 2 hours or more to be sufficiently dispersed. The lauryldimethylamine oxide onium salt prepared above was added thereto, followed by an ion exchange reaction with stirring at 70 ° C. for 1 hour, followed by filtration and washing to remove NaCl and unreacted organic agent by reaction, drying and powdering. To prepare a layered organic clay. A polyester-layered organic clay composite is prepared by mixing and polymerizing the layered organic clay together with monomers (dimethyl terephthalate and 1,4-butanediol) from the initial stage of the polyester polymerization to 3% by weight. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Example 2

288 g of lauryl dimethylamine oxide (Miwon Corporation Co., Ltd.-Organics) was added to 7000 g of water, such as 10% aqueous hydrochloric acid solution 503 g, and stirred for 1 hour at room temperature to completely dissolve the lauryl dimethylamine oxide compound. Manufacture. On the other hand, 1000g of Na ⁺ -montmorillonite manufactured by SPC, USA, having an ion exchange capacity of 92.6 meq / 100g, was sufficiently dispersed in 50 L of 70 ° C. deionized water for 2 hours or more to be sufficiently dispersed. The lauryldimethylamine oxide onium salt prepared above was added thereto, followed by an ion exchange reaction with stirring at 70 ° C. for 1 hour, followed by filtration and washing to remove NaCl and unreacted organic agent by reaction, drying and powdering. To prepare a layered organic clay. Polyamide 6-layered organic clay composite is prepared by mixing and polymerizing the layered organic clay together with monomers (adipic acid and water) from the initial stage of polyamide 6 polymerization to 3% by weight. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Example 3

288 g of lauryl dimethylamine oxide (Miwon Corporation Co., Ltd.-Organics) was added to 7000 g of water, such as 10% aqueous hydrochloric acid solution 503 g, and stirred for 1 hour at room temperature to completely dissolve the lauryl dimethylamine oxide compound. Manufacture. On the other hand, 1000g of Na ⁺ -montmorillonite manufactured by SPC, USA, having an ion exchange capacity of 92.6 meq / 100g, was sufficiently dispersed in 50 L of 70 ° C. deionized water for 2 hours or more to be sufficiently dispersed. The lauryldimethylamine oxide onium salt prepared above was added thereto, followed by an ion exchange reaction with stirring at 70 ° C. for 1 hour, followed by filtration and washing to remove NaCl and unreacted organic agent by reaction, drying and powdering. To prepare a layered organic clay. 3 wt% of the layered organic clay is melt compounded with 97 wt% of the polyester resin to prepare a polyester-layered organic clay composite. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Example 4

288 g of cocoamido propyl amine oxide (Miwon Corp.-Organizer) was added to 7000 g of water, such as 503 g of 10% hydrochloric acid solution, and stirred at room temperature for 1 hour to completely dissolve the amine oxide compound in the form of onium salt. do. On the other hand, 1000g of Na ⁺ -montmorillonite manufactured by SPC, USA, having an ion exchange capacity of 92.6 meq / 100g, was sufficiently dispersed in 50 L of 70 ° C. deionized water for 2 hours or more to be sufficiently dispersed. The cocoamido propyl amine oxide onium salt prepared above was added thereto, followed by an ion exchange reaction with stirring at 70 ° C. for 1 hour, followed by filtration and washing to remove the reaction byproduct NaCl and the unreacted organic agent, followed by drying and powdering. To prepare a layered organic clay. Meanwhile, 2,200 g of polytetramethylene ether glycol (PTMG) having a molecular weight of 1,800 and 500 g of diphenylmethane diisocyanate (MDI) were mixed and polymerized at 80 ° C. for 2 hours to prepare a prepolymer, and then the prepolymer was dimethylacetamide. (DMAc) was dissolved in 3,500 g, cooled to 30 ° C., and then polymerized by adding 40 g of ethylenediamine, 0.5 g of tris (2-aminoethylamine) [TAEA] as a chain extender, and 6 g of diethylamine as a chain stopper, respectively. The spinning dope of the polyurethaneurea polymer was prepared. Subsequently, 3 wt% of the layered organic clay prepared above was added to the spinning dope to disperse the solution, followed by dry spinning in the usual manner to prepare 40 denier polyurethane urea elastic fibers. The results of evaluating the physical properties of the prepared elastic fibers are shown in Table 1. (Modulus represents the value at 300% elongation)

Example 5

200 g of lauryl dimethylamine oxide (Miwon Corporation Co., Ltd.-organizer) is added to 7000 g of water, such as 503 g of 10% hydrochloric acid solution, and stirred for 1 hour at room temperature to completely dissolve the lauryl dimethylamine oxide compound. Manufacture. On the other hand, 1000g of Na ⁺ -montmorillonite manufactured by SPC, USA, having an ion exchange capacity of 92.6 meq / 100g, was sufficiently dispersed in 50 L of 70 ° C. deionized water for 2 hours or more to be sufficiently dispersed. The lauryldimethylamine oxide onium salt prepared above was simultaneously added thereto, followed by an ion exchange reaction with stirring at 70 ° C. for 1 hour, followed by filtration and washing to remove the reaction byproduct NaCl and the unreacted organic agent, drying and powdering. To give a layered organic clay. A polyester-layered organic clay composite is prepared by mixing and polymerizing the layered organic clay together with monomers (dimethyl terephthalate and 1,4-butanediol) from the initial stage of the polyester polymerization to 3% by weight. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Comparative Example 1

The polyester-layered organic clay composite is prepared by mixing and polymerizing 3% by weight of Cloisite 15A of US SCP with organic clay together with monomers (dimethyl terephthalate and 1,4-butanediol) from the initial stage of polyester polymerization. . The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Comparative Example 2

Polyamide 6-layered organic clay composite is prepared by mixing and polymerizing 3% by weight of 15% Cloisite of SCP of the United States with organic clay together with monomers (adipic acid and water) from the initial stage of polyamide 6 polymerization. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Comparative Example 3

Polyamide 6-layered organic clay composite is prepared by mixing and polymerizing 3% by weight of 15% Cloisite of SCP of the United States with organic clay together with monomers (adipic acid and water) from the initial stage of polyamide 6 polymerization. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Comparative Example 4

The organic clay is melt compounded with 3% by weight of Cloisite 15A of SCP, USA, and 97% by weight of polyester resin to prepare a polyester-layered organoclay composite. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Physical property measurement result division Recipe Polymer Type Layered organic clay Complex Interlayer distance Initial decomposition temperature (℃) Dispersibility Tensile Modulus (kg / ㎠) (g / d) Tensile Strength (kg / ㎠) (g / d) Elongation (%) Example 1 Simultaneous polymerization polyester 21.7 298 17,600 622 5 Example 2 Simultaneous polymerization Polyamide 21.7 298 40,200 1,150 10 Example 3 Melt Compounding Method polyester 21.7 298 17,900 594 4 Example 4 Solution Compounding Method Polyurethane Urea 25.4 304 0.125 3.0 1,030 Example 5 Simultaneous polymerization polyester 23.9 298 19,000 803 7 Comparative Example 1 Simultaneous polymerization polyester 31.5 - 16,800 565 3 Comparative Example 2 Simultaneous polymerization Polyamide 31.5 - 37,400 937 7 Comparative Example 3 Simultaneous polymerization Polyamide 19.2 - 34,200 920 8 Comparative Example 4 Melt Compounding Method polyester 31.5 - △ 15,400 532 3

The layered organic clay of the present invention is excellent in heat resistance as organic clay organicized with a stable amine oxide compound, rather than conventional onium ion organicizing agents, and excellent compatibility and dispersibility with various polymer resins. As a result, when the composite with the polymer resin is produced, the effect of increasing physical properties such as strength, elasticity, heat resistance, etc. of the composite is remarkable, and inexpensive organic clay can be manufactured.

Claims (10)

In organic clay organicized with onium ions and having a layered structure, an amine oxide ion-containing layered layer comprising at least one amineoxide ion of the general formula (I) as onium ions Organoclay. Wherein R _1, R ₂ and R ₃ each represent hydrogen, an alkyl group having 1-30 carbon atoms or a hydroxyalkyl, polyethylene oxide, polypropylene oxide compound, an aliphatic compound having 1-30 carbon atoms, or an alicyclic compound having 1-30 carbon atoms. Or an aromatic compound having 1 to 30 carbon atoms. The layered organic clay according to claim 1, wherein the layered organic clay is (i) one or more amine oxide ions of the general formula (I), and (ii) one or more primary-grade IV ammonium ions and imidazolium ions. An amine oxide ion-containing layered organic clay having phosphonium ions, sulfonium ions, imidazolinium ions, pyridinium ions or triazinium ions. The inorganic component of the layered organic clay is montmorillonite, saponite, hectorite, laponite, betelite, bentonite, nontronite, vermiculite, illite, muscobite, pyrophyllite or An amine oxide ion-containing layered organic clay, characterized in that it is Mica. The amine oxide ion-containing layered organic clay according to claim 1, wherein an amide group, an ester group or an ether group (bonding group) is contained in the molecular chain of the organic agent. In the polymer resin-organic clay composite composed of a polymer resin and a layered organic clay dispersed in the polymer resin, the layered organic clay is onium ion and at least one amineoxide ion of the following general formula (I): Polymer resin-organic clay complex comprising a. Wherein R _1, R ₂ and R ₃ each represent hydrogen, an alkyl group having 1-30 carbon atoms or a hydroxyalkyl, polyethylene oxide, polypropylene oxide compound, an aliphatic compound having 1-30 carbon atoms, or an alicyclic compound having 1-30 carbon atoms. Or an aromatic compound having 1 to 30 carbon atoms. The polymer resin-organic clay composite according to claim 5, wherein an amide group, an ester group or an ether group (bonding group) is contained in the molecular chain of the organic agent. The layered organic clay according to claim 5, wherein the layered organic clay is (i) one or more amine oxide ions of the general formula (I), and (ii) one or more primary-grade IV ammonium ions and imidazolium ions. Polymer resin-organic clay complex, characterized in that having a phosphonium ion, sulfonium ion, imidazolinium ion, pyridinium ion or triazinium ion. The inorganic component of the layered organic clay is montmorillonite, saponite, hectorite, laponite, betelite, bentonite, nontronite, vermiculite, illite, muscobite, pyrophyllite or Polymer resin-organic clay composite, characterized in that the mica (Mica). The polymer resin-organic clay composite according to claim 5, wherein the layered organic clay content in the polymer resin-organic clay composite is 0.1-15% by weight. The polymer resin-organic clay according to claim 5, wherein the polymer resin is a polyester resin, a polyamide resin, an epoxy resin, a polyurethane resin, a polyurethane urea resin, a polyimide resin, a polysiloxane resin, an ABS resin or a polyolefin resin. Complex.