KR100545140B1 - A layered organo clay with excellent thermal stability and flame-retardant properties, and a composites comprising the organo clay - Google Patents

Abstract

The present invention relates to a layered organic clay and a composite using the same to improve the flame retardancy, the layered organic clay of the present invention is a phosphorus-based flame retardant component It is characterized in that it is organicized with Onium (ionic) ionic compound containing). The layered organic clay of the present invention has excellent dispersibility with various polymer resins to improve composite physical properties such as strength and elastic modulus. The composite of the present invention is particularly excellent in flame retardancy.

Organoclay, layered, polymer, composite, flame retardant, organic, dispersible, color, onium ion

Description

A layered organo clay with excellent thermal stability and flame-retardant properties, and a composites comprising the organo clay}

The present invention relates to a layered organic clay having excellent heat resistance and flame retardancy, and a polymer resin-organic clay composite (hereinafter referred to as "composite") including the same.

More specifically, the present invention relates to a layered organic clay having an organic ion of Onium ion, which is an organic ion between clay layers, having excellent dispersibility, heat resistance, and flame retardancy, and a composite including the same.

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 the molten state of the resin or under a lipophilic solvent. As a result, polymer resin and layered clay are incompatible, and clay is not well dispersed in the polymer resin during composite production. Therefore, the physical properties of the composite cannot be expected, and the interlayer of layered clay is narrow. There were problems that did not penetrate.

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.

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

However, the layered organic clays disclosed in the U.S. Patents have a low thermal stability level of 100-110 ° C., so that the organic clays are thermally decomposed when the polymer resin-organic clay composite is prepared, thereby deteriorating the physical properties of the composites.

In addition, US Pat. No. 6,057,035 discloses a method of organicizing clay with a phosphorus compound and using silicon as an organic emulsifier to improve the thermal stability of the organic clay. However, the above method can improve the thermal stability of the organic clay to 200 ° C., but it is difficult to apply to composites of polyesters and polypropylenes due to low dispersibility and compatibility with polymer resins. Flame retardancy could not be improved.

In addition, the Republic of Korea Patent Publication No. 1998-0002056 proposes a method of dispersing and processing the oligomer of the phosphorus-based flame retardant with the resin as a method for improving the flame retardancy of the resin, but the method must contain an excessive amount of flame retardant (more than 15% by weight) ) V0 exhibits flame retardancy, but in this case, mechanical properties are deteriorated.

In addition, Korean Patent Laid-Open Publication No. 2002-0027783 proposes a method of dispersing an organophosphorous flame retardant in which a flame retardant is first encapsulated with a thermoplastic resin in a resin in order to minimize such mechanical properties. There was a problem in that the V0 exhibits flame retardancy and the mechanical properties gradually worsen as the content of the flame retardant increases.

In addition, Korean Patent Laid-Open Publication No. 2002-7588 discloses a layered organic clay organicized with an organizing agent in which the functional group of the modified polypropylene and the amine-based non-halogen flame retardant are chemically bonded, (ii) the modified polypropylene and (iii) poly A polypropylene-organic clay composite consisting of propylene resin (metrics) is disclosed. However, the layered organic clay used in the patent has a problem that only compatibility with polypropylene is improved and compatibility with other polymer resins is not improved.

The purpose of the present invention is to solve the problems of the conventional organic clay, dispersibility and compatibility with a variety of polymer resins and the like when manufacturing a polymer resin-organic clay composite, excellent heat resistance and decomposition at the processing temperature of the polymer resin To provide organic clay that is not.

Another object of the present invention is to provide a polymer resin-organic clay composite having the above-mentioned organic clay, which has improved physical properties and colors, and is particularly excellent in flame retardancy.

The present invention is a natural polymer between the sodium or calcium ions existing in each layer between the layered clay of the Onium (Onium) ions compound containing a phosphorus-based flame retardant instead of the conventional organic onium ions and various polymer resins and It is intended to provide a layered organic clay having excellent dispersibility and compatibility, and good heat resistance and flame retardancy.

As described above, the present invention is characterized in that the clay is organicized with a new organic onium ion not previously applied, that is, an onium ion compound containing a phosphorus-based flame retardant component. In addition, the present invention is to provide a polymer resin-organic clay composite with improved layer properties and color, heat resistance and flame retardancy as well as physical properties and colors of the present invention.

In the layered organic clay of the present invention for achieving the above problems, sodium or calcium ions present between each unit layer of the layered clay is phosphorus-based flame-retardant component (9,10-dihydro-9-oxa-10-phosphapenan It is characterized in that it is organic to Onium (Onium) ion compound containing Tren-10-oxide).

In addition, the polymer resin-organic clay composite of the present invention contains a phosphorus flame retardant component (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; hereinafter referred to as "DHOPO"). It is characterized in that the layered organic clay, which is organicized with an onium ion compound, is dispersed in a polymer resin.

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

Onium ion compounds containing phosphorus flame retardant component (DHOPO) include compounds of the following general formula (I) and the like.

이다. 또한 R₄, R₅ 및 R₆ 는 각각 수소, 할로겐, 하이드록시기 또는 탄소수 1-5의 알킬기 이며, Y는 COO, CONH 또는 O 이며, n 은 1-5의 정수이고, m 은 1-20의 정수이다.][In Formula (I), M ⁺ is onium ion of nitrogen, phosphorus, sulfur or iodine, R ₁ and R ₂ are hydrogen, halogen, hydroxy group or alkyl or alkoxy group having 1 to 10 carbon atoms, R ₃ is

to be. R ₄ , R ₅ and R ₆ are each hydrogen, halogen, hydroxy group or alkyl group of 1-5 carbon atoms, Y is COO, CONH or O, n is an integer of 1-5, m is 1-20 Is an integer of.]

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

First, a compound having a reactor capable of reacting with DHOPO, a phosphorus-based flame retardant, and a group having a group capable of forming onium ions, on the other, are reacted with DHOPO, a phosphorus-based flame retardant, to form an organic agent.

The organic agent thus prepared is reacted with an acid to prepare an organic agent in the form of Onium ion of the general formula (I), and then the clay and the solution of clay dispersed in an aqueous solution or an organic solvent or a mixture thereof. After reacting the organic agent of Um ion at room temperature or by heating, the resultant is filtered, washed with water to remove the residual amount of sodium chloride and the unreacted organic agent, and dried and powdered to prepare the organic clay of the present invention.

At this time, the phosphorus-based flame retardant component for making an organic agent capable of forming Onium ions containing the phosphorus-based flame retardant component of the general formula (I) is 1, Sanko HCA of Sanko Co., Ltd. 2- (dimethylamino) ethyl methacrylate is used as 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like, which can form onium ions while reacting with the phosphorus-based flame retardant component. Etc.

In addition, hydrochloric acid or a halogen-containing organic compound may be used as the acid reacted with the organic agent to transform the organic agent into onium ion form.

The clay may be montmorillonite, saponite, hectorite, betelite, bentonite, nontronite or mica.

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 and the organic clay 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 a phosphorous flame-retardant component (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) dispersed in the polymer resin and the polymer resin. It consists of a layered organic clay that is organicized with Onium ionic compounds.

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, ABS resin, polyolefin resin, rubber resin, polystyrene, polyurethane resin, polyurea resin, polyimide resin or polysiloxane resin can be used.

The layered organic clay of the present invention described above is excellent in compatibility and dispersibility with various resins, has excellent heat resistance that does not decompose even at a polyester processing temperature, and contains a flame retardant component, thus containing a small amount of organic clay. The composite of the present invention can obtain a composite having excellent flame retardancy while preventing mechanical color degradation such as strength and preventing discoloration during processing.

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

Interlayer distance of layered organic clay

It is measured by X-ray diffraction. Specifically, RIG-2000 of Rigaku, Japan was used, and Cuka (α = 0.15 nanometer) light was used for observation.

Dispersibility of layered organic clay

The X-diffraction method was used, and the observation results were evaluated by dividing by O and X. O is good in dispersibility, and X-ray diffraction analysis of the composite of organic clay and polymer resin shows that the distance between layers of organic clay is increased when the specific peak of organic clay disappears or the distance between layers increases by 50Å or less. It means that the dispersibility is good. In addition, X means poor dispersibility due to poor dispersibility, unless a specific peak of the layered organic clay is shown as a result of X-ray diffraction or the distance between layers is not increased by 50 Å or more.

Flexural modulus

It was measured at room temperature according to the American Society for Testing and Materials (ASTM) D790.

·The tensile strength

It was measured by ASTM D-638 method.

Impact strength

It was measured by ASTM D-256 method.

Flame retardant

Measurement was made according to the UL 94 standard.

Inherent Viscosity

It was dissolved in a mixed solvent of phenol / tetrachloroethane = 50/50 and measured with a Ubelode viscous tube at a measurement temperature of 30 ° C. and a solid content concentration of 0.1 g / dL.

Melt Index (g / 10min.)

It measured at ASTM D-1238, 230 degreeC.

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

153 g of 1,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and San (Hanko) HCA, Sanko Co., Ltd., Japan, and 111 g of 2- (dimethylamino) ethyl methacrylate were prepared using ethanol (2). 3 liters of water / 1 liter of mixed solvent and dissolve while stirring. 1.5 g of NaOH is added as a catalyst to dissolve and react. After the reaction temperature is also carried out at room temperature for 5 hours, the reaction is finished up to 60 ° C. to complete the reaction, and then neutralized with dilute hydrochloric acid solution and precipitated in water. The precipitated reactant is filtered and dried to obtain an onium-formable amine organizing agent containing a phosphorus flame retardant component. In addition, 800 g of Na-montmorillonite (clay) having a cation exchange capacity of 119 milliquivalents / 100 g was added to 25 liters of distilled water, followed by stirring to disperse to make a thin slurry solution. 250 g of the amine organic agent was added to 5 liters of distilled water. Dispersion and 350 g of 10% by weight aqueous hydrochloric acid solution are added to form a completely dissolved organic agent solution while onionizing the amine organic agent. The organic agent solution is added to the diluted slurry solution in which the clay is dispersed while being stirred and reacted to synthesize a layered organic clay. The reaction was carried out at 40 ° C. for 2 hours. After the reaction was neutralized with diluted aqueous sodium hydroxide solution, filtered and lyophilized to prepare a layered organic clay. Next, in the melt kneading extruder in which the temperature of the cylinder is maintained at 250 ° C., 7 wt% of the layered organic clay prepared as described above and 93 wt% of polybutylene terephthalate resin having an intrinsic viscosity of 0.84 are kneaded and extruded to form a molding resin chip. After manufacturing, the molding chip was dried again and a composite specimen was prepared using an injection molding machine in which the temperature of the cylinder was maintained at the same temperature as the extruder. The results of evaluating the physical properties of the prepared layered organic clay and composite specimens are shown in Table 1.

Example 2

In preparing the composite specimens, the layered organic clay and the composite specimens were prepared in the same manner as in Example 1 except that the amount of the layered organic clay was changed to 10% by weight and the amount of the polybutylene terephthalate was changed to 90% by weight. The results of evaluating the physical properties of the prepared layered organic clay and composite specimens are shown in Table 1.

Example 3

A layered organic clay was prepared in the same manner as in Example 1, and then 7% by weight of the layered organic clay was mixed with dimethyl terephthalate (1 mol) and 1,4-butanediol (2 mol), which are monomers at the beginning of the polymerization of polybutylene terephthalate. Into the reactor together and reacted for 90 minutes at a temperature of 150 ℃ atmospheric pressure, and polymerized for 4 hours at 260 ℃ while applying a vacuum to prepare a polybutylene terephthalate chip having an intrinsic viscosity of 0.86. After drying the polybutylene terephthalate chip was prepared a composite specimen using an injection molding machine having a cylinder temperature of 250 ℃. The results of evaluating the physical properties of the prepared layered organic clay and composite specimens are shown in Table 1.

Example 4

After preparing the layered organic clay in the same manner as in Example 1, in the melt kneading extruder in which the temperature of the cylinder is maintained at 250 ℃ 10 wt% of the layered organic clay prepared as described above and the melt index 5g / 10 minutes (230 ℃ Kneading and extruding 90 wt% of the ethylene-propylene copolymer) to form a resin chip for molding, and drying the molding chip again, and then using the injection molding machine in which the temperature of the cylinder is maintained at the temperature of the extruder. Was prepared. The results of evaluating the physical properties of the prepared layered organic clay and composite specimens are shown in Table 1.

 Comparative Example 1

In the melt kneading extruder in which the temperature of the cylinder is maintained at 250 ° C., 10 wt% of triphenyl phosphate (flame retardant) and 90 wt% of polybutylene terephthalate are kneaded and extruded to prepare a molding resin chip, and the molding chip is again After drying, the composite specimen was prepared using an injection molding machine in which the temperature of the cylinder was maintained at the same temperature as the extruder. The results of evaluating the physical properties of the prepared composite specimens are shown in Table 1.

Comparative Example 2

10% by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (flame retardant) and 90% by weight of polybutylene terephthalate in a melt kneading extruder in which the temperature of the cylinder is maintained at 250 ° C Kneading and extruding to prepare a molding resin chip, and dried the molding chip again to prepare a composite specimen using an injection molding machine in which the temperature of the cylinder is maintained at the same temperature as the extruder. The results of evaluating the physical properties of the prepared composite specimens are shown in Table 1.                     

 Comparative Example 3

In the melt kneading extruder in which the temperature of the cylinder is maintained at 250 ° C., 10% by weight of triphenylphosphate (flame retardant) and 90% by weight of ethylene-propylene copolymer having a melt index of 5 g / 10 minutes (230 ° C.) are kneaded and extruded. A resin chip was prepared, and the molding chip was dried again, and then a composite specimen was manufactured using an injection molding machine in which the temperature of the cylinder was maintained at the same temperature as the extruder. The results of evaluating the physical properties of the prepared composite specimens are shown in Table 1.

Physical property measurement result division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Layered organic clay Interlayer Distance (Å) 22.3 22.3 22.3 22.3 - - - Dispersibility

- - - Complex Flexural modulus (kg / ㎠) 30,500 35,700 34,600 23,100 17,800 20,900 10,300 Tensile Strength (kg / ㎠) 573 598 629 - 487 529 - Impact Strength (kg-cm / cm) 6.3 6.2 6.4 4.1 4.3 1.8 1.6 Flame retardant V0 V0 V0 V0 V2 V2 V2

The layered organic clay of the present invention has excellent compatibility and dispersibility with various polymer resins, and is excellent in heat resistance and does not decompose even at a processing temperature of polyester. As a result, physical properties such as strength, elasticity, and heat resistance of the composite, particularly flame retardancy, are greatly improved when the composite is prepared with the polymer resin, and color improvement (prevention of discoloration) can be obtained.

Claims (10)

Phosphorus-based flame retardant component (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in organic clay having a layered structure which is organicized with an organizing agent capable of forming onium ions Layered organic clay, characterized in that it is organic to Onium (ionic) compound containing. The Onium ion compound according to claim 1, which contains a phosphorus flame retardant component (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), is a compound of the general formula (I) Layered organic clay, characterized in that.

[In Formula (I), M ⁺ is onium ion of nitrogen, phosphorus, sulfur or iodine, R ₁ and R ₂ are hydrogen, halogen, hydroxy group or alkyl or alkoxy group having 1 to 10 carbon atoms, R ₃ is

to be. R ₄ , R ₅ and R ₆ are each hydrogen, halogen, hydroxy group or alkyl group of 1-5 carbon atoms, Y is COO, CONH or O, n is an integer of 1-5, m is 1-20 Is an integer of.] The method according to claim 1 or 2, wherein the onium ion (M ⁺ ) is a class 1-4 ammonium ion, phosphonium ion, sulfonium ion, imidazolium Layered organic clay, characterized in that the ion, pyridinium (ion), triazinium (ion) or iodonium (ion). The layered organic clay according to claim 1 or 2, wherein the inorganic component of the layered organic clay is montmorillonite, saponite, hectorite, betellite, bentonite, nontronite, or mica. 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 a phosphorus flame-retardant component (9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide) polymerized organic-organic clay composite, characterized in that it is organic to Onium (Onium) ionic compound containing. The Onium ion compound according to claim 5, wherein the onium ion compound containing a phosphorus flame retardant component (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is a compound of the general formula (I) Polymer resin-organic clay composite, characterized in that the.

[In Formula (I), M ⁺ is onium ion of nitrogen, phosphorus, sulfur or iodine, R ₁ and R ₂ are hydrogen, halogen, hydroxy group or alkyl or alkoxy group having 1 to 10 carbon atoms, R ₃ is

to be. R ₄ , R ₅ and R ₆ are each hydrogen, halogen, hydroxy group or alkyl group of 1-5 carbon atoms, Y is COO, CONH or O, n is an integer of 1-5, m is 1-20 Is an integer of.] The polymer resin-organic clay composite according to claim 5, wherein the layered organic clay content in the polymer resin-organic clay composite is 0.1-10% by weight. The polymer resin according to claim 5, wherein the polymer resin is a polyester resin, a polyamide resin, an epoxy resin, a polyurethane resin, a polyurea resin, a polyimide resin, a polysiloxane resin, an ABS resin, a rubber resin or a polyolefin resin. Organoclay complex. The method according to claim 5 or 6, wherein the onium ion (M ⁺ ) is a class 1-4 ammonium ion, phosphonium ion, sulfonium ion, imidazolium An organic clay-polymer resin complex characterized in that the ion, pyridinium ions, triazinium ions or iodonium ions. The polymer resin-organic clay composite according to claim 5, wherein the inorganic component of the layered organic clay is montmorillonite, saponite, hectorite, betellite, bentonite, nontronite or mica.