KR20020053199A - Thermoplastic Resin Composite Having Excellent Mechanical Strength and Heat-Resistance and Method of Preparing the Same - Google Patents

Abstract

PURPOSE: A thermoplastic resin composite material and its preparation method are provided to improve mechanical strength and heat resistance without deterioration of impact resistance by dispersing the clay mineral into a thermoplastic resin uniformly. CONSTITUTION: The thermoplastic resin composite material comprises 100 parts by weight of a polymer prepared from a vinyl-based monomer or a mixture of two or more kinds of vinyl-based monomers; and 0.1-50 parts by weight of a clay mineral modified by ion exchange reaction using an onium ion-containing compound having an azo group or peroxide group. The nano-sized clay mineral is dispersed into the polymer uniformly. The method comprises the steps of modifying the clay mineral by ion exchange reaction using an onium ion-containing compound having an azo group or peroxide group; and emulsion polymerizing a polymer prepared from a vinyl-based monomer or a mixture of two or more kinds of vinyl-based monomers by using the modified clay mineral as an emulsifier. Preferably the emulsion polymerization is carried out by using a molecular weight controlling agent.

Description

Thermoplastic Resin Composite Having Excellent Mechanical Strength and Heat-Resistance and Method of Preparing the Same}

Field of invention

The present invention relates to a thermoplastic resin composite material having excellent mechanical strength and heat resistance characteristics, and a method of manufacturing the same. More specifically, the present invention provides a thermoplastic resin composite material having excellent mechanical strength and heat resistance, which is made by uniformly distributing clay minerals in a polymer by emulsion polymerization of a vinyl monomer using a plate-shaped modified clay mineral as an emulsifier, and It relates to a manufacturing method.

Background of the Invention

As a method for improving mechanical strength and thermal stability of thermoplastic resins, which are widely used commercially, there is a method of adding inorganic materials such as glass fiber, talc, mica and the like. However, resins prepared by the general technique of simply blending inorganic additives with resins have other disadvantages. That is, in such a resin, since the bonding strength between the inorganic additive and the resin is not sufficient to exhibit the reinforcing effect required in the actual application portion, there is a problem that the impact resistance is considerably lowered.

Therefore, in order to have appropriate mechanical strength, heat resistance, and other physical properties by only adding a small amount of an inorganic additive to the thermoplastic resin, a method of using a plate-shaped clay mineral has been proposed. Specifically, when polymerizing the resin, a plate-like clay mineral surface-treated with a suitable organic compound is used to improve the bonding strength between the clay mineral and the resin, and in the thermoplastic resin, the clay mineral is uniformly formed into a nano-size layer. To be distributed. However, in the case of surface treatment of plate-shaped clay particles with an organic compound, the dispersion of clay particles depends only on the compatibility of the surface of the clay particles with the thermoplastic resin or monomer used, so that the clay particles are not dispersed uniformly in nano size locally. The part that does not exist. In addition, since the increase in the distance between the clays, which is caused by the resin being inserted into the plate-shaped clay particles, is not sufficient, there is a limit to dispersing the clay particles in the nano-size, which is expected to simultaneously improve the mechanical strength, heat resistance characteristics and impact resistance. It's hard to do.

Therefore, in order to solve the above problems, the present inventors have emulsified and polymerized a clay mineral modified with a hydrophilic organic compound as an emulsifier in polymerizing a thermoplastic resin, thereby making nano-size clay minerals in a thermoplastic resin (nano-size). The present invention provides a thermoplastic resin composite material and a method of manufacturing the same, which are prepared by being uniformly dispersed in a layer, and have improved mechanical strength and heat resistance without deteriorating impact resistance.

An object of the present invention is to provide a thermoplastic resin composite material excellent in mechanical strength and heat resistance.

It is another object of the present invention to emulsify and polymerize a clay mineral modified with a hydrophilic organic compound as an emulsifier, so that the clay mineral is uniformly dispersed in a nano-sized layer in a thermoplastic resin, thereby providing excellent mechanical strength and heat resistance without deteriorating impact resistance. It is to provide a method for producing a resin composite material.

The above and other objects of the invention can be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.

The thermoplastic resin composite material of the present invention is subjected to an ion exchange reaction using an onium ion-containing compound containing 100 parts by weight of a polymer or copolymer prepared from a vinyl monomer or a mixture of two or more vinyl monomers, and an azo or peroxide group. It is composed of 0.1 to 50 parts by weight of modified clay minerals, the resin composite material to modify the clay minerals through an ion exchange reaction using an onium ion-containing compound containing azo groups or peroxide groups, the modified clay minerals as an emulsifier It is prepared by emulsion polymerization of a vinyl monomer or a mixture of two or more vinyl monomers in the presence of a polymerization initiator.

Specifically, 100 parts by weight of a polymer or copolymer prepared from a vinyl monomer or a mixture of two or more vinyl monomers, 0.01 to 1.0 part by weight of an initiator, and 0.1 to 50 parts by weight of a modified clay mineral are sufficiently stirred, and the contents are stirred. Dissolve completely. An appropriate amount of deionized water is added thereto, and the mixture is sufficiently stirred, and then the temperature is raised to perform emulsion polymerization. At this time, the modified clay mineral is swollen by deionized water, exfoliated, and has a hydrophilic group to emulsify the vinyl monomer in deionized water. After the polymerization is completed, it remains in the polymer in a peeled state, thereby improving mechanical strength and heat resistance, and simultaneously maintaining the impact resistance.

The present invention is described in detail as follows.

Examples of vinyl monomers used in the present invention are styrene, alphamethylstyrene, vinyltoluene, styrene having an alkyl substituent on the benzene ring (for example, o-, m- or p-methylstyrene and o-, m- or pt). -Butyl styrene), styrene having halogen substituents on the benzene ring (e.g. o-, m- or p-chlorostyrene and o-, m- or p-bromostyrene), divinylbenzene, acrylonitrile, meta Chrylonitrile, ethacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, acrylic acid, butadiene, isoprene, chloroprene, butene, vinyl chloride, vinylidene chloride, acrylamide , Methyl acrylamide, ethyl acrylamide, vinyl alcohol, vinyl pyridine, vinyl pyrrolidone, vinyl acetate, maleic anhydride, maleimide, N-phenylmaleimide, or mixtures thereof.

As an initiator used in the present invention, an initiator which can be used in emulsion polymerization of a vinyl monomer, examples thereof include an organic peroxide, an azo compound, and more specific examples thereof, such as benzoyl peroxide, t-butylperbenzoate, t- Butyl peracetate, azobisisobutylonitrile, percarbonate, or azobis-2-methylbutylonitrile.

In the present invention, in order to control the molecular weight of the polymer produced, t-dodecyl multicaptan and n-dodecyl multicaptan may be used as the molecular weight regulator if necessary.

Clay mineral, an inorganic additive used in the present invention, is a plate-like mineral having a length and width of about 500-2000 mm 3 and a thickness of 9-12 mm 3, and the distance between each layer is about 10 mm 3, and generally such a plate-like layer. The stacked stacked state forms an agglomerated form. Clay minerals used in the present invention are smectite type clays such as montmorillonite, saponite, hectorite, and these may be used alone or in mixture of two or more thereof. The clay used is a plate-like clay mineral with a cationic exchange capacity of 50 to 200 milligrams per 100 grams, and the clay is easily modified by an onium ion-containing compound such as ammonium ion containing azo or peroxide groups through ion exchange reaction. do. Onium ion-containing compounds used for the organic treatment of clays include dimethyl dihydrotallowalkyl ammonium chloride, dimethyl hydrotallowalkyl benzyl ammonium chloride, dimethyl 2-ethylhexyl hydrotallow alkyl ammonium chloride, and dimethyl diethoxymethyl. Hydrotallowalkyl ammonium chloride, trimethylhydrotallowalkyl ammonium chloride, stearyl bis (2-hydroxyethyl) methyl ammonium chloride, vinylbenzyltrimethylammonium chloride, vinylbenzyltrimethylammonium bromide, vinylbenzyltrimethylammonium iodide, vinyl Benzyltriethylammonium chloride, vinylbenzyltriethylammonium bromide, vinylbenzyltriethylammonium iodide, 2-methacryloyloxy ethyl trimethylammonium chloride, 2-methacryloyloxy ethyl trimethylammonium bromide , 2-methacryloyloxy ethyl trimethylammonium iodide, 2-methacryloyloxy ethyl triethylammonium chloride, 2-methacryloyloxy ethyl triethylammonium bromide, 2-methacryloyloxy ethyl tri Ethylammonium iodide, 2-acryloyloxy ethyl trimethylammonium chloride, 2-acryloyloxy ethyl trimethylammonium bromide, 2-acryloyloxy ethyl trimethylammonium iodide, 2-acryloyloxy ethyl triethyl Ammonium chloride, 2-acryloyloxy ethyl triethylammonium bromide, 2-acryloyloxy ethyl triethylammonium iodide, 3-methacryloylamino propyl trimethylammonium chloride, 3-methacryloylamino propyl trimethyl Ammonium bromide, 3-methacryloylamino propyl trimethylammonium iodide, 3-acryloylamino propyl tri One side such as butylammonium chloride, 3-acryloylamino propyl trimethylammonium bromide, 3-acryloylamino propyl trimethylammonium amide, diallyldimethyl ammonium chloride, diallyldimethyl ammonium bromide, diallyldimethyl ammonium iodide Onium ions capable of ion-exchange reaction with clay and compounds having vinyl groups capable of radical polymerization on the other side are used, and these may be used alone or in mixture of two or more thereof.

Through the organic treatment of the clay, a hydrophilic organic compound exists in the space between the clay layers, and the distance between the clay layers increases according to the molecular size of the organic compound. The modified clay mineral is in a peeled state in which the distance between the layers is further increased by deionized water, and the lamination structure is completely broken. After the lamination structure is broken, each layer acts as an emulsifier having lipophilic and hydrophilic groups at the same time to enable emulsion polymerization of vinyl monomers. The content of the modified clay is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer.

To the resin composition, inorganic additives, antioxidants, other light stabilizers, waxes, pigments, or dyes may be added in necessary amounts depending on the use.

The thermoplastic resin composite material obtained according to the above production method has a high industrial use value because of excellent mechanical strength, heat resistance, and thermal stability without deterioration of impact resistance.

The present invention will be further illustrated by the following examples, which are only described for the purpose of illustrating the present invention and are not intended to limit the protection scope of the present invention. The following parts and percentages are by weight unless otherwise indicated.

Example

Example 1

5 parts of modified clay surface-treated with dimethyl hydrotallowalkyl benzyl ammonium chloride, a monomer mixture of 75 parts of styrene and 25 parts of acrylonitrile, 0.2 parts of azobisisobutylonitrile and 0.2 parts of t-dodecyl multicaptan were added to the reactor, and After mixing, 200 parts of deionized water was added to the reactor, followed by stirring to emulsify. The temperature was raised to 75 ° C. for polymerization for 2 hours, the temperature was raised to 100 ° C. for 1 hour to polymerize, and the polymerization was terminated. The resulting polymer was solidified with sulfuric acid, washed and dried to obtain a thermoplastic composite. The resultant powdered thermoplastic composite was pelleted using an extruder at 220 ° C., and the specimen was made using a 5.3 oz. Injection molding machine to measure physical properties.

By the X-ray diffraction (XRD) the degree of dispersion of the clay in the resin and the distance between the clay was measured, the impact strength was measured by ASTM D-256.

Flexural modulus was measured by ASTM D-790 and tensile strength by ASTM D-638.

The onset temperature of decomposition was measured by thermogravimetric analysis.

Physical property measurement results are shown in Table 1.

Examples 2 to 3

The reaction was conducted in the same manner as in Example 1 except that the content of the modified clay mineral was changed as shown in Table 1, and physical properties were measured. Physical property measurement results for the prepared specimens are shown in Table 1.

Comparative Example 1

Except for adding clay, 75 parts of styrene, 25 parts of acrylonitrile, 0.2 parts of azobisisobutylonitrile, and 0.2 parts of t-dodecyl multicaptan were added to the reactor and polymerized as an initial monomer mixture. It was prepared by the method.

Example 1 Example 2 Example 3 Comparative Example Clay content (% by weight) 5 3 One 0 X-ray diffraction analysis Well dispersed Well dispersed Well dispersed - Impact Strength (kg.cm/cm) 2.7 2.7 2.7 2.7 Flexural modulus (kg / cm ² ) 49,000 45,000 39,000 31,000 Tensile Strength (kg / cm ² ) 850 810 780 710 Decomposition start temperature (℃) 451 440 431 425

As shown in Table 1, the X-ray diffraction analysis of the specimen showed that the characteristic peaks disappeared, indicating that the clay swells and peels and is evenly dispersed in the resin when treated by the method according to the present invention. In addition, in the case of Example 1-3 with the addition of clay, the flexural modulus and tensile strength were improved compared to the comparative example, the decomposition start temperature was increased, the impact strength due to the addition of clay was not observed. Therefore, according to the present invention, it was confirmed that the thermoplastic resin composite material having excellent mechanical strength and heat resistance characteristics can be manufactured while maintaining the impact strength.

The present invention provides a thermoplastic resin composite material having excellent mechanical strength and heat resistance without deteriorating impact resistance by emulsifying and polymerizing clay mineral modified with a hydrophilic organic compound as an emulsifier to uniformly disperse the clay mineral in a nano-sized layer in a thermoplastic resin. It has the effect of providing a method of producing.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (8)

100 parts by weight of a polymer or copolymer prepared from a vinyl monomer or a mixture of two or more vinyl monomers; And 0.1 to 50 parts by weight of clay minerals modified through an ion exchange reaction using an onium ion-containing compound containing an azo or peroxide group; The thermoplastic resin composite material, characterized in that the clay mineral is uniformly dispersed in a nano-sized layer in the polymer or copolymer. The thermoplastic resin composite material according to claim 1, wherein the content of the modified clay mineral is 0.1 to 10 parts by weight. The method of claim 1, wherein the vinyl monomer is styrene, alphamethylstyrene, vinyltoluene, styrene having an alkyl substituent on the benzene ring, styrene having a halogen substituent on the benzene ring, divinylbenzene, acrylonitrile, methacrylonitrile , Ethacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, acrylic acid, butadiene, isoprene, chloroprene, butene, vinyl chloride, vinylidene chloride, acrylamide, methyl acryl Amide, ethyl acrylamide, vinyl alcohol, vinyl pyridine, vinyl pyrrolidone, vinyl acetate, maleic anhydride, maleimide, N-phenylmaleimide, and mixtures thereof. . The clay mineral according to claim 1, wherein the clay mineral is in the form of a plate having a cationic exchange capacity of 50 to 200 milligrams per 100 grams, and the smectite type clay such as montmorillonite, saponite, hectorite, alone or in combination A thermoplastic resin composite material, which is used as a mixture. The onium ion-containing compound used for the clay mineral modification is dimethyl dihydrotallowalkyl ammonium chloride, dimethyl hydrohydrotallowalkyl benzyl ammonium chloride, dimethyl 2-ethylhexyl hydrotallow alkyl ammonium chloride, dimethyl die Methoxymethyl hydrotallowalkyl ammonium chloride, trimethyl hydrotallowalkyl ammonium chloride, stearyl bis (2-hydroxyethyl) methyl ammonium chloride, vinylbenzyltrimethylammonium chloride, vinylbenzyltrimethylammonium bromide, vinylbenzyltrimethylammonium iodide , Vinylbenzyltriethylammonium chloride, vinylbenzyltriethylammonium bromide, vinylbenzyltriethylammonium iodide, 2-methacryloyloxy ethyl trimethylammonium chloride, 2-methacryloyloxy ethyl trimethylammonium broma Id, 2-methacryloyloxy ethyl trimethylammonium iodide, 2-methacryloyloxy ethyl triethylammonium chloride, 2-methacryloyloxy ethyl triethylammonium bromide, 2-methacryloyloxy ethyl Triethylammonium iodide, 2-acryloyloxy ethyl trimethylammonium chloride, 2-acryloyloxy ethyl trimethylammonium bromide, 2-acryloyloxy ethyl trimethylammonium iodide, 2-acryloyloxy ethyl tri Ethylammonium chloride, 2-acryloyloxy ethyl triethylammonium bromide, 2-acryloyloxy ethyl triethylammonium iodide, 3-methacryloylamino propyl trimethylammonium chloride, 3-methacryloylamino propyl Trimethylammonium bromide, 3-methacryloylamino propyl trimethylammonium iodide, 3-acryloylamino propyl Methylammonium chloride, 3-acryloylamino propyl trimethylammonium bromide, 3-acryloylamino propyl trimethylammonium amide, diallyldimethyl ammonium chloride, diallyldimethyl ammonium bromide, diallyldimethyl ammonium iodide and mixtures thereof Thermoplastic resin composite material, characterized in that selected from the group consisting of. The thermoplastic resin composite of claim 1, further comprising an inorganic additive, an antioxidant, other light stabilizers, waxes, pigments, or dyes. Modified clay minerals through ion exchange reaction using onium ion-containing compounds containing azo or peroxide groups, and using the modified clay minerals as emulsifiers, a vinyl monomer or a mixture of two or more vinyl monomers in the presence of a polymerization initiator. A process for producing the thermoplastic resin composite of claim 1 by emulsion polymerization under the following. The method for producing a thermoplastic resin composite material according to claim 7, further comprising an emulsion molecular weight modifier.