KR100835821B1 - Manufacturing method for polyester nanocomposite - Google Patents

Abstract

The present invention relates to a polyester nanocomposite and a fiber comprising a layered organic clay, and after preparing a layered organic clay having excellent thermal stability and containing a reactive group, and dispersing it with ultrasonic waves in ethylene glycol, Since the polyester nanocomposite chip which improved the dispersibility of the clay layer was formed through the polymerization reaction with the ester monomers, the fiber formed from the polyester nanocomposite has a high modulus of elasticity, low shrinkage rate, excellent dimensional stability, tires, belts, etc. It can be usefully used for reinforcing rubber products or other industrial purposes.

Polyester, Nanocomposite Fiber, Layered Clay, Silane Compound, Melt Spinning, Ultrasonic

Description

Manufacturing Method of Polyester Nanocomposite {Manufacturing method for polyester nanocomposite}

The present invention relates to a method for producing a polyester nanocomposite, and in particular, to prepare a layered organic clay having excellent thermal stability and to effectively disperse it in a solvent, and then polymerized with the polyester monomer to improve thermo-mechanical stability and gas barrier properties, etc. A method for producing a polyester nanocomposite.

A general polymer resin nanocomposite is a material in which a clay mineral having a layered structure is separated into a nano-sized plate-shaped basic unit and dispersed in a polymer resin, and a material that significantly improves thermo-mechanical properties and gas barrier properties, etc., than a conventional polymer resin. . Such

The properties of the polymer resin nanocomposite are due to the fact that the clay mineral has a plate-like structure, which has a high aspect ratio and a large area that can interact with the polymer.

However, the polymer resin nanocomposite as described above has excellent properties, but it is not easy to uniformly peel and disperse the layered clay in the polymer resin. This is because the layered clay mineral is hydrophilic and does not mix well with the hydrophobic polymer resin so that the polymer resin is not easily inserted between the layers of clay. Therefore, an organic agent, for example, alkylammonium, is inserted between the clay layers to widen the gap between the plates to facilitate the penetration of the polymer resin to prepare a nanocomposite.

The clay mineral may be separated into a nano-sized plate-shaped basic unit and dispersed in a polymer resin, such as a solution method, a compounding method, a polymerization method, or the like.

The solution method is a method in which the organic clay is immersed in the polymer resin solution so that the solvent penetrates between the layers of the clay to disperse the clay layers, and the clay layers are dispersed in the polymer resin during the drying process. Here, the solution method is very limited solvent that can dissolve the polymer resin, there is a difficulty in recovering the solvent after manufacture.

In addition, the compounding method is a method of inserting and dispersing the polymer resin in the molten state between the clay layer by mechanical mixing, easy manufacturing process and low cost, but the nano-composite material is not uniformly dispersed in the polymer resin There is a problem of poor physical properties.

In addition, the polymerization method is a technique of dispersing the clay layers in the polymer resin by inserting a monomer between the clay layer, and then polymerized with the polymer resin, the clay and the monomer is mixed at the beginning of the reaction to easily insert the monomer between the clay layer There is an advantage that the production of nanocomposites in which the clay layers are completely peeled off in the polymer.

In order to use the above methods for producing the polyester nanocomposite, a process of modifying the surface and interlayer properties of the layered clay dispersed in the polyester into a layered organic clay that is compatible with the polyester is required. A layered organic clay is prepared by substituting a hydrophilic inorganic cation with a hydrophobic organic cation, and the organic cation is intercalated between clay layers to increase the layer spacing of the clay so that monomers or polymers can be easily inserted between the clay layers. And improve the compatibility of the clay with the polyester resin.

As the most widely used organic agent for producing the layered organic clay, ammonium ions are used. The ammonium ions are easily derived from various kinds of amines, so the manufacturing process is simple and inexpensive. However, the ammonium ions are poor in thermal stability, and thermal decomposition starts at about 200 ° C. so that the hydrophobicity of the layered organic clay is eliminated. Therefore, the organic clay substituted with ammonium ions is difficult to be used for the production of polyester resin nanocomposites requiring a processing temperature of 200 ° C. or higher, and the nanocomposites are discolored or decomposed during the polymerization or extrusion process, thereby deteriorating physical properties. .

In order to solve this problem, a layered organic clay having excellent thermal stability should be used.

To this end, methods for using phosphonium ions as organic agents have been studied, and World Patent No. 98/10012 discloses a method for preparing organic clay having high thermal stability by inserting phosphonium ions between clay layers. , WO 00/78540 and WO 00/78855 disclose a method for producing nanocomposites by melt compounding organic clay substituted with phosphonium ions with a polymer resin.                         

In the above-described layered organic clay manufacturing method, phosphonium ions have excellent thermal stability, but are mainly composed of aliphatic carbon chains, which makes it difficult to prepare nanocomposites with polar polymers.

The present invention is to solve the above problems, an object of the present invention is to form a layered organic clay excellent in thermal stability and affinity with a polar polymer, and easily formed polyester nanocomposites and fibers with improved dispersibility It is to provide a method for producing a polyester nanocomposite having a high modulus of elasticity, low shrinkage, excellent dimensional stability.

Features of the method for producing a polyester nanocomposite according to the present invention for achieving the above object,

Mixing a layered clay with an organic agent comprising a reactive group to form a layered clay substituted with an organic agent,

Adding a silane compound to the layered clay substituted with the organic agent to form a layered organic clay compound,

Adding ethylene glycol to the layered organic clay compound and dispersing it with ultrasonic waves;                     

And polymerizing the dispersed layered organic clay mixture with polyester monomers to form a polyester nanocomposite.

Another feature of the method for producing a polyester nanocomposite according to the present invention, the layered clay is a natural or synthetic mineral consisting of a plate-like layer having a length and width of 100 ~ 5,000㎛, thickness of 6 ~ 15Å, aspect ratio 100 ~ 5,000 Cation exchange capacity of 20 meq / 100g-200meq / 100g, the layered clay is montmorillonite, bentonite, hectorite, fluoride hectorite, Weidelite, saponite, nontronite, vermiculite, macadamite, mica or fluorinated Mica,

The organizing agent is a phosphonium cation salt having a structure of Formula 1, and the silane compound is vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, octadecyltrimethoxysilane, gammaaminopropyltrimethoxysilane , Gamma aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-vinylbenzylaminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl Gamma aminopropyltrimethoxysilane, gamma glycidoxypropyltrimethoxysilane, gamma methacryloxypropyltrimethoxysilane, gamma mercaptopropyltrimethoxysilane, gamma-aminopropylphenyldimethoxysilane, gamma propionami Is formed of trimethoxysilane, N-trimethoxysilylpropyl-N (beta-aminoethyl) amine, trimethoxysilylundecylamine or trimethoxysilyl-2-chloromethylphenylethane, the ultrasonic waves being 20 kHz To 100 With a frequency of kH, the polyester resin is made of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate or a copolymer thereof.                     

In addition, another feature of the method for producing a polyester nanocomposite according to the present invention is to form a suspension by dispersing layered clay in water or a co-solvent of water and alcohol, and adding a phosphonium cation salt containing a reactive group to the suspension. After stirring for 1 to 48 hours at 25 ~ 100 ℃ to form a mixture, the mixture is centrifuged to obtain a solid, to remove the remaining anions of the solid to prepare a substituted layered organic clay, the layered organic clay Phosphonium cations in the cation are contained in a molar equivalent of 0.1 to 5 times the cation exchange capacity of the layered clay, and the layered organic clay is dispersed in water or a co-solvent of water and alcohol to form a suspension, and a silane compound in the suspension. After adding to form a mixture by stirring for 1 to 48 hours at 25 ~ 200 ℃, the mixture was centrifuged to obtain a solid, and frozen Drying to form the layered organic clay compound, wherein the silane compound in the layered organic clay is included in a molar equivalent of 0.1 to 5 times the cation exchange capacity of the layered clay, and is used in the mixing process with the ethylene glycol. The layered organic clay is added in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the polyester monomer, and the polymerization process is mixed at a constant molar ratio of ethylene glycol and terephthalic acid in a slurry reaction tank, and the mixture is stirred at room temperature. After the polymerization reaction to form an oligomer, the dispersed layered organic clay compound solution is added and stirred with ultrasonic waves for 1 to 20 minutes and polymerized. The polyester nanocomposite is an antioxidant, a heat stabilizer, a colorant, an antistatic agent, It is characterized in that it comprises a UV absorber or a flame retardant.

In addition, the polyester nanocomposite fiber manufacturing method is characterized in that the process of melt spinning the polyester nanocomposite prepared by the above method using an extruder,

Solidifying the spun uncalculated sand through a heating zone and a cooling zone;

And stretching the undrawn yarn in two steps to form the drawn yarn.

In addition, another feature of the polyester nanocomposite fiber manufacturing method according to the invention, the heating zone is heated to a temperature of 100 to 800mm, 300 to 400 ℃ temperature, the cooling zone is open cooling, circular hermetic cooling or radial outflow cooling Applying a method, oiling the discharged yarn solidified while passing through the cooling zone to 0.5 to 1.0% by means of an emulsion applying device, wherein the undrawn yarn has a birefringence index of 0.001 to 0.1 at the feed roller. The speed is 200 to 5,000 m / min, and the two-stage stretching process is 1 to 10% pre-draw, the first stage stretching to 1.2 to 7 times at 80 to 200 ℃, and then again from 1.2 to 130 ℃ The second step is drawn twice, and the drawn yarn is heat-set to a temperature of 200 to 260 ℃ after stretching, characterized in that to relax 1 to 6%.

Hereinafter, a method for producing a polyester nanocomposite according to the present invention will be described in detail.

The present invention

(One). Reacting the layered clay with an organic agent comprising a reactor to form a layered organic clay,

(2). Reacting the layered organic clay with a coupling agent including a reactive group to form a layered organic clay that is easily bonded to the polyester,

(3). The layered organic clay is mixed with a polyester resin in a solvent and polymerized to form a polyester nanocomposite,

(4). The fiber is spun into chips of the polyester nanocomposite.

At this time, the physical properties are measured and compared after the steps (3) and (4).

Looking at the characteristics of the materials and processes according to the present invention.

First, the layered clay uses natural or synthetic minerals composed of a plate-like layer having a length and width of 100 to 5,000 µm, a thickness of 6 to 15 microns, and an aspect ratio of about 100 to 5,000. The cation exchange capacity of the layered clay is 20 meq / Preference is given to 100 g-200 meq / 100 g, more preferably a layered clay having a cation exchange capacity of 50 meq / 100 g to 150 meq / 100 g. The layered clay may include montmorillonite, bentonite, hectorite, fluoride hectorite, bidelite, saponite, nontronite, vermiculite, macadamite, mica and fluorinated mica, and one or more of them may be used. For example, montmorillonite is used.

In addition, the organic agent including a reactive group is preferably a phosphonium cation salt that does not thermally decompose at a temperature of 300 ° C or more, and includes at least one reactive group capable of chemical bonding with the silane compound and the polyester monomer, and has a structure represented by the following Chemical Formula 1. .

[Formula 1] P ⁺ R ₁ R ₂ R ₃ R ₄

In Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ are chains of 4 to 40 carbons, and at least one of R ₁ to R ₄ is a carboxyl group or an amine group capable of chemically bonding to a silane compound and a polyester monomer. And reactive groups such as hydroxy group, ester group, epoxy group, silanol group, carbonate group or imide group.

In addition, a silane compound is used as a coupling agent, and the silane compound may chemically bond with the reactive group of the phosphonium cation salt, an organic agent existing between the layers of the organic clay, and chemically bond with the polyester monomers during the polymerization reaction. Acts as a coupling agent to connect the polyester resin, the silane compound may be characterized by R-SiX ₃ . Where R is an organic functional group having a reactive group and X means a methoxy group or an ethoxy group which can be converted to a silanol group by hydrolysis. Representative silane compounds include vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, octadecyltrimethoxysilane, gammaaminopropyltrimethoxysilane, gammaaminopropyltriethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, N- (2-vinylbenzylaminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-gammaaminopropyltrimethoxysilane, gamma glycidoxypropyl tree Methoxysilane, gamma methacryloxypropyltrimethoxysilane, gamma mercaptopropyltrimethoxysilane, gamma-aminopropylphenyldimethoxysilane, gamma propionamido trimethoxysilane, N-trimethoxysilylpropyl-N (Beta-aminoethyl) amine, trimethoxysilyl undecylamine, trimethoxysilyl-2-chloromethylphenylethane and the like.

In addition, the ultrasonic wave used in the present invention uses a low frequency region ultrasonic wave, which is an ultrasonic wave having a frequency of 20 kHz to 100 kH used for washing machines, welding of plastics or metals, and about 1 kHz to 10 used for medical devices or nondestructive testing. Ultrasound having a relatively lower frequency than that of a high frequency region having a frequency of kH.

When the ultrasonic wave is applied in a liquid medium, the distance of molecules is increased by repeated compression / expansion cycles, and the pupils are formed. When the ultrasonic waves are over a predetermined size, the ultrasonic waves are instantaneously high temperature and high pressure, and the molecules are destroyed to activate a chemical reaction. Therefore, when the ultrasonic wave is irradiated during the polymerization process of the polymer, in the mixed system of the organic treatment agent and the layered compound, the pulverized layered compound can be effectively crushed by the high energy ultrasonic vibration, the layered structure can be broken down, and the dispersion can be efficiently carried out. .

In addition, the polyester resin is at least one selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and copolymers thereof, more preferably polyethylene terephthalate Use

Looking at the manufacturing method of the polyester nanocomposite according to the present invention using such materials and equipment as follows.

First, to form a suspension by dispersing the layered clay in water or a co-solvent of water and alcohol, and adding a phosphonium cation salt containing a reactive group to the suspension and sufficiently stirred for 1 to 48 hours at 25 ~ 100 ℃ mixed solution After forming, the mixed solution is centrifuged to obtain a solid.

The solids are then washed several times with water to remove residual anions and lyophilized to produce layered organic clays substituted with phosphonium cation salts containing reactive groups. Here, the phosphonium cation in the layered organic clay is preferably included in a molar equivalent of 0.1 to 5 times the cation exchange capacity of the layered clay. In the molar equivalent of 0.1 times or less, the substituted phosphonium cation is too small to improve physical properties, and in the molar equivalent of 5 times or more, the excessive phosphonium cation acts as an impurity in the polyester nanocomposite, thereby reducing the physical properties.

Thereafter, the layered organic clay is dispersed in water or a co-solvent of water and alcohol to form a suspension, and a silane compound is added to the suspension to sufficiently stir at 25 to 200 ° C. for 1 to 48 hours to form a mixed solution. The mixture was centrifuged to obtain a solid, washed several times with water, and lyophilized to prepare a layered organic clay having a silane compound bonded to a phosphonium cation salt. Here, the silane compound in the layered organic clay is preferably included in a molar equivalent of 0.1 to 5 times the cation exchange capacity of the layered clay. It is difficult to improve the physical properties of the silane compound introduced at a molar equivalent of 0.1 times or less, so that the reaction with the polyester monomers is difficult due to the reaction between the silane compounds at a molar equivalent of 5 times or more.

Then, an appropriate amount of ethylene glycol and antimony trioxide were added to the layered organic clay compound prepared above, followed by stirring with ultrasonic waves to improve dispersibility.

Form a layered organic clay compound solution.

Thereafter, a polyester monomer or oligomer is mixed with the stirred ethylene glycol and the layered organic clay mixture, followed by polymerization to prepare a polyester nanocomposite. At this time, the layered organic clay is used 0.05 to 10 parts by weight, more preferably 0.5 to 2 parts by weight based on 100 parts by weight of the polyester monomer. This is because the amount of the layered organic clay is less than 0.05 parts by weight, it is difficult to improve the physical properties, at 10 parts by weight or more, the dispersibility of the layered clay is lowered and the physical properties are reduced.

The polymerization process is as follows.

First, ethylene glycol and terephthalic acid are mixed at a constant molar ratio in a slurry reaction tank and stirred at room temperature, and then the mixture is gradually added to the DE reaction tank maintained at 258 ° C. over about 3 hours to prepare an oligomer. In this case, the same amount of oligomer as the mixture added to promote the esterification reaction is preliminarily introduced into the DE reaction tank.

The oligomer is then transferred to a PC reactor maintained at 285 ° C., and then the dispersed layered organic clay compound solution is added and stirred for 1 to 20 minutes with ultrasonic waves.

Thereafter, the polymerization reaction is carried out at a pressure of 0.5 Torr or lower for about 3 hours, and when the desired intrinsic viscosity is reached, the reaction is stopped and discharged to form a polyester nanocomposite, which is processed into a chip state to form a polyester nanocomposite chip. To form. Here, the polyester nanocomposite may be added an antioxidant, a heat stabilizer, a colorant, an antistatic agent, a UV absorber and a flame retardant as necessary.

Looking at the spinning process using the polyester nanocomposite chip formed as described above are as follows.

First, the polyester nanocomposite chip is melt-spun through a pack and a nozzle at 280 to 310 ° C. temperature without lowering the viscosity of the polymer by pyrolysis and hydrolysis. At this time, the nanocomposite chip may be uniformly mixed, and a static mixer or the like may be installed in the upper part of the pack in order to improve the uniformity of melt viscosity for each part.

The melt discharged yarn may then be solidified cooled to obtain undrawn yarn. The solidification cooling process solidifies the melt-discharged sand produced in the spinning step through a cooling zone, passing through a delayed cooling zone or heating zone in which a heating device is installed from below the nozzle to the start of the cooling zone, if necessary. The heating zone is heated to a temperature of about 300 to 400 ° C. about 100 to 800 mm long.

In addition, the cooling zone for solidifying cooling may be applied with an open quenching method, a circular closed quenching method and a radial outflow quenching method according to a method of blowing cooling air. It is not limited to this.

It is also possible to oil the discharged yarn solidified while passing through the cooling zone to 0.5 to 1.0% by the emulsion applying device.

In the drawing step of the undrawn yarn, the undrawn yarn is wound at a spinning speed such that the birefringence rate of the undrawn yarn is 0.001 to 0.1 in the feed roller, and the preferred spinning speed is 200 to 5,000 m / min. If the birefringence of the undrawn yarn is less than 0.001, the radiation tension is not taken during spinning, so the unstable yarn becomes uneven, and the undrawn yarn becomes non-uniform, and if it exceeds 0.1, it is difficult to post-stretch and it is difficult to manufacture low shrinkage yarn.

Thereafter, the undrawn yarn having passed through the feed roller is taken out, and then drawn through a series of draw rollers by a spin draw method to multistage to obtain a final drawn yarn. More specifically, 1 to 10% of free draw is given first, followed by the first stage stretching at 1.2 to 7 times at 80 to 200 ° C, and the second stage stretching to 1.2 to 2 times at 130 to 200 ° C. Do it. Here, in order to increase the uniformity of high magnification stretching during the first stage stretching, a steam jet method may be applied.

The finished drawn yarn can then be heat set to a temperature of 200 to 260 ° C. and relaxed by 1 to 6% according to conventional methods.

As described above, the present invention provides a polyester nanocomposite fiber comprising a nano-compound dispersed clay compound, wherein the nanocomposite fiber formed therefrom has a high elastic modulus, a low shrinkage rate, excellent dimensional stability, and a reinforcing agent of a rubber product or It can be usefully used for other industrial purposes.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

The evaluation method of the physical property used in the Example and the comparative example is as follows.

[Property evaluation method]

1) Differential Scanning Thermal Analyzer (DSC): melting point and crystallization temperature measurement.

2) X-ray diffraction experiment: Measurement of interlayer distance of layered organic clay layer of polyester nanocomposite.                     

3) Scanning electron microscope: Considering the dispersibility (number of particles) of layered organic clay particles of polyester nanocomposite chip.

4) Intrinsic Viscosity (IV): 0.1g of sample was dissolved in 90g at 90 ℃ for 90 minutes in a reagent mixed with phenol and 1,1,2,2-tetrachloroethane at a weight ratio of 6: 4. The resultant was transferred to a Ubbelohde viscometer, held for 10 minutes in a 30 ° C. thermostat, and the number of seconds of the drop of the solution was determined using a viscometer and an aspirator. The intrinsic viscosity was calculated after obtaining the falling seconds of the solvent by the same method.

5) Tensile Properties: Strength, modulus, elongation and elongation were measured under standard conditions (20 ℃, 65% relative humidity) under standard conditions (20 ℃, 65% relative humidity) under a sample length of 250mm, tensile speed of 300mm / min, and 20 turns / m. . Intermediate elongation was determined as elongation at load 6.8 kg.

6) Shrinkage: After leaving the sample at 20 ° C and 65% relative humidity for more than 24 hours, weigh the weight equivalent to 0.05g / d and measure the length (L ₀ ), and in the drying oven maintained at 180 ° C. The shrinkage rate was calculated by measuring the length L after the treatment for 2 minutes.

<Example 1>

10 g of montmorillonite, a clay, was dispersed in 500 ml of water, and a phosphonium cationic salt, HOC ₁₁ H ₂₂ (C ₆ H ₅ ) ₃ P ⁺ Cl ^- 10 g was added thereto, and the mixture was sufficiently stirred at 70 ° C. for 24 hours. The mixture was centrifuged to obtain a solid, washed with water, and then centrifuged again for three times. The obtained solid is freeze-dried to prepare a layered organic clay in powder form.

Then, a suspension was prepared by dispersing 10 g of the layered organic clay prepared above in 500 ml of water, and adding 2 g of a silane compound NH ₂ (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ to 24 hours at 70 ° C. Was stirred sufficiently. The mixture was centrifuged to obtain a solid, washed with water, and then centrifuged again for three times. The obtained solid is freeze-dried to prepare a layered organic clay in powder form.

Thereafter, 100 g of the layered organic clay and 2.8 g of the antimony trioxide are added to 1,000 g of ethylene glycol, and then stirred to obtain a layered organic clay compound solution. At this time, by stirring the ultrasonic wave for 10 minutes to improve the dispersibility.

Thereafter, 8.6 kg of terephthalic acid and 3.8 kg of ethylene glycol were mixed in the slurry reactor and stirred at room temperature, and the mixture was slowly added to the DE reactor maintained at 258 ° C. over about 3 hours to perform an esterification reaction to prepare an oligomer. At this time, the same amount of oligomer as the mixture introduced in order to promote the esterification reaction was previously added into the DE reactor.

Thereafter, half of the prepared oligomer was transferred to a PC reactor maintained at 285 ° C., the layered organic clay compound solution was added and stirred, and the polymerization reaction was performed under reduced pressure to 0.5 Torr or less for about 3 hours, and then When the viscosity reaches 0.63 dL / g, the reaction is stopped and discharged to prepare a nanocomposite in the chip state.                     

Then, the polyester nanocomposite chip was subjected to solid phase polymerization to prepare a nanocomposite chip having an intrinsic viscosity of 1.0, and the nanocomposite chip was melt-spun at an ejection rate of 440 g / min at a temperature of 300 ° C. using an extruder to form undrawn yarn. Then, it extends | stretches and forms a stretched yarn.

Here, in the extrusion process, a static mixer having two units is installed in the polymer conduit of the pack to uniformly mix the melt-spun polymer, and the discharge yarn is a heating zone having a length of 200 mm directly under the nozzle and an ambient temperature of 320 ° C., and a length of 500 mm. It is solidified by passing through a cooling zone in which cooling air having a wind speed of 20 ° C. and 0.5 m / sec is blown and then oiled with a spinning emulsion. In addition, the stretching process winds the undrawn yarn at a spinning speed of 525 m / min, and stretches in two stages. The first stage stretching is 4.15 times at 150 ° C., the second stage stretching is 1.4 times at 170 ° C., and the heat is heated at 230 ° C. After fixing, 3% of the present invention was wound up to prepare a final stretched yarn of 1500 denier.

The physical properties of the polyester nanocomposite and the stretched yarn prepared above were evaluated, and the results are shown in Table 1.

<Example 2>

10 g of montmorillonite was dispersed in 500 ml of water to form a suspension, and thereto, phosphonium cationic salt HOC ₁₁ H ₂₂ (C ₆ H ₅ ) ₃ P ⁺ Cl ^- 10 g was added thereto, followed by sufficient stirring at 70 ° C. for 24 hours. The mixed solution is centrifuged to obtain a solid, and then washed with water, and the process of centrifugation is repeated three times to freeze-dry the solid to prepare a layered organic clay in powder form.

Then 10 g of the layered organic clay prepared above was dispersed in 500 ml of water to form a suspension, and ₂ g of the silane compound NH ₂ (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ was added thereto for 24 hours at 70 ° C. After sufficiently stirring for a while, the mixed solution was centrifuged to obtain a solid, washed with water, and then the centrifuged process was repeated three times to dry the solid obtained at room temperature to prepare a layered organic clay in the form of a slurry.

Thereafter, the polyester nanocomposite was prepared in the same manner as in Example 1 using the slurry-type layered organic clay, and the prepared nanocomposite chip was subjected to solid phase polymerization, and then the polyester nanocomposite in the same manner as in Example 1. Prepare the fibers.

The physical properties of the prepared polyester nanocomposite and stretched yarn were evaluated, and the results are shown in Table 1.

<Comparative Example 1>

8.6 kg of terephthalic acid and 3.8 kg of ethylene glycol were mixed in the slurry reactor and stirred at room temperature, and the mixture was slowly added to the DE reactor maintained at 258 ° C. over about 3 hours to perform an esterification reaction to prepare an oligomer. At this time, in the DE reactor, the oligomer of the same amount as the mixture to be introduced to promote the esterification reaction is introduced in advance.                     

Then, half of the prepared oligomer was transferred to a PC reactor maintained at 285 ° C., followed by addition of 2.8 g of antimony trioxide, polymerization reaction for about 3 hours under reduced pressure of 0.5 Torr or less, and an intrinsic viscosity of 0.63 dL / g. When the reaction is reached, the reaction is stopped and discharged to prepare a polyester polymer chip in a chip state.

Thereafter, the polyester polymer chips thus prepared are subjected to solid phase polymerization, and then polyester stretched yarn is manufactured in the same manner as in Example 1.

The physical properties of the polyester polymer and the stretched yarn prepared above were evaluated, and the results are shown in Table 1.

<Comparative Example 2>

To 1,000 g of ethylene glycol is added 100 g of unorganized montmorillonite and 2.8 g of antimony trioxide to form a layered clay mixture. In this case, the ultrasonic wave was stirred for 10 minutes to improve dispersibility.

Thereafter, 8.6 kg of terephthalic acid and 3.8 kg of ethylene glycol were mixed in the slurry reaction tank and stirred at room temperature, and the mixture was slowly added to the DE reaction tank maintained at 258 ° C. over about 3 hours to perform an esterification reaction to prepare an oligomer. do. At this time, the same amount of oligomer as the mixture to be introduced in order to promote the esterification reaction in the DE reactor is put in advance.

Thereafter, half of the prepared oligomer was transferred to a PC reactor maintained at 285 ° C., and then the layered clay mixture was added and stirred, and the polymerization reaction was carried out for about 3 hours under reduced pressure of 0.5 Torr or less to inherent viscosity of 0.63 dL / After reaching the g, the reaction was stopped and then discharged to prepare a polyester nanocomposite in chip state.

Thereafter, the prepared nanocomposite chip is subjected to solid phase polymerization, and then, polyester nanocomposite stretched yarn is manufactured in the same manner as in Example 1.

The physical properties of the prepared polyester nanocomposite and stretched yarn were evaluated, and the results are shown in Table 1.

<Comparative Example 3>

Prepare a polyester nanocomposite in the same manner as in Example 1, but does not have an ultrasonic wave when the organic layered clay compound is dispersed in ethylene glycol.

Thereafter, the prepared nanocomposite chip is subjected to solid phase polymerization, and then, polyester nanocomposite stretched yarn is manufactured in the same manner as in Example 1.

The properties of the prepared nanocomposite and stretched yarn were evaluated and the results are shown in Table 1.

<Comparative Example 4>

In the same manner as in Example 1 to form a polyester nanocomposite material and the _{filament, HOC 11 H 22 (C 6} H 5) 3 P + Cl - instead of _{C 12 H 25 (C 6 H} 5) 3 P + Cl - a Formed by applying, and evaluated the physical properties of the prepared nanocomposite and stretched yarn are shown in Table 1 the results.

As shown in Table 1, Examples 1 and 2 are applied to the ultrasonic wave during the mixing of the layered organic clay according to the present invention to form a polyester nanocomposite, the layered organic clay mixture is in the form of a powder or slurry, Comparative Example 1 is a polyester polymer was formed without adding a layered organic clay, Comparative Example 2 is an example using an unorganized layered clay, Comparative Example 3 is a polyester nanocomposite was formed without applying an ultrasonic wave, the comparison Example 4 is an example in which the organic agent was changed.

It can be seen that the polyester nanocomposite of the present invention improves the dispersibility of the clay layer than the comparative examples, and the fibers have a high elastic modulus, a low shrinkage ratio, and excellent dimensional stability.

Table 1

As described above, the method for producing a polyester nanocomposite according to the present invention has excellent thermal stability and after preparing a layered organic clay containing a reactive group, and then dispersing it with ultrasonic waves in ethylene glycol, polyester Since the polyester nanocomposite chip which improved the dispersibility of the clay layer was formed through the polymerization reaction with the monomers, the fibers formed from the polyester nanocomposite had a high modulus of elasticity, low shrinkage, and excellent dimensional stability, and thus, rubber such as tires and belts. There is an advantage that can be usefully used as a product reinforcement or other industrial uses.

Claims (11)

Mixing a layered clay with a phosphonium cation salt containing a reactive group as an organic agent comprising a reactive group to form a layered clay substituted with an organic agent; Adding a silane compound to the layered clay substituted with the organic agent to form a layered organic clay compound, Adding ethylene glycol to the layered organic clay compound and dispersing it with ultrasonic waves; And polymerizing the dispersed layered organic clay mixture with polyester monomers to form a polyester nanocomposite. The method of claim 1, wherein the layered clay is one selected from the group consisting of montmorillonite, bentonite, hectorite, fluoride hectorite, Weidelite, saponite, nontronite, vermiculite, macadamite, mica and fluorinated mica Method for producing a polyester nanocomposite, characterized in that formed from the above material. The method of claim 1, wherein the phosphonium cation salt has a structure of Formula 1 below. [Formula 1] P ⁺ R ₁ R ₂ R ₃ R ₄ In Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ are chains of 4 to 40 carbons, and at least one of R ₁ to R ₄ is a carboxyl group or an amine group capable of chemically bonding to a silane compound and a polyester monomer. And reactive groups such as a hydroxy group, an ester group, an epoxy group, a silanol group, a carbonate group and an imide group. The method of claim 1, wherein the silane compound is vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, octadecyltrimethoxysilane, gammaaminopropyltrimethoxysilane, gammaaminopropyltriethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-vinylbenzylaminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-gammaaminopropyltrimethoxysilane, gamma Glycidoxypropyltrimethoxysilane, gamma methacryloxypropyltrimethoxysilane, gamma mercaptopropyltrimethoxysilane, gamma-aminopropylphenyldimethoxysilane, gamma propionamido trimethoxysilane, N-trimeth Polyester nanocomposite, characterized in that at least one selected from the group consisting of oxysilylpropyl-N (beta-aminoethyl) amine, trimethoxysilyl undecylamine and trimethoxysilyl-2-chloromethylphenylethane The method of manufacture. The method of claim 1, wherein the polyester resin is characterized in that one or more selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and copolymers thereof. The manufacturing method of the polyester nanocomposite which uses it. The process of claim 1, wherein the forming of the layered clay substituted with the organic agent comprises dispersing the layered clay in water or a co-solvent of water and alcohol to form a suspension, and the phosphonium cation salt containing a reactive group in the suspension. After adding to form a mixture by stirring for 1 to 48 hours at 25 ~ 100 ℃, the mixture is centrifuged to obtain a solid, characterized in that to remove the remaining anions of the solid to prepare a substituted layered organic clay Method for producing a polyester nanocomposite. 7. The method of claim 6, wherein the phosphonium cation in the layered organic clay is included in a molar equivalent of 0.1 to 5 times the cation exchange capacity of the layered clay. The method according to claim 1, wherein the layered organic clay is used in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the polyester monomer. The method of claim 1, wherein the polymerization step is mixed with ethylene glycol and terephthalic acid in a constant molar ratio in a slurry reaction tank and stirred at room temperature, and the mixture is esterified to form an oligomer, and then a dispersed layered organic clay compound solution is added. And stirring for 1 to 20 minutes with ultrasonic waves, and polymerizing the polyester nanocomposite. Melting and spun the polyester nanocomposite prepared by the method of any one of claims 1 to 9, Solidifying the spun uncalculated sand through a heating zone and a cooling zone; A method for producing a polyester nanocomposite fiber comprising the step of stretching the undrawn yarn in two steps to form a drawn yarn. 12. The method of claim 10, wherein the undrawn yarn has a spinning speed of 200 to 5,000 m / min so that the birefringence of the undrawn yarn is 0.001 to 0.1 at the feed roller, and the two-stage stretching process has a free draw of 1 to 10%. And 1.2 to 7 times the first step stretching at 80 to 200 ° C., and then to the second step at 1.2 to 2 times again at 130 to 200 ° C. for producing the polyester nanocomposite fibers.