KR100847044B1 - Method of preparing clay nanoparticels-distributed polyol for producing urethane form - Google Patents

Abstract

The present invention relates to a method for producing a polyol for producing urethane foam in which clay-based nanoparticles are dispersed. The method for preparing a slurry is prepared by dispersing plate-like clay-based particles in water, and stirring the slurry in a polyol for 30 minutes to Dropwise for 1 hour and fractional distillation of the resulting mixture to remove water.

The production method by uniformly dispersing the plate-shaped clay nanoparticles in a polyol which is a raw material of the urethane production, by producing a polyol can be used to prepare a urethane foam excellent flame retardant without using a flame retardant.

Urethane, Polyol, Clay Nanoparticles, Flame Retardant

Description

METHODS OF PREPARING CLAY NANOPARTICELS-DISTRIBUTED POLYOL FOR PRODUCING URETHANE FORM}

1 is a graph showing the results of X-ray diffraction measurement of the polyol of Example 1 and Comparative Example 2 of the present invention.

[Industrial use]

The present invention relates to a method for producing a polyol for producing urethane foam in which clay-based nanoparticles are dispersed, and more particularly, to a method for producing a polyol for producing urethane foam in which clay-based nanoparticles are not required to use a flame retardant.

[Prior art]

In general, a lot of materials that are excellent in energy absorption effects, such as shock and sound insulation are used in the automotive and construction fields. Although a felt made by the resin treatment of the recycled surface and the synthetic fiber is used as the energy absorbing material, the felt has a disadvantage of high manufacturing cost. Due to these drawbacks, polyurethane foams, which are inexpensive and easy to process, have advantages such as excellent energy absorption ability, molding of complex parts, low specific gravity, and low processing cost, are frequently used.

Polyurethane foams having these properties are prepared by mixing a polyol and an isocyanate and adding a blowing agent, a flame retardant or the like to the mixture. At this time, due to the flame retardant used, if a fire occurs there is a problem that toxic gas harmful to the human body is generated from the flame retardant contained in the polyurethane foam. For this reason, the use of flame retardants has been gradually regulated in recent years.

It is an object of the present invention to provide a method for producing a polyol for preparing urethane foam in which clay-based nanoparticles are dispersed, which can produce a flame retardant urethane foam without using a flame retardant.

In order to achieve the above object, the present invention is to prepare a clay-based nanoparticle slurry by dispersing the plate-shaped clay-based particles in water; Adding the clay nanoparticle slurry to the polyol dropwise with stirring; Provided is a method for producing a polyol for producing urethane foam in which clay-based nanoparticles are dispersed, including a step of fractionally distilling the obtained mixture to remove water.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a method for producing a polyol capable of producing a flame retardant urethane foam without using a flame retardant that generates toxic gases harmful to the human body in case of fire.                     

The production method of the present invention is to disperse the plate-shaped clay-based particles in a nano-size polyol, which is a raw material for the production of flame-retardant urethane foam, and to disperse uniformly dispersed clay-based nano-particles without polyol and nano-sized plate-like clay-based precipitation To prepare a polyol. That is, by using the polyol to which the inorganic particles are added, it is possible to produce a urethane foam having excellent flame retardancy without using a flame retardant, and also to prevent the problem that the inorganic particles are precipitated because the inorganic particles are dispersed in nano size. have.

As the inorganic particles, plate-like clay-based particles were used, and when plate-like clay-based particles were added to the water and stirred, water molecules were inserted into the interlaminar layers of plate-like clay particles and swelled to remove the interlayers, that is, in water It is a method that can impart sufficient flame retardancy to polyol by adding a small amount of inorganic particles, that is, clay particles, to the polyol by using the property of completely collapsed to become nano-sized and the polyol is well mixed in water. . That is, in general, an organic agent of the amine compound was used to disperse the plate-shaped clay particles in the polymer material at a nano size, but when preparing the urethane using the polyol, the amine compound acted as an accelerator of the urethane reaction, causing an instant reaction. In the present invention, it was not possible to use the organizing agent, and the plate-like clay-based particles could be dispersed between the polyols at a nano size by using the above-described absorption and peeling properties of water of the plate-like clay-based nanoparticles.

The manufacturing method of the present invention first prepares a slurry in which clay-based particles are dispersed in a nano state by dispersing plate-shaped clay-based particles in water.

The plate-shaped clay particles are smectite-based clays in which a three-layer structure (Si-Al-Si) is collected at a ratio of 2: 1 of Si and Al octahedra to form a plate, for example, montmorillonite , Hectorite or bentonite. One plate is about 1 nm thick and the distance between the plates is known to be about 1 nm. In addition, such a plate forms a layer structure composed of several layers. In addition, an exchange cation such as Na ⁺ or Ca ⁺ exists between the plate of the smectite-based clay and when the smectite-based clay is added to water by such exchange cations, the water absorbs the water and expands or forms a layer. Hydration occurs when each plate in the structure collapses. Usually these smectite-based clay-based particles are known to absorb 20 to 30 times their volume.

You may further add a silane type compound to the said slurry. The amount of the silane compound added is preferably 0.1 to 5% by weight based on the weight of the plate-like clay particles, and when the amount of the silane compound is less than 0.1% by weight, the effect of further addition of the silane compound has little effect. In the case where the wt% is added, there is a possibility that the physical properties may decrease when the urethane foam is manufactured using the prepared polyol, which is not preferable.

The silane-based compound is a silane reaction on the hydroxy group (-OH) on the surface of the plate-like clay particles to widen the interlaminar layer, and this chemical bond effectively prevents precipitation of the plate-like clay particles Can be. As such a silane-based compound, a silane in a form well mixed with water is advantageous if possible, and general silane is also possible. Representative examples thereof include 3-aminopropyl triethoxy silane, 3-mercaptopropyl triethoxy silane, 3-mercaptopropyl trimethoxy silane or vinyltriethoxysilane.

Polyol is added to the slurry in which the clay-based nanoparticles are dispersed. The addition amount of the polyol is adjusted so that the mixing ratio of the polyol and the clay-based nanoparticles is 0.5 to 15 parts by weight of the clay-based nanoparticles based on 100 parts by weight of the polyol. When the amount of the clay-based nanoparticles is less than 0.5 parts by weight with respect to 100 parts by weight of polyol, the amount of nanoparticles added is too small to obtain the effect of the addition of minerals. It is not preferable because there is difficulty in processing the urethane production reaction going up too much.

At this time, since the polyol is mixed well with water uniformly, the polyol is added dropwise to the slurry with stirring to disperse the plate-like clay slurry in the polyol. The dropping time is preferably 30 minutes to 1 hour, and when the dropping time is shorter than 30 minutes, the dispersion of plate-like clay-based slurry in the polyol does not occur effectively, and 1 hour is sufficient, so it is not necessary to carry out a longer time. . Since this reaction does not have a big influence on temperature, it is good to carry out at normal temperature. The mixture is vigorously stirred through a high speed stirrer for 6 to 24 hours. If the stirring time is less than 6 hours, the clay-based particles in the slurry phase may be agglomerated to form micro-sized particles, and in the case of more than 24 hours, the polyol is sufficiently inserted into the interlayer of the clay-based nanoparticles. However, the clay-based nanoparticles may not be preferable because of the continuous collisions, which may re-aggregate and precipitate after the reaction.

The mixture is then fractionally distilled to remove water. In the obtained product, plate-like clay particles are dispersed in a polyol in a nano state. After the water is removed, if there are many bubbles, a step of removing a small amount of residual water and bubbles in the vacuum oven may be further performed.

Hereinafter, examples and comparative examples of the present invention are described. However, the following examples are only one preferred embodiment of the present invention and the present invention is not limited to the following examples.

(Example 1)

50 grams of plate-based montmorillonite particles were dispersed in a liter of water at room temperature and dispersed through a high speed stirrer for about 2 hours until fully expanded. After the reaction is completed, when the plate-like clay-based inorganic particles are completely peeled off, a slurry in which viscous clay-based nanoparticles are dispersed is obtained.

The slurry was added dropwise to 2 liters of polyol for about 30 minutes while mixing through a high speed stirrer. The mixture was vigorously stirred at a speed of 5000 rpm through a high speed stirrer for 6 hours. Subsequently, the mixture was fractionally distilled to remove water, and a small amount of residual water and bubbles were removed in a vacuum oven to finally obtain a polyol in which plate-like clay particles were dispersed in a polyol in nano size.

(Example 2)

3-aminopropyl triethoxy silane, a silane-based compound, was added in the same manner as in Example 1 except that the mixture was added to the clay-based nanoparticle mixture in an amount of 0.1 wt% and reacted for 6 hours.

(Comparative Example 1)

To 2 liters of polyol was added 50 grams of inorganic particles calcium carbonate and the mixture was strongly dispersed through a high speed stirrer. The obtained mixture was removed in a vacuum oven to prepare a polyol in which calcium carbonate was dispersed.

(Comparative Example 2)

50 grams of platy clay particles were added to 2 liters of polyol and the mixture was strongly dispersed through a high speed stirrer. The resulting mixture was removed from the vacuum oven to prepare a polyol solution in which plate-like clay particles were dispersed.

However, in the polyol prepared by the method of Comparative Example 2, since the attractive force between the layers and layers of the plate-like clay-based particles act so strongly that the polyol particles are not inserted or the separation of the plate-like clay-based particles does not occur, the inorganic dispersed in the reaction polyol The particles were all precipitated within 1 hour and did not fully nanonize.

(Comparative Example 3)

The same process as in Example 1 was carried out except that plate-like clay particles treated with an amine organizing agent were used. The organic agent-treated plate-like clay particles used in the method of Comparative Example 3 did not expand in water and as a result, the desired polyol was not obtained.

The precipitation state of the Examples 1 to 2 and Comparative Examples 1 to 3 was measured and visually observed, and the results are shown in Table 1 below.

1 hours 5 hours 24 hours 5 days 15th 30 days Comparative Example 1 Sedimentation Sedimentation Sedimentation Sedimentation Sedimentation Sedimentation Comparative Example 2 Sedimentation Sedimentation Sedimentation Sedimentation Sedimentation Sedimentation Comparative Example 3 Sedimentation Sedimentation Sedimentation Sedimentation Sedimentation Sedimentation Example 1 Not settled Not settled Not settled Not settled Not settled Not settled Example 2 Not settled Not settled Not settled Not settled Not settled Not settled

As shown in Table 1, Examples 1 and 2 are not precipitated even after 30 days, Comparative Examples 1 to 3 it can be seen that precipitation occurred in 1 hour. Therefore, it can be estimated from this result that plate-like clay particles are dispersed in nano size in the polyol solution of Examples 1-2.

In order to determine whether the clay particles are present in the polyol of Example 1 in nano size, X-ray diffraction was measured and the results are shown in FIG. 1. As shown in FIG. 1, it can be seen that in Example 1, since no peak appears, it was nano-ized, and in Comparative Example 2, in a region of 6.5-7 ° similar to the peak (about 7 °) of a general plate-like clay particle. As the peak appeared, it can be seen that it was not nanonized.

The production method of the present invention by uniformly dispersing the plate-shaped clay nanoparticles in a polyol which is a raw material for the production of urethane, by producing a flame-retardant polyol can be used to prepare a urethane foam excellent flame retardant without using a flame retardant.

Claims (6)

A slurry was prepared by dispersing plate-shaped clay-based nanoparticles in water; Adding the slurry to the polyol dropwise with stirring; Fractional distillation of the resulting mixture to remove water A method for producing a flame retardant polyol for producing urethane foam comprising a step. The method for producing a flame retardant polyol for producing urethane foam according to claim 1, further comprising adding a silane compound to the slurry. The method of claim 2, wherein the amount of the silane compound added to the slurry is 0.1 to 5% by weight. The compound according to claim 2, wherein the silane compound is selected from the group consisting of 3-aminopropyl triethoxy silane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl trimethoxy silane and vinyltriethoxysilane. Method for producing a flame retardant polyol for producing urethane foam. The method of claim 1, wherein the dropping time is 30 minutes to 1 hour. The method of claim 1, wherein the plate-shaped clay-based nanoparticles are selected from the group consisting of montmorillonite, hectorite and bentonite.

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