KR101204717B1 - Polyol using organo clay and polyurethane for shoes middle layer using the organo clay - Google Patents

Abstract

The present invention relates to a polyol using an organic clay having a hydroxyl group and a polyurethane for shoe soles using the same, and more particularly, to a mixture of diacid or triacid, organic clay, a solvent, and a catalyst at room temperature. After stirring for a certain period of time, a suspension is prepared by reacting at a constant temperature and time, and the polyol using organic clay prepared by esterifying the prepared suspension with diol or triol and shoes using the same. It relates to a midsole polyurethane.

Organic, Clay, Polyol, Polyurethane, Composite, Diol, Diexide, Sole

Description

POLYOL USING ORGANO CLAY AND POLYURETHANE FOR SHOES MIDDLE LAYER USING THE ORGANO CLAY}

The present invention uses an organic clay prepared by esterifying a suspension prepared by mixing a diacid or a triacid, an organic clay, a solvent, and a catalyst with a diol or a triol. It relates to a polyol and a polyurethane for shoe sole using the same.

Beginning with Toyota, Japan, in 1986, nano-scale inorganic materials were introduced into polymers. Nano clays have been applied to many polymers because they bring great physical properties even in small amounts. Recently, many reports have reported that the mechanical properties of polymers are improved when they are made of clays and nanocomposites are used. have.

For reference, natural clay has cations between layers and is packed in 0.1 ~ 10㎛ size. Particles of clay consist of many layers, the total height of which is 8 ~ 10nm, and the thickness of one plate is about 0.96. ˜1.0 nm. And the layer is spaced by the Waldelwald force with Na ⁺ ions, and the distance between them is about 1 nm.

The clay used in the present invention is made by ion exchange of Na ⁺ ions of natural clay with ammonium organics having hydroxyl groups.

Conventional clay modification techniques are divided into a method of inserting a polymer into an organic clay layer and an in-situ method of reacting specific functional groups of organic substances in organic clay, and the present invention belongs to the latter.

Currently, there are few techniques for reacting the specific functional groups, although most of the intercalation by simple mixing is performed, and in the case of the technique for reacting specific functional groups of organic substances in organic clay, the specific functional groups are used as simple catalysts. Staying. In addition, when the modified polyol clay is left for a long time by these techniques, there is a problem in that the layer is separated as shown in Figure 3 it is difficult to apply industrially.

In order to solve the above problems, in the present invention, after reacting an organic clay having a hydroxyl group with a diacid or triacid, and then again with a diol or triol By the esterification reaction, the polyol is present between the clay layers, so that the intercalation is easy, and the clay and the polyol form stable bonds. To provide a polyol and polyurethane for shoe soles using the same.

In order to achieve the above object, the present invention is 30 to 48% by weight of a diacid or triacid (diacid) in a reactor in a nitrogen atmosphere, 1 to 19% by weight of organic clay having a hydroxyl group, dimethylformamide (DMF ; dimethylformamide) 50 to 60% by weight, 0.1 to 1% by weight of the catalyst was stirred for 1 to 15 hours at room temperature, and then reacted at 100 to 160 ° C for 5 to 24 hours to prepare a suspension, and the prepared suspension was A polyol using an organic clay having a hydroxyl group prepared by esterification with a diol or a triol,

0.01 to 5 parts by weight of the toner, 0.1 to 5 parts by weight of catalyst, 0.1 to 5 parts by weight of catalyst, 30 to 60 parts by weight of isocyanate based on 100 parts by weight of the polyol mixture composed of 0.1 to 50% by weight of the prepared polyol and 50 to 99.9% by weight of the new polyol. Polyurethane for shoe sole using the organoclay polyol prepared by the addition reaction is the main technical configuration.

The diacid (diacid) is any one or a mixture of two or more selected from adipic acid (AA), terephthalic acid, phthalic anhydride, susnic acid, sebacic acid composed of a carbon chain or a phenyl group between two carboxyl groups. Was created,

The triacid is composed of one, two or more selected from 1,3,5-benzenetricarboxylic acid, tricavalic acid, betamyltricavalic acid, and trans-aconic acid. .

The diol is diethylene glycol, 1,4-butanediol, dipropylene glycol, polyethylene glycol, polyester polyol (polyester polyol by the condensation reaction of adipic acid (AA) and DEG, of adipic acid and Glycerine Polyester polyol by condensation reaction, polyester polyol by condensation reaction of adipic acid and Pentaerythritol), or a mixture of any one or two or more selected from

The triol is any one or two selected from glycerol, 1,2,4-butanetriol, 1,2,6-trihydroxyhexane and 1,1,1-trishydroxymethylethane. It is comprised by the above mixture.

The catalyst is characterized in that an organic metal catalyst composed of any one or a mixture of two or more selected from tetrabutoxy titanium, zinc (Zn), tin (Sn), iron (Fe), chromium (Cr).

Hereinafter, the technical configuration will be described in more detail.

The polyol using the organic clay of the present invention is prepared by reacting a hydroxyl group in organic clay with a diacid or triacid and then esterifying it with a diol or triol.

That is, diacid or triacid, organic clay, dimethylformamide, and a catalyst are added to a reactor in a nitrogen atmosphere equipped with a cooler, stirred at room temperature, and then reacted at 100 to 160 ° C. for 5 to 24 hours. Suspensions are prepared and prepared suspensions are esterified with diols or triols.

The diacid or triacid is used in an amount of 30 to 48% by weight based on the total weight, and when used in an amount less than 30% by weight, sufficient amount of diacid or triacid and organic clay is used. If a problem occurs that the reaction does not occur, and when used in excess of 48% by weight, the diacid or triacid is not sufficiently dissolved in dimethylformamide, so the diacid or triacid is It is preferable to use in the range of 30 to 48 weight% with respect to the total weight.

The organic clay is used in 1 to 19% by weight based on the total weight, if less than 1% by weight of the organic clay after the reaction occurs a problem, the use of more than 19% by weight In this case, since the viscosity of the suspension is too high to induce an effective reaction due to the swelling organoclay, the organoclay is preferably used in the range of 1 to 19% by weight based on the total weight.

The dimethylformamide (DMF; dimethylformamide) is used in an amount of 50 to 60% by weight based on the total weight, when less than 50% by weight is insufficient amount of dimethylformamide as a solvent sufficient wetting of the suspension (wetting ) Can not be induced, and when used in excess of 60% by weight, the concentration of the suspension is too dilute so that the reaction does not occur well, the dimethylformamide (DMF; dimethylformamide) is the total weight It is preferable to use in the range of 50 to 60% by weight.

When the catalyst is used in 0.1 to 1% by weight, when used in less than 0.1% by weight, the concentration of the catalyst is too low, the reaction rate is too slow, and when used in excess of 1% by weight Since the reaction rate does not increase any more, it is meaningless, it is preferable to use the catalyst in the range of 0.1 to 1% by weight based on the total weight.

In order to prepare a polyol using the organic clay having a hydroxyl group of the present invention, first, the diacid or triacid, organic clay, dimethylformamide, and a catalyst are introduced into a nitrogen reactor equipped with a cooler, followed by room temperature. 1 to 15 hours in the stirring, if the stirring is less than 1 hour, there is a problem that does not cause sufficient swelling (swelling) occurs, if the stirring for more than 15 hours already the expansion is completed and no longer Since no swelling, the stirring time is preferably maintained for 1 to 15 hours. Furthermore, it is preferable to limit the stirring time to 8 hours.

After the stirring process as described above to produce a suspension by reacting again at 100 ~ 160 ℃ for 5 to 24 hours, when the reaction temperature is maintained at less than 100 ℃ because the reaction is endothermic reaction does not occur well If a problem occurs and the temperature is maintained above 160 ° C., since the solvent evaporates because the dimethylformamide has a boiling point or more, the reaction temperature is preferably maintained at 100 to 160 ° C.

If the reaction time is maintained in less than 5 hours in relation to the reaction temperature, there is a problem that a sufficient reaction does not occur, and if it exceeds 24 hours, the organic clay is deformed by heat and discolored, The reaction time is preferably maintained for 5 to 24 hours.

When the suspension is prepared through the reaction process, a polyol is prepared by esterifying 0.1 to 50% by weight of the suspension and 50 to 99.9% by weight of diol or triol.

When the suspension is used at less than 0.1% by weight, the influence of the organic clay is insignificant, and when the suspension is used in excess of 50% by weight, the viscosity of the polyol becomes too large, so that the reaction may not occur well. The suspension is preferably used at 0.1 to 50% by weight based on the total weight of the polyol.

In addition, when the diol or triol is used in less than 50% by weight, the viscosity of the polyol becomes too large to cause a problem in which the reaction does not occur well, and when used in excess of 99.9% by weight. Since the influence of the organic clay is insignificant, it is preferable to use the diol or triol at 50 to 99.9% by weight based on the total weight of the polyol.

The above-mentioned polyol using organic clay can control the ratio of clay to 0.1 to 50% by weight of the total polyol, and a certain ratio with other types of polyols (the manufactured polyol contains 0.1 to 50% by weight of clay. When mixed with polyols of the same type, the weight percentage of clay can be adjusted, i.e., polyols made by reacting a specific weight% of clay with polyols can be mixed with other polyols to control the amount of clay freely.) After mixing, the polymer material may be reacted with diisocyanate.

In detail, the polyol using the organic clay prepared by the present invention is mixed with a new polyol (virgin polyol) to prepare a shoe sole polyurethane. At this time, the mixing ratio is 0.1 to 50% by weight of the polyol using the organic clay prepared according to the present invention, 50 to 99.9% by weight of the new polyol.

In addition, it is preferable to mix 15 to 25% by weight of the polyol using the organic clay prepared according to the present invention and 75 to 85% by weight of the new polyol in consideration of economic properties and economic properties of the polyurethane resin for the sole.

In this way, after mixing the polyol using the organic clay and the new polyol, the polyol mixture and the catalyst, toner, and isocyanate are reacted to produce polyurethane for footwear.

In this case, the mixing ratio is prepared by adding and reacting 0.01 to 5 parts by weight of the toner, 0.1 to 5 parts by weight of the catalyst, and 30 to 60 parts by weight of the isocyanate based on 100 parts by weight of the polyol mixture of the polyol and the new polyol using the organic clay. The reaction rate of the isocyanate with respect to the total polyol depends on the physical properties corresponding to the sole and the dosage is selected according to the physical properties.

The physical properties of the polyurethane resin produced by the above method was measured as follows.

 Tensile strength, tear strength and elongation were measured in accordance with KSM 6518, hardness was measured in accordance with KSM 6518 (C type), and specific gravity was measured in accordance with KSM 6519.

 An advantage of the nanocomposite such as the polyurethane resin is that the mechanical strength is increased compared to the general polymer. Usually the mechanical strength of a polymer is proportional to its density. When the density is lowered, the polymer content per unit volume is reduced, resulting in cost savings.

As described above, the polyol using the organic clay according to the present invention is very excellent in physical properties as confirmed in Tables 1 to 6 below, and may have physical properties of the conventional polymer even at a density lower than that of the conventional polymer, It is very economical because the amount of polyol or diisocyanate can be reduced by the lower density.

In addition, the in-situ method of reacting specific functional groups of organic substances in organic clay makes it easier to increase the interlayer distance between clays by reacting hydroxyl groups in organic clay with diacids and then reacting with diols in clay. The synthesized polyol can prevent the sedimentation of clay in the polyol since the polyol and the clay are not separated.

In addition, the polyol using the organic clay of the present invention can be applied to all polymer materials using polyols to synthesize various polymer nanocomposites, and the synthesized polymer nanocomposites have excellent mechanical strength, elongation and thermal stability. Has

Hereinafter, the technical configuration will be described in more detail with reference to the following examples. However, such embodiments are presented in detail to aid the understanding of the present invention, and the present invention is not limited to the scope of the embodiments.

Example 1

250 g of adipic acid (AA), 30 g of organic clay (Closite®30B), 300 g of dimethylformamide, and 0.4 g of tetrabutoxytitanium catalyst were added to a reactor equipped with a cooler and stirred at room temperature for 8 hours, and then at 140 ° C. The suspension obtained by reacting for 12 hours is washed three times with dimethylformamide and five times with ethanol to obtain organic clay (30BAA) modified with adipic acid.

The modified organic clay (30BAA) was added to 400 g of polyester polyol (polAA) having a hydroxy value of 280, prepared by condensation of adipic acid and DEG, respectively, in an amount corresponding to 0, 1, 3, 5 wt% and tetrabutoxytitanium. The esterification reaction of 0.4g at 210 ° C. for about 12 hours yielded a polyol (30BAApolAA) using organic clay, and the corresponding infrared spectroscopic spectrum is shown in FIG. 1.

The polyol using organic clay prepared as in Example 1 was designated as a-1 and measured for physical properties. And, polyol (30BAApolAA) synthesized by the synthesis method of Example 1 is shown in Figure 2, polyol by a general melting method is shown in Figure 3. (The official name of the organic clay used in the above example is Closite® 30BA, 30BAA, 30BAApolAA, etc., which are described later, are specified to distinguish 30B as a derivative derived from the manufacturing process from 30B, and polyol is also distinguished and specified as 30BAApolAA, 30BSApolAA, etc.).

Example 2

Prepared in the same manner as in Example 1, using diacid (diacid) instead of using adipic acid 250g of phthalic anhydride. The polyol (30BPApolAA) using the organic clay prepared as in Example 2 was designated as a-2, and the physical properties thereof were shown in Table 1 below.

Example 3

Prepared in the same manner as in Example 1, but instead of using adipic acid, diexide 250g sebaic acid is used. The polyol (30BSApolAA) using the organic clay prepared as in Example 3 was designated as a-3, and the physical properties thereof were shown in Table 1 below.

Example 4

Prepared in the same manner as in Example 1, a polyester polyol having a hydroxyl value of 320 by the condensation reaction of adipic acid and glycerin (Glycerine) instead of a polyester polyol (polAA) having a hydroxyl value of 280 by the condensation reaction of adipic acid and DEG ( 300 g of polAG) was added to prepare a polyol (30BAApolAG). The polyol (30BAApolAG) using the organic clay prepared as in Example 4 was designated as a-4, and the physical properties thereof were shown in Table 1 below.

Example 5

Prepared in the same manner as in Example 1, the polyester having a hydroxyl value of 400 by the condensation reaction of adipic acid and pentaerythritol instead of the polyester polyol (polAA) having a hydroxyl value of 280 by the condensation reaction of adipic acid and DEG 300 g of polyol (polAP) is added to prepare a polyol (30BAApolAP). The polyol (30BAApolAP) using the organic clay prepared as in Example 5 was designated as a-5, and the physical properties thereof were shown in Table 1 below.

Example 6

The organic clay (30BAA) was prepared in the same manner as in Example 1, except that 0.4 g of zinc acetate was used instead of tetrabutoxytitanium catalyst. The polyol using organic clay prepared as in Example 6 was designated as a-6 and measured for physical properties.

Example 7

Prepared in the same manner as in Example 1, instead of stirring for 8 hours at room temperature diexide and organic clay ultrasonic wave is added for 30 minutes to prepare a modified organic clay (u30BAA). The polyol (u30BAApolAA) using the organic clay (u30BAA) prepared by the method of Example 7 was designated as a-7, and the physical properties thereof were shown in Table 1 below.

Table 1: Prepared in Examples 1-7 Polyol Properties of physical properties of clay

Psalm No. a-1 a-2 a-3 a-4 a-5 a-6 a-7 Molecular Weight 400 432 432 526 561 387 400 OHV 280 260 260 320 400 290 280 Acid 0.90 0.79 0.89 0.95 0.84 0.98 0.86

Example 8

In the process of Example 1 was prepared by reacting the organic clay (30BAA) modified with adipic acid with 300g of polyol having a hydroxyl value of 65, a functional group 3, a viscosity of 1300 by 0, 1, 3, 5% by weight relative to the polyol, triethylene Diamine / ethylene glycol is mixed at 1% by weight relative to the polyol.

Polyurethane was prepared by administering a polymeric diisocyanate having a functional group of 2 and an NCO of 35% at 60% by weight relative to the polyol. In this case, the prepared polyurethanes were designated as b-1, b-2, b-3, and b-4, respectively, and the physical properties thereof were shown in Table 2 below.

Table 2: Measurement of physical properties of Example 8

Psalm No. b-1 b-2 b-3 b-4 Polyol / clay 100/0 100/1 100/3 100/5 Specific gravity (g / cc) 0.26 0.22 0.25 0.24 Hardness (C type) 36 30 36 30 Tensile Strength (kg / ㎠) 10.7 13.0 13.3 7.9 Tear strength (kg / cm) 8.8 7.8 8.8 8.1 Elongation (%) 448 667 712 720

Example 9

In the process of Example 7, the organic clay (u30BAA) modified with adipic acid was prepared by the method of Example 8. The prepared polyurethanes were determined as c-1, c-2, c-3, and c-4, respectively, and the physical properties thereof were shown in Table 3 below.

Table 3: Measurement of physical properties of Example 9

Psalm No. c-1 c-2 c-3 c-4 Polyol / clay 100/0 100/1 100/3 100/5 Specific gravity (g / cc) 0.26 0.28 0.24 0.28 Hardness (C type) 36 36 36 37 Tensile Strength (kg / ㎠) 10.7 17.0 14.5 11.3 Tear strength (kg / cm) 8.8 11.3 10.3 8.4 Elongation (%) 448 548 598 563

Example 10

The polyol (30BAApolAA) prepared in Example 1 was added with a polyol having a molecular weight of 280 and a functional group of 0, 1, 3, and 5%, respectively, based on the total polyol weight, and dimethylcyclohexylamine as a catalyst was 0.2 g per 100 g of the polyol. , 1.5 g of polyol B-8404 (Goldschmit), a silicone copolymer bonded with ((Si-O) n-) and an alkyl group) as a surfactant, per 100 g of polyol, and distilled water as a blowing agent. Add 1.5 g per 100 g.

Diisocyanate (M20R) having a functional group of 2.9 and an NCO of 31% was prepared in a ratio of 1: 1.2 equivalents based on 100 parts by weight of polyol, and then d-1, d-2, d-3, and d-4, respectively. It is represented by, and measured in physical properties are shown in Table 4 below.

Table 4: Measurement of physical properties of Example 10

Psalm No. d-1 d-2 d-3 d-4 Polyol / clay 100/0 100/1 100/3 100/5 Specific gravity (kg / cm 3) 78 78 78 78 Tensile Strength (kg / ㎠) 7.24 7.38 7.75 7.76 Compressive strength (kg / ㎠) 6.05 6.24 6.79 6.81 Thermal Conductivity (kcal / hm ℃) 218 211 206 194

Example 11

Except for using the polyol (30BAApolAG) using the organic clay prepared in Example 3 in the same manner as in Example 9 for the contents of organic clay 0, 1, 3 and 5 e-1, e-2, e- 3, e-4, and the properties of each were measured and shown in Table 5 below.

Table 5: Measurement of physical properties of Example 11

Psalm No. e-1 e-2 e-3 e-4 Polyol / clay 100/0 100/1 100/3 100/5 Specific gravity (kg / cm 3) 65 65 65 65 Tensile Strength (kg / ㎠) 6.85 6.99 7.18 7.24 Compressive strength (kg / ㎠) 4.62 5.16 5.31 5.55 Thermal Conductivity (kcal / hm ℃) 208 201 197 191

Example 12

Except for using the polyol using the organic clay prepared in Example 4 in the same manner as in Example 7 for the content of organic clay 0, 1, 3 and 5 f-1, f-2, f-3, f Designated as -4, and measured by the respective physical properties are shown in Table 6 below.

Table 6: Measurement of physical properties of Example 9

Psalm No. f-1 f-2 f-3 f-4 Polyol / clay 100/0 100/1 100/3 100/5 Specific gravity (kg / cm 3) 56 56 56 56 Tensile Strength (kg / ㎠) 5.76 6.84 6.74 6.47 Compressive strength (kg / ㎠) 4.29 4.73 5.11 5.25 Thermal Conductivity (kcal / hm ℃) 190 188 184 180

In summary of the physical properties of the polyol using the organic clay through the data of Tables 1 to 6, the tensile strength increases and decreases as the clay content increases, and the compressive strength tends to increase. see.

In addition, when the ultrasonic wave is used in the clay reforming, the dispersion of the clay in the polyol can be more effectively performed, and thus the physical properties are further improved.

In addition, the hydroxyl value (OH ^- Value) of the polyol using the synthesized organic clay was measured according to ASTM D2849, and since the hydroxyl value was almost the same as the polyol before the modification, it was confirmed that there is no problem in using it as a polyol. This increase slightly changes the fish value, but does not differ by more than 10%, considering that the economic content of the synthesis was confirmed that 20% by weight of clay is suitable.

1 is a graph showing an infrared spectroscopy spectrum of a polyol using an organic clay according to the present invention.

Figure 2 is a photo of polyol using organic clay prepared according to the present invention.

Figure 3 is a photograph showing a layer separation phenomenon of the conventional polyol.

Claims (9)

delete delete delete delete delete delete delete delete Triacid, organoclay having hydroxyl group, dimethylformamide (DMF) and a catalyst were added to a reactor in a nitrogen atmosphere, stirred at room temperature for 1 to 15 hours, and then reacted at 100 to 160 ° C for 5 to 24 hours. To 100 parts by weight of a polyol mixture composed of a mixture of a polyol and a hard polyol using an organic clay prepared by preparing a suspension, and the obtained suspension is esterified with triol. 0.2g per 100g of polyol as a catalyst, dimethylcyclohexylamine, 1.5g per 100g of polyol as a surfactant, and 1.5g per 100g of polyol as distilled water as a blowing agent. The polyol mixture is triacid composed of any one or a mixture of two or more selected from 1,3,5-benzenetricarboxylic acid, tricavalic acid, betamyltricarvalic acid, and trans-aconic acid. ) 30-48% by weight, 1 to 19% by weight of organic clay having a hydroxyl group, 50 to 60% by weight of dimethylformamide, 0.1 to 1% by weight of an organometallic catalyst composed of any one or a mixture of two or more selected from tetrabutoxytitanium, zinc (Zn), tin (Sn), iron (Fe), and chromium (Cr) at room temperature 0.1 to 50% by weight of the suspension prepared by heating after the reaction; And, 50 to 99.9% by weight of triol; an organic clay polyol, characterized in that the composition is composed of a mixture of 0.1 to 50% by weight of polyol and 50 to 99.9% by weight of hard polyol using an organic clay prepared by esterification Polyurethane for sole use.

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