KR100606983B1 - Manufacturing method of ionic polyols containing metal sulfoisophthalate in the main chain and Composition for water-dispersible polyurethane elastomer based on the ionic polyols - Google Patents

Abstract

The present invention relates to a method for preparing an ionic polyol, wherein a polyol and a metal salt of sulfoisophthalic acid (RSO ₃ M, where R is isophthalic acid and M is Na or Li) and a tin-based catalyst are reacted. It relates to a method for producing an ionic polyol containing a sulfonic acid metal salt of isophthalic acid in the polyol backbone and to a composition for producing a polyurethane elastomer using an ionic polyol.

The present invention includes sulfonate-based ionic groups in the main chain of ether polyols or ester polyols, thereby introducing additional ionic groups such as dimethylol propionic acid and dimethylol butanoic acid, which have high melting points, which are essentially used in preparing conventional water-dispersed polyurethanes. It does not require the use of organic solvents to dissolve it, and there is an effect that can simplify the manufacturing process. In addition, neutralizing agents used in carboxylic ionic polyols are also not necessary.

Ionic Polyols, Sulfonates, Water Dispersible Polyurethanes, Paints, Adhesives

Description

Manufacturing method of ionic polyols containing metal sulfoisophthalate in the main chain and Composition for water-dispersible polyurethane elastomer based on a method for preparing an ionic polyol containing a metal salt of sulfoisophthalic acid in the main chain the ionic polyols}             

1 is a tensile strength of the dry film of the water-dispersed polyurethane prepared in Example 3 and Comparative Example 2 using the ionic polyol of Example 1 of the present invention and the conventional carboxyl-based ionic polyol (Comparative Example 1) Relatively comparable graph.

The present invention relates to a method for preparing an ionic polyol containing sulfonate-based ionic groups in a polyol main chain and a composition for producing a water-dispersible polyurethane elastomer using the same.

Polyurethane is used in a wide range of applications such as fibers, foams, rubber, adhesives, paints, and molded products. In particular, polyurethane has excellent heat resistance, gloss, chemical resistance, and solvent resistance, and has good adhesiveness, and is also usefully used as a coating material, paint, adhesive, and the like.

Polyurethane paints include oil-based urethane paint (Oil Paint) composed of polyurethane and organic solvent and water-based urethane paint (Polyurethane Emulsion Paint) prepared by dispersing polyurethane in water.

Polyurethane is prepared by reacting a polyol (Polyhydroxy Compound: Polyol) and an isocyanate compound. The polyol used here is a condensation reaction of an ether polyol containing an ether bond (-O-), alcohol and acid in the main chain. Various types of polyols, such as an ester polyol which consists of, are used.

The present invention relates to an ionic polyol containing a metal salt of sulfoisophthalic acid in an ether polyol or ester polyol main chain and a composition for preparing a water-dispersible polyurethane elastomer using the same.

Water-dispersible polyurethane has been developed to solve the problem of organic solvent-type polyurethane adhesives and coatings that emit bad smells due to the use of volatile organic solvents. And manufacturing costs are still below the level of organic solvent type, but the demand is increasing in terms of environmental protection. Generally, lower alcohols such as dimethylol propionic acid (DMPA) or dimethylol butanoic acid (DMBA) are introduced as ionic groups to exhibit water dispersion characteristics. Although it is manufactured, the water resistance and storage stability are weak, and the ionic group is located in the hard part of the urethane, which has a limited disadvantage in controlling the film properties after drying. In addition, dimethylol propionic acid and dimethylol butanoic acid are present in a solid state at room temperature and have a high melting point. Thus, dimethylol propionic acid and dimethylol butanoic acid are dissolved in an organic solvent and then dispersed in water.

Korean Unexamined Patent Publication (Kokai) No. 195-0011571 discloses a urethane resin composition for room temperature crosslinking type water-based paints that is suitable for painting interiors, exteriors, bridges, and the like, and has an advantage of safety and hygiene without smell.

In the composition, ionic groups were introduced into the main chain of the polyol to overcome much of the conventional problems, but this was limited to carboxylic acids and its application range was extremely limited.

The polymer containing the metal salt of the carboxyl group (Carboxylic Group) will exist in the form of an ionic carboxyl group (Carboxylate Ion Group) having ionicity in water.

Korean Laid-Open Patent Publication No. 2003-0011871 discloses a technique in which an acrylic modified polyester resin using trimellitic anhydride is used for an aqueous coating composition for inner coating of a can.

U.S. Patent No. 4,268,426 discloses techniques and compositions for preparing ionic polyester polyols with trimellitic anhydride and applying them to water-dispersed polyurethanes.

U.S. Patent No. 4,268,426 relates to a water-dispersible urethane polymer, but uses a high softening point such as dimethylol propionic acid or dimethylolbutanoic acid in the manufacture of water-dispersible urethane polymer, in which case Use a certain amount of organic solvent to give. This water-dispersible polyurethane is called a solvent-modified water-dispersible polyurethane. Solvent-treated water-dispersible polyurethane also maintains water dispersibility, but has a disadvantage in that it cannot completely inhibit odor emission.

Recently, as the environmental problems are rising, many solvent-free or aqueous type paints and coatings that do not use organic solvents have been developed and applied. However, as described above, in addition to the raw material problem, the existing water-dispersed polyurethane has to use a certain amount of organic solvent in the manufacturing process, so it should be considered that the oily drawback due to the smell. In addition, ancillary ionic groups introduced to exhibit water dispersing properties are significantly limited in the scope of application because they have a great influence on the basic physical properties such as polyurethane water resistance. Therefore, there is a demand for development of a raw material suitable for producing a water-dispersed polyurethane having excellent mechanical properties and requiring no use of an organic solvent.

 An object of the present invention is to provide a method for producing an ionic polyol that does not use an organic solvent at all, and a composition for producing a water-dispersible polyurethane elastomer using the ionic polyol. Water-dispersible polyurethane elastomers can be usefully used in the production of water-based urethane paints and adhesives.

The inventors of the present invention introduce the metal salt of sulfoisophthalic acid into the polyol main chain to prepare an ionic polyol containing sulfonate-based ionic groups, and when the composition is formed into a water-dispersible polyurethane elastomer composition using the ionic polyol, no organic solvent is used. The present invention was completed by confirming that a polyurethane elastic body having excellent mechanical properties can be manufactured by a simple manufacturing process without doing so.

The present invention relates to an ionic ether and ester polyol containing a metal salt of sulfoisophthalic acid in the main chain and a composition for producing a water-dispersed polyurethane elastomer using the same.

The polymer containing the metal salt of sulfoisophthalic acid of the present invention is present in the form of an ionic sulfonic acid group showing ionicity in water.

The present invention provides a method for producing an ionic ether polyol, 500-2000 non-ionic ether polyol having a weight average molecular weight of 50 ~ 2000 or alcohol and a metal salt of sulfoisophthalic acid in a ratio of 1: 0.3 ~ 1: 0.9 500 It should have a weight average molecular weight of 6,000.

The metal salt of sulfoisophthalic acid used in the present invention (Metal Sulfoisophthalate) is selected from 5-sodium sulfoisophthalate or 5-lithium-sulfoisophthalate.

The metal salt of sulfoisophthalic acid can be represented by the following general formula.

R-SO ₃ -M

Wherein R is isophthalic acid and M is Na or Li.

Method for producing an ionic ether polyol in the present invention,

a) Propylene oxide nonionic ether polyols or alcohols having a weight average molecular weight of 50 to 2000 and 5-sodium sulfoisophthalate (hereinafter referred to as 5-SSIPA) are 1: 0.3 to 1: Mixing at a rate of 0.9;

b) reacting the mixture by adding 0.01 to 0.1% of a tin catalyst;

  i) dehydrating under high temperature vacuum after completion of the reaction.

In addition, in the present invention, a method for producing an ionic ester polyol,

a) mixing low molecular weight nonionic diols and 5-SSIPA in a ratio of 1: 0.1 to 1: 0.3;

b) a one-step reaction for reacting by adding 0.01 to 0.1% of a tin catalyst to the mixture;

 i) a two-stage reaction in which a nonionic divalent carboxylic acid is reacted by mixing in an unreacted alcohol ratio of 1: 0.1 to 1: 0.9 after the completion of the reaction;

 i) dehydrating under high temperature vacuum.

In addition, the water-dispersed polyurethane elastomer using the ionic polyol prepared in the above process has a weight average molecular weight of 500 to 6000 by mixing an aromatic disocyanate and an alicyclic diisocyanate in a ratio of 1: 1 to 0.1: 1 by weight. It is composed based on the reaction of ionic polyols or lower alcohols and amines, and the preparation thereof is

a) mixing the aromatic diisocyanate and the alicyclic diisocyanate in a ratio of 1: 1 to 0.1: 1 by weight;

b) reacting the diisocyanate mixture with a sulfate-based ionic polyol or short alcohol having a weight average molecular weight of 500 to 6000 to prepare a urethane prepolymer having an unreacted isocyanate group content of 1 to 5%;

c) adding water and dispersing;

d) chain extending using an amine having 2 to 4 functional groups.

Hereinafter, the present invention will be described in detail.

Ionic ether polyol or ester polyol having a sulfonate-based ionic group containing a metal salt of sulfoisophthalic acid in the main chain according to the present invention and a composition for producing a water-dispersed polyurethane elastomer using the same;

The ionic ether polyol preparation step is basically the same as the method for preparing a polyol by reacting with a conventional nonionic ether polyol or an alcohol except using a sulfonate carboxylic acid in a constant ratio. That is, propylene oxide-based nonionic ether polyols or alcohols are reacted at a constant ratio with 5-SSIPA to contain sulfonic acid salts (-SO ₃ M: where M is Na or Li) in the main chain of the ether polyol. Is to add. The basic form of this reaction is the reaction between alcohols and 5-SSIPA.

 In the present invention, propylene oxide-based polyols or alcohols used in the production of propylene oxide-based ionic ether polyols or alcohols are propylene oxide-based nonionic ether polyols (Polypropylene glycol: PPG) and propylene having a weight average molecular weight of 50 to 2,000. Propylene glycol (PG), Dipropylene glycol (DPG), Tripropylene glycol (TPG), Glycerine, and the like, and 5-SSIPA to add ionic groups to the main chain of the ether polyol Or 5-lithium sulfoisophthalate (5-Litium sulfoisophthalate: hereafter referred to as 5-LiSIPA) was used. In this case, the reaction between the ethylene oxide nonionic ether polyol or alcohol having a weight average molecular weight of 50 to 2000 and the metal salt of sulfoisophthalic acid in an equivalent ratio is in the range of 1: 0.3 to 1: 0.9, more preferably 1: 0.5. ˜1: 0.7. If the content of the metal salt of sulfoisophthalic acid in excess of the above ratio is excessive, the molecular weight distribution of the ionic polyol produced is not constant, so the variation of physical properties after the production of the water-dispersed polyurethane is severe, the viscosity of the ionic polyol itself It also increases considerably. On the contrary, when the content of the sulfate-based divalent carboxylic acid is less than the ratio, the content of ionic groups of the ionic polyol is insufficient, and thus stable dispersion of polyurethane particles cannot be obtained. In the reaction, a tin-based catalyst is essentially used, and is controlled in the range of 0.01 to 0.1%, more preferably 0.03 to 0.08%. When the amount of the catalyst used exceeds the above range, the reaction rate may be increased, but the molecular weight distribution of the propylene oxide ionic ether polyol becomes uneven. On the contrary, when the content is too low, the molecular weight distribution is uniformly produced, but the reaction time is It is too slow.

In addition, the ionic ester polyol preparation step is based on the first reaction with excess lower alcohols and metal salts of sulfoisophthalic acid, and then the second unreacted dihydric acid at a constant ratio with the remaining unreacted alcohols. . In other words, the lower alcohols 5-SSIPA are reacted at a constant ratio to prepare diols containing metal salts of sulfoisophthalic acid in the main chain first, and then condensation reaction is performed by adding a proportion of divalent acid to the ionic ester ionicity. To prepare. The basic form of this reaction is shown below with an example.

In the present invention, as the alcohols used in the preparation of the ionic ester polyols or alcohols, ethylene glycol (Ethylene glycol: EG), propylene glycol (PG), diethylene glycol (Diethylene) having a weight average molecular weight of 50 to 300 glycol: DEG), Dipropylene glycol (DPG), butylene glycol (Butylene glycol: 1,4 BD), etc., and 5-SSIPA or 5 to add ionic groups by reacting these short alcohols with primary LiSIPA was used. Adipic acid (Adipic acid: AA) was used as the divalent acid used in the second reaction. In this case, the reaction between the lower alcohols having a weight average molecular weight of 50 to 300 and 5-SSIPA is in the range of 1: 0.1 to 1: 0.3 in an equivalent ratio, and more preferably 1: 0.1 to 1: 0.2. If the content of the metal salt of sulfoisophthalic acid exceeds the ratio, the solubility of the metal salt to be prepared is low, and the reaction is difficult. On the contrary, when the content is less than the ratio, the content of the ionic group of the ionic polyol is insufficient. No waterborne polyurethane particles can be obtained. In the reaction, a tin-based catalyst is essentially used, and is controlled in the range of 0.01 to 0.1%, more preferably 0.03 to 0.08%. When the amount of the catalyst used exceeds the above range, the reaction rate may be increased, but the molecular weight distribution of the ionic ester polyol may not be uniform. On the contrary, when the content is too low, the molecular weight distribution is uniformly produced, but the reaction time may be too slow. It is a phenomenon.

The water-dispersed polyurethane using the sulfonate-based ionic ether or ester polyol of the present invention is a basic water-dispersed polyurethane composition, that is, an aromatic and aliphatic diisocyanate and a sulfonate-based ionic polyol prepared in the present invention, and a short chain extender. It is composed of diols, diamines, and the like, and amines and metal ions as neutralizing agents used in conventional water-dispersed polyurethanes are not necessary in the present invention.

A water-dispersed polyurethane resin prepared by mixing the above aromatic diisocyanate and alicyclic diisocyanate with a nonionic ether polyol has already been known.

Representative examples of the aromatic diisocyanate include 4,4'-diphenylmethane diisocyancate (MDI), 2,4- or 2,6-toluene diisocyanate (2,4- or 2, 6-toluene diisocyanate (TDI), carbodiimide-modified MDI, polymeric MDI, and the like.

In addition, as the alicyclic diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), 1,4-cyclohexylmethane Diisocyanate (1,4-cyclohexylmethane diisocyanate: CHDI).

In the present invention, the aromatic and cycloaliphatic diisocyanates may be used in the form of single compounds or mixtures, respectively, and are not limited to the above-mentioned kinds as long as the object of the present invention can be achieved.

On the other hand, in the present invention, the polyol used to prepare the water-dispersed polyurethane is to use the sulfate-based ionic ether or ester polyol prepared by the above-described method, the amount of the diol isocyanate and equivalent ratio 1: 0.8 to 1: 1.2 More preferably, it is in the range of 1: 1.

In the case where the above range is exceeded or falls short of the theoretical equivalent ratio, the physical properties of the polyurethane elastomer cannot be exhibited.

Finally, after dispersing the prepolymer prepared through the above process and finally extending the chain to amines having 2 to 4 functional groups, a water-dispersed polyurethane elastomer having excellent mechanical properties is produced. Examples of the amines that can be used here include divalent amines such as ethylenediamine (EDA), butylenediamine (BDA), hexanediamine (HDA), and isophorone diamine (IPDA). Polyvalent amines such as diethylene triamine (DETA) and triethylene tetramine (TETA). The amount of the polymer should be added in an amount ratio of 1: 1 to the residual unreacted cyan group and the equivalent ratio of the prepolymer produced in the above process, and if the content is over or under, the molecular weight of the polyurethane does not increase sufficiently to show the inherent physical properties of the polyurethane. There will be no.

Hereinafter, a method for preparing a sulfonate-based ionic ether and ester polyol and a composition for preparing a water-dispersed polyurethane using the same will be described in detail. The ionic polyol is carried out for about 2 to 20 hours in a nitrogen atmosphere not in contact with air and at a temperature of about 170 to 220 ° C., more preferably at about 5 to 10 hours at a temperature of 190 to 200 ° C. And the production reaction of the water-dispersed polyurethane is generally known in the art, in the case of the present invention, preferably for about 1 to 8 hours under a nitrogen atmosphere and a temperature condition of about 40 to 90 ℃ more preferably in contact with air, more preferably Is carried out at about 60-80 ° C. for about 5-6 hours.

According to the present invention, in the case of the sulfonate-based ionic ether or ester polyol, the content of the carboxyl group produced in the manufacturing process should be measured to find the end point of the reaction, which is generally tracked through an acid value analysis below.

Acid value = (V * N * 0.06005 * 100) / sample weight (g)

(V: KOH (ml) consumed in sample titration, N: KOH normal concentration)

Finding the end point of the reaction by measuring the acid value is the most important factor in the molecular weight distribution and quality uniformity of the ionic polyol, the reaction temperature or time should be appropriately controlled within the above range based on this.

In addition, in the case of water-dispersed polyurethane, the unreacted isocyanate content of the diisocyanate may be adjusted according to the reaction ratio of the diisocyanate and the polyol in the manufacturing process, and the hardness of the polyurethane elastomer is finally produced. And strength and reactivity. The higher the content of the unreacted isocyanate group, the higher the hardness and strength, but the reactivity also increases, making it difficult to obtain stable particles in the water dispersion process. Therefore, it is important to have an appropriate isocyanate group content in the prepolymer, and the mixing ratio of the above-mentioned diisocyanate, polyol, and short alcohols is such that the content of unreacted isocyanate group is about 1-5%, most preferably about 2-4%. And design the structure. For example, when the amount of the unreacted isocyanate group exceeds 5%, the content of the rigid segment of the urethane is increased so that the strength and hardness are improved, but the reactivity is increased, so that stable dispersion of polyurethane particles cannot be obtained. On the other hand, when the amount of unreacted isocyanate group is less than 1%, the molecular weight of the prepolymer and the hydrogen bond in the prepolymer are accompanied by excessive viscosity increase, resulting in poor workability and when the content of the unreacted isocyanate group is exceeded. Similarly, stable dispersion of polyurethane particles cannot be obtained. Therefore, it is important to maintain an appropriate level of the content of unreacted isocyanate groups, which should be determined in consideration of the particle stability of the water-dispersed polyurethane within the allowable property of the product. Through the above process, water is added to and dispersed in a prepolymer, which is appropriately prepared. In the water dispersion step, not only temperature and time conditions but also mechanical conditions such as water input speed, stirring speed, and stirring time are important factors for obtaining stable water dispersion polyurethane particles. In the present invention, it is prepared by adding water while stirring at 30 to 60 ° C., a stirring speed of 500 to 2000 times per minute for 5 to 30 minutes, more preferably 40 to 50 ° C., and a stirring speed of 800 to 1200 times for 10 to 20 minutes. do. At this stage, if the temperature is too high, unreacted isocyanate groups and water react to cause side reactions. If the temperature is too low, it is difficult to obtain stable dispersed polyurethane particles due to the high viscosity. In addition, if the stirring speed is too slow or the stirring time is short, it is difficult to sufficiently disperse in water, so that stable water-dispersed polyurethane particles are not obtained. If the stirring time is too long, side reactions of unreacted isocyanate groups and water occur, such as the effect of temperature. Done. Finally, the chain dispersion is completed by adding a divalent tetravalent amine, which is a chain extender, to the water-dispersed polyurethane produced through the above processes, thereby completing a completely dispersed polyurethane elastomer. As described above, divalent or polyvalent amines are added so as to be 1: 1 in an equivalent ratio of unreacted isocyanate groups, but the temperature is 40 to 80 ° C, preferably 50 to 60 ° C. If the temperature is too low, the reaction between the amines and the unreacted isocyanate group is slowed down, rather than reacting with water, which will adversely affect the water-dispersed polyurethane final physical properties. In addition, if the temperature is too high, it is important to properly control the temperature because the volatile amines may volatilize before participating in the reaction.

Water-dispersed polyurethane elastomers using sulfonate-based ionic ethers or ester polyols prepared according to the present invention simultaneously form sulfonic acid ions and their counterions in the polyurethane backbone depending on the type of ionic polyols used and the content of ionic groups. Since it does not require the addition of amines or metals as a neutralizing agent as in the conventional water-dispersed polyurethane, it is possible to completely solve the yellowing or odor problem caused by this.

The present invention can be more clearly understood by the following examples, which are only intended to illustrate the present invention and are not intended to limit the scope of the invention.

In the examples below, the reactivity of polyols or alcohols with sulfonate dihydric carboxylic acids in the preparation of sulfonate ionic ethers or ester polyols, the particle stability of water-dispersed polyurethanes, and the mechanical properties of the final film product The evaluation is according to the following method.

-Reactivity of metal salts of polyols or alcohols with sulfoisophthalic acid

Reactivity showed the change of reactivity by comparing the time to reach the reference acid value by collecting the acid value mentioned above by the time of the reaction when preparing the sulfonate-based ionic ether or ester polyol.

-Particle stability

Particle stability was measured by comparing the particle size of the water-dispersed polyurethane finally prepared by using a sulfonate-based ionic ether polyol by light scattering method at room temperature.

-Mechanical property (tensile strength)

Mechanical properties are shown in Figure 1 by comparing the dry film of the water-dispersed polyurethane prepared in this example and the comparative example by measuring the tensile strength. Tensile strength was measured by five times using UTM (Universal Tensile Machine; Instrone) to obtain an average value.

Example 1

115.2 parts by weight of 5-SSIPA was added to 660 parts by weight of a polypropylene glycol polyol having a weight average molecular weight of 600 g / mole, completely dissolved in 170 ^° C. of nitrogen atmosphere, and then the temperature was raised to 190 ^° C. as a catalyst. 0.415 parts by weight of dibutyl tin dilaurate was added to start the reaction.

Then, the sample was taken with time and the acid value mentioned above was measured and when the reference acid value was reached, the reaction was terminated after a total of 6 hours.

The change in acid value with time is shown in Table 1 below.

Time (Hr) Acid value (mgKOH / g) Remarks 0 80.6  * Acid value based on completion of reaction: 43.2 2 66.7 4 52.2 6 43.9

Example 2

580 parts by weight of diethylene glycol having a weight average molecular weight of 250 g / mole, 66 parts by weight of 5-LiSIPA, and 0.68 parts by weight of dibutyl tin dilaurate as a catalyst were subjected to the first reaction in the same manner as in Example 1 615 parts by weight of adipic acid (AA: Dongyang Steel Chemical Co., Ltd.) having a molecular weight of 146 g / mole and a secondary reaction were added thereto. Samples were taken with time, and the acid value mentioned above was measured. When the reference acid value was reached, the reaction was terminated after a total of 9 hours.

The change in acid value with time is shown in Table 2 below.

Time (Hr) Acid value (mgKOH / g) Remarks 0 27.8  * Acid value at the end of reaction: 5 or less 3 13.7 6 6.4 9 3.4

Comparative Example 1

580 parts by weight of diethylene glycol having a weight average molecular weight of 250 g / mole, 115 parts by weight of trimellitic anhydride, and 0.68 parts by weight of dibutyl tin dilaurate were added to the primary reaction in the same manner as in Example 1 615 parts by weight of adipic acid (AA: Dongyang Steel Chemical Co., Ltd.) having an average molecular weight of 146 g / mole and a secondary reaction were added thereto. Samples were taken with time, and the acid value mentioned above was measured. When the reference acid value was reached, the reaction was terminated after a total of 9 hours.

The change in acid value with time is shown in Table 3 below.

Time (Hr) Acid value (mgKOH / g) Remarks 0 27.2  * Acid value based on termination of reaction: 9.1 3 13.4 6 11.4 9 10.1

Example 1 is a sulfonate-based ionic ether polyol reacted with a metal salt of a nonionic ether polyol and a sulfoisophthalic acid, and Example 2 is a first reaction with a lower alcohol (diethylene glycol) and a sulfoisophthalate metal salt. It is a sulfonate-based ionic ester polyol prepared by secondary reaction of adipic acid which is a divalent acid. In Comparative Example 1, the carboxyl ionic polyol prepared using trimellitic anhydride was used as an example to compare with the sulfonate ionic ester polyol of Example 2.

Examples 3 and 4 below are examples of water-dispersed polyurethanes prepared using the respective ionic polyols obtained in Example 2 and Comparative Example 1.

Example 3

4,4'-diphenylmethane diisocyanate (MDI; Kumho Mitsui's trade name (Cosmonate PH) and alicyclic diisocyanate isophorone diisocyanate (IPDI; Degussa) in 0.5: 1 mixture 3500 g (24% by weight) of the sulfate-based ionic ester polyol prepared in Example 2 was added to 1140 g (g% by weight) and reacted for 4 hours at 80 ^° C. Then, the temperature was lowered to 50 ° C. and water 10,000 g (67.5% by weight) was added and the dispersion was allowed to proceed for 15 minutes while the stirring speed was 800 times per minute Ethylenediamine (EA; Dongyang Steel Chemical) was added to the prepolymer dispersed in water as described above. 74 g (0.5% by weight) was added and reacted for 2 hours at 80 ° C. to prepare a water-dispersed polyurethane elastomer, the water-dispersed polyurethane prepared as described above was a milky white viscous liquid having a particle size of about 20 to 30 nm. And awards Tensile strength of the dried film of the water-dispersed polyurethane obtained in the example is shown in Fig. 1. Compared with the carboxyl-based water-dispersed polyurethane elastomer in Comparative Example 2 below, the equivalent strength is shown. The amount of polyol and polyol used is 1: 1 in the reaction equivalence ratio, but the isocyanate compound and the polyol may be used in the equivalence ratio range of 1: 0.8 to 1.2.

Comparative Example 2

4,4'-diphenylmethane diisocyanate (MDI; Kumho Mitsui's trade name (Cosmonate PH) and alicyclic diisocyanate isophorone diisocyanate (IPDI; Degussa) in 0.5: 1 mixture 1140 g of 3500 carboxyl ionic ester polyol prepared in Comparative Example 1 was added and reacted at 80 ^o C for 4 hours, the temperature was lowered to 60 ^o C, and triethylamine (TEA) was added as a neutralizing agent. The mixture was stirred for 30 minutes to sufficiently induce a neutralization reaction, and then the temperature was lowered to 50 ° C., and then water dispersion was carried out while adding 10,000 g of water over 15 minutes, and the stirring speed was 800 times per minute. 74 g of ethylene diamine (EA; Tong Yang Steel Chemical) was added to the prepolymer dispersed in water and reacted at 80 ° C. for 2 hours to prepare a water-dispersed polyurethane elastomer. Lee urethane was a milky white viscous liquid having a particle size of about 50 ~ 70nm., And exhibited a tensile strength of the polyurethane dispersion of the dry film obtained in the above-mentioned example in Fig.

 The present invention does not introduce additional ionic groups such as dimethylol propionic acid or dimethylol butanoic acid, which have a high melting point, which is essential for preparing a water-dispersed polyurethane, by including sulfonate-based ionic groups in the main chain of the polyol, thereby dissolving them. There is no need for the use of organic solvents for the manufacturing process and there is an effect that can be simplified. In addition, neutralizing agents used in carboxylic ionic polyols are also not necessary.

Claims (10)

In the method for preparing an ionic polyol, the polyol main chain is reacted with a metal salt of polyol and sulfoisophthalic acid (RSO ₃ M, wherein R is isophthalic acid and M is Na or Li) and a tin-based catalyst. A method for producing an ionic polyol containing a sulfonic acid metal salt of isophthalic acid. 2. The polyol of claim 1, wherein the polyol is an ether polyol or an ester polyol and the metal salt of sulfoisophthalic acid is 5-sodium sulfoisophthalate or 5-lithium sulfoisophthalate and the tin catalyst is dibutyltindi. A process for preparing an ionic polyol which is dibutyl tin dilaurate. The method of claim 2, wherein ether polyol having an average molecular weight of 50 to 2,000 and 5-sodium sulfoisophthalate are mixed at a weight ratio of 1: 0.3 to 0.9, and then heated to 190 ° C in a nitrogen atmosphere, and dibutyltin laurate is added thereto. A method for producing an ionic ether polyol having an average molecular weight of 500 to 6,000 by adding and reacting 0.01 to 0.1% by weight. The method of claim 3, wherein the ether polyol is selected from polypropylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerin, or a mixture thereof. The lower alcohol having a weight average molecular weight of 50 to 300 and 5-sodium sulfoisophthalate are mixed in a weight ratio of 1: 0.1 to 0.3, and then heated to 190 ° C. in a nitrogen atmosphere, and dibutyl tin dilau is added thereto. Preparation of an ionic ester polyol to which adipic acid is added to the reactant reacted by adding a rate of 0.01 to 0.1% by weight so that the weight ratio of the reactant and adipic acid is 1: 0.3 to 0.9 and the acid value of the reactant is 5 or less. Way. 6. The method of claim 5, wherein the lower alcohol is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol or a mixture thereof. A composition for producing a water-dispersible polyurethane elastomer prepared by dispersing an ionic polyol, a diisocyanate compound, and an amine compound in a main chain containing a metal salt of sulfoisophthalic acid in water. The composition for producing a water-dispersible polyurethane elastomer according to claim 7, wherein the metal salt of sulfoisophthalic acid is 5-sodium sulfoisophthalate or 5-lithium sulfoisophthalate. The diisocyanate compound of claim 7, wherein the diisocyanate compound is 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, carbodiimide, modified MDI, polymeric MDI, 4 A composition for producing a water-dispersible polyurethane elastomer selected from, 4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate and 1,4-cyclohexyl methane diisocyanate. The composition for producing a water-dispersible polyurethane elastomer according to claim 7, wherein the amine compound is selected from ethylenediamine, butylenediamine, hexanediamine, isophoronediamine, diethylenetriamine, and triethylenetetraamine.

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