KR101705868B1 - Method for Preparing Liquid Dialkyl Sulfosuccinate - Google Patents

Abstract

Disclosed is a method for producing liquid dialkyl sulfosuccinate. The method produces 100 wt% of liquid dialkyl sulfosuccinate by adding 15-40 wt% of dialkyl sulfosuccinate represented by chemical formula 1 and 5-10 wt% of an antioxidant in 5-20 wt% of dimethylacetamide or dimethylformamide, by conducting the reaction of a mixture at 75-95C, and by adding dimethylacetamide or dimethylformamide as a balance. In chemical formula 1, R_1 and R_2 are the same or different from each other, and are independently hydrogen or a C1 to 30 alkyl group, and M^+ is a H^+, Li^+, Na^+, K^+, or NH_4^+ based cation.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing a dialkyl sulfosuccinate,

This disclosure relates to a process for the preparation of liquid dialkyl sulfosuccinates.

In general, dialkyl sulfosuccinates are added to the polyurethane composition at any point in the composition treatment process, for example, in the manufacture of polyurethane fibers, to inhibit the generation of static electricity in products made of polyurethane fibers, It is possible to provide an elastic fiber having an excellent adhesive force.

The dialkyl sulfosuccinate may be added to the solution or dispersion of another polyurethane (PU) or PU fiber additive in the form of a solution or slurry. During the treatment process for fabricating the fibers, they can be mixed with the polymer solution or injected into the final upstream of the fiber spinneret. In addition, the dialkyl sulfosuccinate may be added separately as a wax or as a solution or as a slurry in a suitable medium, to the polymer (spinning) solution. Moreover, dialkyl sulfosuccinates can be added in the form of the above-mentioned formulations in the conventional polyurethane production.

In addition, the dialkyl sulfosuccinate can be deposited as a finish agent in the manufacture of polyurethane fibers. For example, the dialkyl sulfosuccinate may be incorporated into the polydialkylsiloxane or mineral oil of the previously known low viscosity for finishing treatment of the polyurethane fibers as a wax-like material or in the form of a slurry or solution in a suitable solvent .

Due to the good solubility of the dialkylsulfosuccinates in the polydialkylsiloxanes and mineral oils, homogeneous solutions are formed and are formed on the polyurethane fibers by conventional manufacturing techniques such as, for example, production rollers or fiber guides or sprays Can be deposited.

However, the dialkyl sulfosuccinate added to the polyurethane fiber requires a purity of 98 or more in terms of reactivity and physical properties, and therefore, it is a solid wax-like solid. Therefore, the dialkylsulfosuccinate has inherent viscosity, and foreign substances and precipitates are often introduced into the process in the process. When used alone, the dialkylsulfosuccinate tends to be carbonized at a temperature above a certain temperature have.

Accordingly, one aspect of the present disclosure is to provide a process for preparing dialkyl sulfosuccinates in liquid phase which can solve the above-mentioned problems.

In order to achieve the above-mentioned aspects, a method for preparing a liquid dialkyl sulfosuccinate according to an embodiment of the present disclosure comprises adding 5 to 20% by weight of dimethylacetoamide or dimethylformamide to a dialkyl sulfosuccinate 15 to 40% by weight of an antioxidant and 5 to 10% by weight of an antioxidant and then reacted at 75 to 95 占 폚, and then adding dimethylacetoamide or dimethylformamide as a balance to form 100%

[Chemical Formula 1]

Wherein R ₁ and R ₂ are independently of each other hydrogen or an alkyl group of 1 to 30 carbon atoms and M ⁺ is a cation of the H ⁺ , Li ⁺ , Na ⁺ , K ⁺ or NH ₄ ⁺ series.

According to another embodiment of the disclosure, the antioxidant is a phenolic antioxidant.

According to another embodiment of the present disclosure, the phenolic antioxidant is 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenol) propionic acid stearyl ester or terakis methylene- - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

According to another embodiment of the present disclosure, the reaction time is 4 to 6 hours.

According to another embodiment of the present disclosure, the method comprises the steps of reacting at 75 to 95 캜 and adding 1 to 5% by weight of at least one additive selected from the group consisting of a heat resistant additive, a UV absorber, a dyeability improver and a yellowing inhibitor .

According to another embodiment of the present disclosure, the heat resistant additive is triethylene glycol-bis-3- (3-tet-butyl-4-hydroxy- Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzene) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) The UV absorber is 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, Benzotriazole, and the dyeability-improving agent is poly (N, N-diethyl-2-aminoethyl methacrylate).

According to another embodiment of the present disclosure, the reaction is conducted under reduced pressure to maintain the moisture content of the final product below 5000 ppm.

The liquid dialkyl sulfosuccinate produced according to one embodiment of the present disclosure has excellent heat resistance even when a relatively small amount of an antioxidant and / or a heat resistant additive is added, so that carbonization does not occur, and the yarn And the polyurethane fiber can be radiated at a high temperature. It is very easy to use as a liquid phase, and it is filtered to 4 micrometers or less, and there is no clogging of the filter during impregnation or the like.

The features and advantages of the present invention will become more apparent from the following detailed description based on the accompanying drawings.

FIG. 1A is a photograph showing the results of a dialkyl sulfosuccinate baked in an oven at 220 DEG C for 4 hours in accordance with a comparative example of this disclosure. FIG.
1B is a photograph showing the results of a dialkyl sulfosuccinate baked in an oven at 220 DEG C for 4 hours in accordance with one embodiment of the present disclosure.
2A is a photograph showing the result of dissolution of a dialkyl sulfosuccinate at 25 DEG C according to a comparative example of this disclosure.
2B is a photograph showing the result of dissolving the dialkyl sulfosuccinate at 85 캜 according to another embodiment of the present disclosure.

Before describing the invention in more detail, it is to be understood that the words or words used in the present specification and claims are not to be construed in a conventional or dictionary sense, It should be interpreted as meaning and concept consistent with the technical idea of the present invention. Therefore, it is to be understood that the constitution of the embodiments described herein is merely a preferred example of the present invention, and does not represent all of the technical ideas of the present invention, so that various equivalents and modifications It should be understood.

Hereinafter, preferred embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

As described above, the present disclosure relates to a process for producing a dialkyl sulfosuccinate represented by the following formula (1) in a liquid phase.

[Chemical Formula 1]

Wherein R ₁ and R ₂ are independently of each other hydrogen or an alkyl group of 1 to 30 carbon atoms and M ⁺ is a cation of the H ⁺ , Li ⁺ , Na ⁺ , K ⁺ or NH ₄ ⁺ series.

The dialkyl sulfosuccinate is available from Mr. Al. C. Carly, Ind. Eng. Chem., Vol. 31, page 45, 1939).

Such a dialkyl sulfosuccinate is a solid wax-like solid and has inherent viscosity. When used in the process, foreign substances and precipitates are often introduced together. When used singly, the dialkyl sulfosuccinate has a carbonization width There is a big tendency.

In particular, preferred dialkyl sulfosuccinates are sodium diisobutylsulfosuccinate, sodium dioctylsulfosuccinate, sodium dihexylsulfosuccinate, sodium diamylsulfosuccinate and sodium dicyclohexylsulfosuccinate. More preferred dialkyl sulfosuccinates are sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate. The most preferred dialkyl sulfosuccinate is sodium dioctyl sulfosuccinate. Such dialkyl sulfosuccinates may be used as individual materials or as a mixture of plural dialkyl sulfosuccinates.

According to one embodiment of the present disclosure, a method for preparing the dialkyl sulfosuccinate represented by the above formula (1) in a liquid phase comprises adding 5 to 20% by weight of dimethylacetoamide or dimethylformamide to 15 to 40 dialkyl sulfosuccinates By weight and 5 to 10% by weight of an antioxidant, and then reacting at 75 to 95 占 폚, and then adding dimethylacetoamide or dimethylformamide as a balance to form 100% by weight.

In one embodiment, the solvent used in the process is preferably dimethylacetamide or dimethylformamide, which is commonly used as a solvent for the dialkylsulfosuccinate, but is not necessarily limited thereto, The use of any solvent is also possible.

The dimethylacetoamide or dimethylformamide is generally used in the present disclosure at a weight ratio of about 1.5-3 times the dialkylsulfosuccinate to the dialkylsulfosuccinate, taking into account the solubility of the dialkylsulfosuccinate and the subsequent overall reaction efficiency. , Or preferably about twice or more. It is used in two steps in order to obtain a transparent homogeneous solution. The amount used in the first step is 5 to 20 wt% based on the total amount of the dialkyl sulfosuccinate in the liquid phase, and the amount used in the second step is determined as the balance forming 100 wt%. If the amount is less than 5% by weight, the solubility of the final product may be opaque. If the amount is more than 20% by weight, a product having a large amount of opalescent suspensions (highly likely to precipitate) may be produced.

According to another embodiment, the antioxidant is preferably a phenol-based antioxidant having a high thermal decomposition temperature. Typical examples of the antioxidant include 3- (3 ', 5'-di-tert-butyl- Hydroxyphenol) propionic acid stearyl ester or terakis methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

According to another embodiment, the reaction is carried out at a temperature of 75 to 95 캜, preferably 80 to 90 캜, or more preferably 80 to 85 캜 for 4 to 6 hours, preferably 4 to 6 hours, More preferably 5 to 6 hours. If the temperature is less than 75 占 폚 or exceeds 95 占 폚, there is a tendency to re-agglomerate. If the reaction time is less than 4 hours, the unreacted dialkyl sulfosuccinate acts as a seed and recrystallizes. When the reaction time exceeds 6 hours, the dialkyl sulfosuccinate tends to yellow.

According to another embodiment, the method comprises the steps of reacting at 75 to 95 캜 and then adding 1 to 5% by weight of at least one additive selected from the group consisting of a heat resistant additive, a UV absorber, a dyeability improver and a yellowing inhibitor .

Typical heat resistant additives include triethylene glycol-bis-3- (3-tet-butyl-4-hydroxy-5-methylphenyl) propionate or 1,3,5-tris (4- -Hydroxy-2,6-dimethylbenzene) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -tione.

Representative UV absorbers include 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) (N, N-diethyl-2-aminoethyl methacrylate), and the like. Suitable additives known to those skilled in the art can be used without any particular limitation .

Further, according to another embodiment, antioxidants such as hindered phenol series and sulfur series which are various stabilizers; Light stabilizers such as hindered amine type, triazole type, benzophenone type, benzoate type, nickel type and salicyl type; Molecular adjusters such as antistatic agents; Organic and inorganic nucleating agents; corrector; Fluorescent brightener; Fillers; Flame retardant; And / or a flame retardant auxiliary may be added to the extent that the effect of the present disclosure is not impaired.

On the other hand, according to another embodiment, the reaction is carried out under reduced pressure to maintain the moisture content of the final product below 5000 ppm. When the liquid dialkyl sulfosuccinate contains more than 5,000 ppm of water, such a decompression reaction may cause a decrease in reactivity and physical properties of the elastomer, so that a decompression process may be added. Optionally, for removal of this material, i.e. dialkylsulfosuccinate is a viscous, solid product, external dust may be introduced, which may be filtered after filtration with a 2 micro or 4 microemulsion filter .

BRIEF DESCRIPTION OF THE DRAWINGS The embodiments of the disclosure are described in greater detail below by way of example, but these embodiments are for purposes of illustration only and are not to be construed as limiting the scope of protection of the disclosure.

The physical properties of the polyurethane-urea yarn mentioned in the following Examples and Comparative Examples are as follows.

Kang Shin-do:

Using a tensile tester (UTM, manufactured by INSTRONG Co., Ltd.), the sample is measured at a length of 10 cm and a tensile speed of 100 cm / min. At this time, the strength and elongation value at break are measured, and the load (100%, 300% Modulus) applied to the yarn at the time of 100% yarn and 300% elongation is also measured.

Combination strength between monofilaments:

A polyolefin-based elastic yarn composed of a plurality of filaments, separating one strand of monofilaments by about 5 cm, separating each end of the monofilaments that are not separated from the separated single-strand monofilaments into separate monofilaments and mono- The filament was attached to an induction machine equipped with a load cell of not more than 1 kg so that the contact point to which the filaments were attached was located at the center of a 5 cm cage. The filament was stretched at a constant speed of 1000% Measure the force when the remaining monofilaments are separated by the kidneys. The results are obtained by measuring the mean value of the combined forces during elongation and taking the average of the measured values by measuring more than 5 times per sample.

Heat resistance test:

The samples were treated at 200 < 0 > C for 10 minutes in a hot air oven. The yellowing value "b" of the sample was measured before and after the treatment of the sample with a color-view (Gardener, USA). The difference between b value after treatment and b value before treatment is indicated by Δb. The smaller Δb, the less yellowing.

Comparative Example 1

7 g of dimethylacetamide and 3 g of dialkyl sulfosuccinate were mixed at about 80 ° C. for about 5 hours to obtain a liquid dialkyl sulfosuccinate. It was ignited in an oven at about 220 DEG C for about 4 hours. The results are shown in Fig. As can be seen from FIG. 1A, the baked dialkyl sulfosuccinate is considerably carbonized.

Example 1

2 g of dimethylacetamide, 3 g of dialkyl sulfosuccinate and 1 g of 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenol) propionic acid stearyl ester were added thereto at about 80 ° C. for about 5 hours After mixing, 4 g of dimethylacetamide was added to obtain a liquid dialkyl sulfosuccinate. It was ignited in an oven at about 220 DEG C for about 4 hours. The results are shown in FIG. As can be seen from Fig. 1b, the ignited dialkyl sulfosuccinate can be confirmed to be free of carbonization.

Comparative Example 2

6 g of dimethylacetamide, 3 g of dialkyl sulfosuccinate and 1 g of 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenol) propionic acid stearyl ester were added thereto at about 25 ° C. for about 4 hours To obtain a liquid dialkyl sulfosuccinate. This was allowed to stand at room temperature for about 4 hours. As a result, Fig. 2a was obtained. As can be seen from the upper part of Fig. 2A, the turbidity of the solution in the vessel becomes higher, and a slight layer separation phenomenon can be visually confirmed. Further, it was ignited in an oven at about 220 deg. C for about 4 hours, and as can be seen from the lower portion of Fig. 2a, the dialkyl sulfosuccinate was considerably carbonized.

Example 2

2 g of dimethylacetamide, 3 g of dialkyl sulfosuccinate and 1 g of 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenol) propionic acid stearyl ester were reacted at about 85 ° C for about 5 hours After mixing, 0.2 g of triethylene glycol-bis-3- (3-tet-butyl-4-hydroxy-5-methylphenyl) propionate as a heat resistant additive was added and 4 g of dimethylacetamide was added, Alkyl sulfosuccinate was obtained. This was allowed to stand at room temperature for 1 month to obtain Figure 2b. As can be seen from the top of Figure 2b, it can be visually confirmed that the solution in the vessel remains transparent. Further, it was ignited in an oven at about 220 DEG C for about 4 hours. As can be seen from the lower portion of Fig. 2B, the dialkyl sulfosuccinate did not undergo carbonization.

Comparative Example 3

The polyol was prepared by mixing 2288 g of polytetramethylene ether glycol (molecular weight 1815) and 545.625 g of 4,4'-diphenylmethane diisocyanate. As the chain extender solution, a mixture of (ethylenediamine 42.9 g / 1,2-diaminopropane 13.2 g = molar ratio 80/20), a chain terminator solution (diethylamine 5.25 g) and a crosslinking agent diethylenetriamine And the mixture is introduced into a polymerization reactor.

The amount of diethylamine added is 1/18 (amine equivalent ratio) to the chain extender solution. The amount of amine introduced causes the equivalent of amine groups to be about 4 mole% over the isocyanate groups present in the prepolymer. The polymerization reaction is stopped until the content of the unreacted amine becomes about 4 mol% or less. Dimethyl acetamide was used as the solvent. 1.0 wt% of triethylene glycol-bis-3- (3-tet-butyl-4-hydroxy-5-methylphenyl) propionate as an additive to the solids content of the polymer, 0.5% by weight, 1,1,1 ', 1 ', 5 ' 0.5% by weight of tetramethyl-4,4 '(methylene-di-p-phenylene) disilecarbazide, 0.7% by weight of poly (N, N-diethyl-2-aminoethyl methacrylate) 0.1% by weight were added and mixed to obtain a polyurethane-urea spinning stock solution.

A 40 denier 3 filament polyurethane-urea elastic yarn was prepared by spinning the spinning solution obtained above at a spinning speed (spinning temperature: 250 ° C) at a speed of 900 m / min, and its properties were evaluated and shown in Table 1.

Comparative Example 4

The polyol was prepared by mixing 2288 g of polytetramethylene ether glycol (molecular weight 1815) and 545.625 g of 4,4'-diphenylmethane diisocyanate. As the chain extender solution, a mixture of (ethylenediamine 42.9 g / 1,2-diaminopropane 13.2 g = molar ratio 80/20), a chain terminator solution (diethylamine 5.25 g) and a crosslinking agent diethylenetriamine And the mixture is introduced into a polymerization reactor.

The amount of diethylamine added is 1/18 (amine equivalent ratio) to the chain extender solution. The amount of amine introduced causes the equivalent of amine groups to be 4 mol% excess relative to the isocyanate groups present in the prepolymer. The polymerization reaction is stopped until the content of the unreacted amine becomes about 4 mol% or less. Dimethyl acetamide was used as the solvent.

1.0 wt% of triethylene glycol-bis-3- (3-tet-butyl-4-hydroxy-5-methylphenyl) propionate as an additive to the solids content of the polymer, 0.5% by weight, 1,1,1 ', 1 ', 5 ' 0.5% by weight of tetramethyl-4,4 '(methylene-di-p-phenylene) disilecarbazide, 0.7% by weight of poly (N, N-diethyl-2-aminoethyl methacrylate) And 0.1 wt% of a solid phase (wax type) dialkyl sulfosuccinate were added and mixed to obtain a polyurethane-urea spinning stock solution.

A 40 denier 3 filament polyurethane-urea elastic yarn was prepared by spinning the spinning solution obtained above at a spinning speed (spinning temperature: 250 ° C) at a speed of 900 m / min, and its properties were evaluated and shown in Table 1.

Example 3

The polyol was prepared by mixing 2288 g of polytetramethylene ether glycol (molecular weight 1815) and 545.625 g of 4,4'-diphenylmethane diisocyanate. As the chain extender solution, a mixture of (ethylenediamine 42.9 g / 1,2-diaminopropane 13.2 g = molar ratio 80/20), a chain terminator solution (diethylamine 5.25 g) and a crosslinking agent diethylenetriamine And the mixture is introduced into a polymerization reactor.

The amount of diethylamine added is 1/18 (amine equivalent ratio) to the chain extender solution. The amount of amine introduced causes the equivalent of amine groups to be 4 mol% excess relative to the isocyanate groups present in the prepolymer. The polymerization reaction is stopped until the content of the unreacted amine becomes about 4 mol% or less. Dimethyl acetamide was used as the solvent.

0.8 wt% of triethylene glycol-bis-3- (3-tet-butyl-4-hydroxy-5-methylphenyl) propionate as an additive to the solids content of the polymer, 1,3,5- 0.5% by weight, 1,1,1 ', 1 ', 5 ' 0.45% by weight of tetramethyl-4,4 '(methylene-di-p-phenylene) disilecarbazide, 0.7% by weight of poly (N, N-diethyl-2-aminoethyl methacrylate) 0.1% by weight, and 3.3% by weight (1% by weight based on solids) of the liquid dialkyl sulfosuccinate obtained in Example 1 were added and mixed to obtain a polyurethane-urea spinning stock solution.

A 40 denier 3 filament polyurethane-urea elastic yarn was prepared by spinning the spinning solution obtained above at a spinning speed (spinning temperature: 250 ° C) at a speed of 900 m / min, and its properties were evaluated and shown in Table 1.

strong
(g) Shindo
(%) SS100
(g) SS300
(g) Cohesiveness
(g) Heat resistance
(? B) Heat-resistant additive
Addition amount Comparative Example 3 61.0 595 4.30 11.2 0.18 3.5 to 3.7 1.0% Comparative Example 4 65.5 550 4.26 12.2 0.29 3.5 to 3.7 1.0% Example 3 69.8 561 4.31 12.1 0.30 3.5 to 3.7 0.8%

As can be seen from the above Table 1, the polyurethane-urea elastic yarns according to Comparative Examples 3-4 and Example 3 are excellent in physical properties such as elongation, strength 100%, strength 300%, and adhesion strength between filaments and filaments, It can be seen that no difference is shown. However, it can be confirmed that the polyurethane-urea elastic yarn according to Example 3 is superior to the polyurethane-urea elastic yarn according to Comparative Example 3-4 in terms of strength and heat resistance (substantially the same effect even when added in small amounts).

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the present invention. It is obvious that the modification or improvement is possible.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

15 to 40% by weight of a dialkyl sulfosuccinate represented by the following formula 1 and 5 to 10% by weight of an antioxidant are added to 5 to 20% by weight of dimethylacetoamide or dimethylformamide, followed by reaction at 75 to 95 캜 Followed by adding dimethylacetoamide or dimethylformamide as the balance to form 100 wt% of the dialkyl sulfosuccinate.
[Chemical Formula 1]

Wherein R ₁ and R ₂ are independently of each other hydrogen or an alkyl group of 1 to 30 carbon atoms and M ⁺ is a cation of the H ⁺ , Li ⁺ , Na ⁺ , K ⁺ or NH ₄ ⁺ series. The method according to claim 1,
Wherein the antioxidant is a phenol-based antioxidant. The method of claim 2,
The phenolic antioxidant may be a 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenol) propionic acid stearyl ester or terakis methylene- Butyl-4-hydroxyphenyl) propionate. ≪ / RTI > The method according to claim 1,
Wherein the reaction time is 4 to 6 hours. The method according to claim 1,
The method may further comprise adding 1 to 5 wt% of at least one additive selected from the group consisting of a heat resistant additive, a UV absorber, a dyeability improver and a yellowing inhibitor after the reaction at 75 to 95 ° C. Alkyl sulfosuccinate. The method of claim 5,
The heat-resistant additive is selected from the group consisting of triethylene glycol-bis-3- (3-tet-butyl-4-hydroxy-5-methylphenyl) propionate or 1,3,5- 2,6-dimethylbenzene) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -tione, and the yellowing inhibitor is bis (1.2.2.6.6. (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole and the dyeability improver is poly ( N, N-diethyl-2-aminoethyl methacrylate. The method according to claim 1,
Wherein the reaction is carried out under reduced pressure to maintain the moisture content of the final product below 5000 ppm.

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