KR810000265B1 - Sulfur-containing complexesters - Google Patents

Abstract

Esters are prepd. by reaction of thiodiproponic acid(I) with polyhydric acid with polyhydric(>=3 OH groups) alcs, and C5-24 monobasic aliph. acids and are used as heat stable lubricants in compns. contg. surfactants and antistatic agents for improving the processability of synthetic fibers. Thus, a mixt. of 1 mol pentaerythritol, 0.5 mol I, 2.9 mol 3:72:25 caproic-caprylic-capric acid mixt., 3.5 g p-MeC6H4SO3H and 700 g xylene was refluxed under N with removal of liberated H2O neutralized, and stripped by heating in vacuo to give a product(II) with acid No. 0.1, sapon No. 364, and av. mol wt. 1042.

Description

Preparation of Sulfur-Containing Complex Ester

1 is an infrared absorption spectral diagram of the sulfur-containing complex ester in Example 1. FIG.

2 is a nuclear magnetic resonance absorption spectrum diagram of the compound.

3 is an infrared absorption spectral diagram of the sulfur-containing complex ester obtained in Example 2. FIG.

4 is a nuclear magnetic resonance absorption spectrum diagram of the compound.

The present invention relates to a process for producing novel sulfur-containing complex esters by esterifying thio dipropionic acid, a polyhydric alcohol and a monobasic acid.

The polyhydric alcohol used by this invention is a trihydric alcohol or more, and there exist a trimethylol propane, a trimethylol ethane, glycerin, pentaerythritol, diplaerythritol, sorbitol, etc.

Monobasic acids used in the present invention are fatty acids derived from animal and vegetable fats and synthetic fatty acids obtained by paraffin oxidation method, oxo method, coho method, alkali melting method and the like. For example, acetyl acetic acid, isogyl acetic acid, capronic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myriric acid, penratecanoic acid, palmitic acid, Margarinic acid, stearic acid, nonadecanoic acid, arachinic acid, behenic acid, lignocerinic acid, oleic acid, isostearic acid, 2-ethylhexanoic acid, neoheptanic acid, neononanoic acid, and mixtures thereof and palm oil fatty acid, uric acid , Etc.

The molecular weight of the sulfur-containing complex ester obtained in the present invention is determined by the molecular weight and the molar ratio of the thiodipropionic acid, the polyhydric alcohol and the monobasic acid, respectively, and the preferred molecular weight is 700 to 3000.

The esterification reaction in the present invention is a conventional esterification reaction, using the esterification catalyst of thiodipropionic acid, polyhydric alcohol, and monobasic acid under an atmosphere of an inert gas such as nitrogen gas under normal pressure or reduced pressure. The reaction is carried out at a temperature of 70 to 240 ° C. for 2 to 20 hours, preferably at a temperature of 100 to 150 ° C. for 2 to 10 hours. At this time, an esterification reaction may be performed by adding a solvent that forms an azeotropic mixture with water such as toluene or xylene. As esterification catalysts, catalysts used in conventional esterification reactions such as sulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, perchloric acid, paratoluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, dodecylbenzenesulfonic acid, zinc powder, tin Powder, tin chloride, zinc oxide, calcium hydroxide and the like.

After completion of the esterification reaction, the unreacted or excess monobasic acid is distilled off under a reduced pressure of 0.1 to 40 mmmHg. Subsequently, water is washed after neutralizing the remaining monobasic acid and the catalyst using an aqueous alkali solution such as caustic soda.

If it is necessary to decolorize, decolorization is carried out using an adsorbent such as activated carbon or activated backhoe.

The sulfur-containing complex ester obtained by the present invention contains thiodipropionic acid as a component thereof, and also contains a sulfur atom as a sulfide bond in the ester chain, so the sulfur-containing complex ester is excellent in heat resistance. It also has excellent lubricity in terms of low friction coefficient, load resistance, and high viscosity index.

Therefore, the sulfur-containing complex esters obtained by the present invention are particularly useful as lubricants used at high temperatures. That is, it is useful as base oil or additives, such as hydraulic oil, rolling oil, cutting oil, grease, and a fiber oil.

In the case of using the sulfur-containing complex ester obtained in the present invention as a rolling oil, it exhibits good performance as a complex ester at the time of rolling, and is easily decomposed and volatilized at the time of annealing. It can be used as rolling oil which does not require a washing step. This is because the sulfide bonds are cleaved in the annealing process around 700 ° C. to be broken down into low molecular weight esters and volatilized easily. Many mixtures containing sulfide bonds are used as extreme pressure additives for lubricating oil. However, due to the low molecular weight, odors and sludges are generated by volatilization, and extreme pressure decreases with time, and other undesirable phenomena are caused.

On the other hand, since the sulfur containing complex acetate obtained by this invention is a high molecular weight sulfide compound, it does not have such a fault. Moreover, since the sulfur atom is firmly bonded to the metal surface together with the ester group, it exhibits excellent extreme pressure resistance.

The fiber emulsion for synthetic fibers is usually prepared by blending a smooth component, a surfactant, an antistatic agent and the like.

As the smoothing component, minerals, animal and vegetable fats and oils, synthetic esters, and the like are used, and problems such as fuming, coloring, tarting, and polymerization occur during the manufacturing processes such as melt-spinning, braiding, and other processing of synthetic fibers. Therefore, heat resistance is calculated | required by the smooth content.

When the sulfur-containing complex ester obtained in the present invention is used as a smoothing component, the chain reaction of pyrolysis is stopped by the free radical entrapment action of the sulfide bond, so that smoke, coloring, tarring and polymerization are suppressed.

The sulfur-containing complex ester obtained in accordance with the present invention is excellent in heat resistance and is preferable as a smoothing component of a fiber emulsion for synthetic fibers, particularly a smoothing component of a spinning emulsion.

The spinning oil which uses the sulfur containing complex ester obtained by this invention as a smoothing component is prepared by mix | blending surfactant and the antistatic agent of a required amount.

The spinning oil contains 50 to 98% by weight of sulfur-containing complex ester, 1 to 45% by weight of surfactant and 0 to 5% by weight of antistatic agent, and preferably 70 to 98% by weight of sulfur-containing complex ester and surfactant 2 To 30 wt% and 0 to 5 wt% antistatic agent.

The blending ratio of these is determined by the conditions of use of the spinning oil. Surfactants are surfactants commonly used in spinning oils, for example, polyoxyethylene, lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene adducts of castor oil, polyethylene glyco di Laurate, monostearic acid glyceride, monooleic acid glyceride, and the like.

When the spinning emulsion is used in the form of an aqueous emulsion, it is preferable that the surfactant be used as a mixture of two or more kinds for stabilization of the emulsion.

The antistatic agent is a surfactant commonly used in the spinning oil, and for example, sodium lauryl phosphate, sodium oleyl phosphate, potassium polyoxyethylene lauryl ether phosphate, cetyl potassium sulfate and the like.

In addition, the spinning emulsion may be used in combination with a sulfur-containing complex and the smoothing component normally used in the spinning emulsion.

In this case, at least 10% by weight, preferably at least 30% by weight of the total smoothing component is required to be a sulfur-containing complex ester.

Smoothing components commonly used in spinning oils include mineral oils, animal and vegetable oils, and synthetic esters, for example spindle oil, soybean oil, rapeseed oil, butyl stearate, isopropyl stearate, 2-ethylhexyl stearate, oleic oleate , Trimethylol propane of delagonate, trimethylol propane of tricaphrine, and trimethylol propane of trilauric acid.

The spinning emulsion is attached in an amount of 0.1 to 2% by weight with respect to the synthetic fiber yarn in the form as it is or in the form of an aqueous emulsion.

The synthetic fiber to which the above-mentioned spinning oil is applied may be polyamide, polyester, polyacrylonitrile, polyolefin, or the like, and the shape of the fiber yarn may be filament and yarn.

The spinning emulsion is used in the melt spinning process of synthetic fibers, and may also be used in the stretching process, twisting process and other processing processes.

Next, the melting of the method for producing the sulfur-containing complex ester according to the present invention and the obtained sulfur-containing complex ester for the spinning oil agent will be explained by way of examples, but the present invention is not limited to these examples.

In addition, in an Example,% represents weight%.

Example 1

Pentaerythritol 136g (1mol), thiodipropionic acid 89g (0.5mol), monobasic acid mixture (3% caproic acid, 72% caprylic acid, 25% capric acid) 436g (2.9mol), paratoluene sulfonic acid 3.5 g and 700 g of xylene are taken in a 3-liter four-necked fresco equipped with a reflux condenser, stirrer, thermometer and nitrogen blowing tube with a water vapor, and eluted under reflux of xylene at 145 to 155 ° C for 10 hours while removing water to be separated. When the reaction was carried out, the acid value of the reaction mixture decreased to 2.3.

The reaction mixture was then cooled to 90 ° C., added with 0.5% aqueous solution of sodium hydroxide, stirred for 30 minutes to neutralize the free fatty acids and the catalyst, and the aqueous layer was separated and washed with hot water. Subsequently, xylene was distilled off under reduced pressure of 1 to 2 mmHg, and the temperature was finally raised to 200 ° C to completely remove volatiles.

Next, the mixture was cooled to 70 ° C and decolorized using 3 g of activated carbon.

The obtained sulfur-containing complex ester (Compound A) had an acid value of 0.1, a saponification value of 364, an average molecular weight of 1042 by the vapor pressure balance method, an elemental analysis value of C: 62.76%, H: 9.84, S: 2.44, (calculated value C: 65.28%, H: 9.84%, S: 2.76%).

Other analyzes are shown in Table 1.

In addition, the infrared absorption spectral diagram of this ester is shown in FIG. 1 and the nuclear magnetic resonance absorption spectral diagram is shown in FIG.

Example 2

Reaction was carried out in the same manner as in Example 1 using 134 g (1 mol) of trimethylol propane, 119 g (0.67 mol) of thiodipropionic acid, a fatty acid for curing fat (acid value 204.6), 439 g (1.60 mol), 3.3 g of paratoluene sulfonic acid and 700 g of xylene. As a result, the acid value of the reaction mixture became 2.8.

This was purified in the same manner as in Example 1.

The obtained sulfur-containing complex ester (Compound B) had an acid value of 0.2, a saponification value of 238, an average molecular weight of 1796 by vapor pressure equilibrium method, an elemental analysis value of C: 70.58%, H: 10.89, and S: 3.02% (calculated value C: 72.14, H: 10.22 %, S: 3.21%).

Other analyzes are shown in Table 1.

In addition, the infrared absorption spectrum diagram of this ester is shown in FIG. 3, and the nuclear magnetic resonance absorption spectrum diagram is shown in FIG.

Example 3

The reaction and purification were carried out in the same manner as in Example 1 using 134 g (1 mol) trimethylol propane, 89 g (0.5 mol) thiodipropionic acid, 380 g (1.9 mol) lauric acid, 4 g paratoluene sulfonic acid and 700 g xylene. It was done.

Table 1 shows the analyzed values of the obtained sulfur-containing complex ester (Compound C).

Example 4

The reaction and purification were carried out in the same manner as in Example 1, using glycerin 92% (1 mol), thiodipropionic acid 89 g (0.5 mol), caprylic acid 274 g (1.9 mol), 5 g sulfuric acid, and 700 g xylene.

Table 1 shows the analysis values of the obtained sulfur-containing complex ester (Compound D).

Example 5

The reaction and purification were carried out in the same manner as in Example 1 using 254 g (1 mol) of dipentaerythritol, 89 g (0.5 mol) of thiodipropionic acid, 649 g (4.5 mol) of caprylic acid, 5 g of methanesulfonic acid, and 700 g of xylene. It was.

Table 1 shows the analysis values of the obtained sulfur-containing complex ester (unionyl E).

Example 6

The reaction and purification were carried out in the same manner as in Example 1 using 120 g (1 mol) of trimethylolpropane, 89 g (0.5 mol) of thiodipropionic acid, 274 g (1.9 mol) of 2-ethylenoic acid, 5 g of ethanesulfonic acid and 700 g of xylene. .

Table 1 shows the analysis values of the obtained sulfur-containing complex ester (Compound F).

TABLE 1

Example 7

Table 2 shows the results of the heat resistance test on the sulfur-containing complex ester, the sulfur-containing complex ester and the mixture of other esters and the comparative sample obtained in the present invention.

Comparative samples were synthesized from two complex esters conventionally used in fiber emulsions: complex esters contained in pentaerythritol, aceline acid and caprylic acid (compound G average molecular weight 1089), trimethylol propane, adipic acid and palmitic acid. Complex esters (Compound H, average molecular weight 1911), three esters and one mineral oil were used.

In the heat resistance test, 0.5 g of each sample was accurately weighed on a glass plate having a diameter of 90 mm, and heated at 220 ° C. for 3 hours in a hot air dryer.

The volatilization loss was expressed as a percentage of the weight of the sample before the test, and the tar loss, color, and gelation were visually determined.

It can be seen from Table 2 that the sample containing the sulfur-containing complex ester obtained by the present invention has good heat resistance.

TABLE 2

Example 8

Table 3 shows the results of measuring the coefficient of friction between the fiber and the metal by attaching each sample to the fiber in Example 7 by the method.

And the measurement was performed on condition of the following.

Thread Polyester Filament 75 Denier Metal Iron

Adhesion 1.5% Relative Humidity 65%

Travel speed of the yarn 300m / min Temperature 20 ℃

TABLE 3

It can be seen from Table 3 that the sample containing the sulfur-containing complex ester obtained by the present invention has a coefficient of friction almost equivalent to that of a comparative sample which is a conventional smooth component and has good smoothness.

Example 9

About the spinning emulsion of the composition shown in Table 4, it was made to adhere | attach 1% as a component to polyester filament (75 denier, 24 filaments) as a 15% water emulsion, and it extended | stretched twice at the heater plate temperature 200 degreeC by the conventional method.

In the case of treatment with the spinning oils Nos. 1 to 8 containing the sulfur-containing complex esters obtained by the present invention, there was little fuming and gelation on the heater plate during the thermal stretching, and the operation of the thermal stretching process was extremely smooth.

In the case of the conventional spinning oils Nos. 9 to 12 used for comparison, heat generation and tarring were caused on the heater plate.

TABLE 4

Claims (1)

A process for producing a sulfur-containing complex ester characterized by esterifying a thio dipropionic acid with a trivalent or higher polyhydric alcohol and a three-component monobasic acid having 5 to 24 carbon atoms.

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