CS235200B1 - Emulgating agent - Google Patents

Description

The present invention provides an emulsifier or a component thereof for organic compounds, in particular phosphorus.

From economic and ecological reasons, water is the most important raw material - the solvent of many compounds that we want to get into solution. Compounds that are not normally water-soluble and do not want to be used to dissolve organic solvents, often expensive, flammable or health-defective, are then introduced into the aqueous system by another additive called an emulsifier. Generally we can divide emulsifiers according to their origin into natural and synthetic. In practice, however, synthetic, characterized by their surface activity predominates. All types of surfactants are used as emulsifiers. The most widely used surfactants are based on oxyethylated fatty alcohols, alkylphenols, higher fatty acids, higher amines, sorbitol fatty acid esters and pentaerythritol. In addition to the nonionic surfactants to be exchanged, anionic surfactants which are coated to a lesser extent with cationic and amphoteric surfactants are used as emulsifiers in order to achieve the desired emulsion stability. U.S. Pat. No. 2,824,832, U.S. Pat. No. 2,839,464; U.S. Pat. No. 55,803). For pesticidal formulations, in particular types of phosphoric, thiophosphoric and dithiophosphoric esters, the composition of several emulsifiers is also known. CSL. No. 174,368 discloses an emulsifier consisting of three components, namely, dodecylbenzenesulfonic acid calcium salt, oxyethylated ricinoleic acid, and ethylene oxide / propylene oxide copolymer. English Patent 854 952 describes the preparation of polyglycol ethers with 10 to 20 moles of ethylene oxide from a compound prepared by reacting styrene or its derivatives such as vinyltoluene, α-methylstyrene and dllnylbenzene with phenol or its derivatives such as xylene, xylenol. DAS 1 542 875 discloses the preparation of 50 to 80 percent emulsion concentrates of pesticides with the addition of 50 to 20% by weight of a mixed emulsifier consisting of a copolymer of ethylene oxide with propylene oxide and a calcium (barium, strontium, magnesium) salt of a higher alkyl aryl sulfo acid. MS. pat. No. 89,827 discloses as an emulsifier for plant protection agents a naphthenic core nonionic surfactant substituted one to three times with a monovalent substituent containing an aromatic or hydroaromatic ring. Antenna and nonionic surfactant mixtures are described by most patents (Ang. Pat. 769 736, Eng. Pat. 815 001, US Pat. 2 946 721, US Pat. 2 898 267, US Pat. 353,016, French Pat. 1,166,568).

A disadvantage of these emulsifiers is their raw material intensity. Dodecylbenzenesulfonic acid calcium salts often contain only about 30% by weight of the active ingredient and the remainder are solvents. It is difficult to prepare a product of 100% active ingredient. Worldwide, calcium dodecylbenzenesulfonate is prepared to emulsify 70% by weight of the active ingredient and the remainder to 100% by weight are solvents. Water as a solvent is unsuitable as emulsion concentrates containing as an emulsifying component organic phosphorus compounds may be subject to hydrolysis and thus to loss of activity. The presence of organic solvents in the system such as isopropanol, butanol and the like. in many cases it is a defect because of its flammability. The range of emulsifiers for special organic compounds containing the most phosphorus is small. There is a need to expand the range of emulsifiers for organic compounds containing phosphorus in their molecule, especially for phenylphosphite-type stabilizers and natioxidants based on raw materials and technically readily available products.

According to the present invention, the emulsifier or component thereof for organic compounds, in particular phosphorus, consists of a mixture of a monoester and a diester of phosphoric acid having a phosphorus content in its acid form of 1 to 2.5% by weight of the general formulas

ABOUT

II

XO-P-O (C 2 H 4 O) _X -R OH o

XO (C 2 H 4 O) _y -O-P-O (C 2 H 4 O) _Z R ox wherein

X is hydrogen, sodium, potassium, an aliphatic and / or cyclic amine having a carbon number of 2 to 10,

ABOUT

^C n ^H 2n 4 1 x, y, z are integers positive and their sum * is 10 to 25, and n is 6 to 15.

The advantage of the emulsifiers according to the invention is the raw material availability and ease of preparation. Phosphatization can be carried out according to known procedures, as the most commonly used phosphorylating agent is phosphorus pentoxide. The use of phosphorus pentoxide produces a primary and secondary ester. The tertiary ester is hardly formed, and acidic hydrogens can also be neutralized by various inorganic and organic bases. The ratio of primary to secondary ester is in the range of 30 to 80% of the primary ester to 20 to 45% of the secondary ester. An emulsifier without undesirable solvents containing an active ingredient content of 100% by weight can be prepared. The emulsifier is not flammable and harmful to health. It has not only an emulsifying ability but also antistatic activity.

The emulsifier of the invention may also be applied in combination with other surfactants, emulsion stabilizers and solvents. It can also be used in addition to emulsifying organic phosphorus compounds to emulsify other compounds, especially for pesticide formulations. Further details regarding the emulsifier of the present invention are evident from the examples.

Example 1 p-cumylphenol of mol. of mass 213.2 is oxyethylated at 135 ° C with 20 moles of ethylene oxide. 327 g (0.30 mol) of the product thus obtained are phosphated with 15 g (0.1 mol) of P2O5 at 80 to 90 ° C. The phosphorus content of the acid product is 1.9% by weight, the pH of the 1% aqueous solution is 3, The emulsifier has the appearance of a waxy substance and the following physicochemical constants: density at 50 ° C (kg. Cm ^-3 ) = 1123, viscosity at 50 ° C (mPa. Sj = 238.5, water content (%) = 0 06, refractive index at 70 ° C = 1.4791.

The emulsifying capacity is determined on a mixture of tri / 1-phenylethylphenylphosphites characterized by a phosphorus content of 3.48% by weight. and formula

With stirring at 900 rpm, 75 cm ^{3 of} heated water to 50 ° C are added over 30 minutes. The pH of the emulsion is adjusted to 7-8 with dilute sodium hydroxide solution. After the addition of water, the emulsion is stirred for one hour at the same speed and temperature. The emulsion obtained is poured into a 100 cm ³ graduated cylinder and visually monitored for stability. The emulsion was stable for 4 hours.

Example 2

A mixture of phenylethylphenylphenols also named as styrenated phenol of approximate formula

OH r-i

in mol. weight 220 is oxyethylated at 135-140 ° C using an alkaline catalyst for 15 moles of ethylene oxide. 396 g (0.46 mol) of the product is phosphated at 80-90 ° C with 22 g of P2O5 (0.16 mol). The acidic product contains 2.3 percent by weight. phosphorus. Neutralization is done with diethylamine. The emulsifier has the appearance of a viscous liquid having the following physicochemical values: density at 50 ° C (kg. M- ³ ) = 1141; viscosity at 50 ° C (mPa · sj - 1896; refractive index at 70 ° C = 1.4912).

The emulsifying ability is determined according to the procedure described in Example 1, but instead of the tri / 1-phenylethylphenyl phosphite mixture, an emulsified mixed triaryl phosphate with a predominant tris / isopropylphenyl phosphate content of phosphorus content of 7.48% is emulsified

The emulsion is stable for 2 hours.

Example 3

The mixture of phenylethylphenols is oxyethylated under the conditions of Example 2 with 20 moles of ethylene oxide. 330 g (0.30 mol) of the product is phosphated with 15 g (0.1 mol) of P2O5 at 80 to 90 ° C. The acidic product contains 1.8% phosphorus. Neutralization is performed with monoethanolamine to pH = 7.2. The emulsifier has a paste-like appearance having the following physicochemical values: density at 50 ° C (kg. M- ³ ) = 1135, viscosity at 50 ° C (mPa · s) = 1815; refractive index at 70 ° C = 1.4849. The emulsifying ability is determined according to the procedure described in Example 1 for a mixture of tri / 1-phenylethylphenylphosphites. The emulsion cost 24 hours.

Example 4

Nonylphenol of mol. weight 220 is oxyethylated at 135 ° C using an alkaline KOH catalyst with 20 moles of ethylene oxide. 68 kg (0.06 mol) of the obtained alkylphenol polyglycol ether are phosphated with 2.6 kg (0.02 mol) of P2O5 at 80 to 90 ° C. The phosphorus content of the acid product is 1.6% by weight. Neutralization is carried out with 50% aqueous sodium hydroxide solution to pH = 6.9. The emulsifier has a wax appearance of the substance and the following physicochemical constants: density at 50 degrees Celsius (kg.m ^-3 ) = 1088, viscosity at 50 ° C (mPa.s) = 232, refractive index at 70 ° C = 1, 4684th The emulsifying ability is determined on a tri / 1-phenylethylphenylphosphite mixture according to the procedure described in Example 1. The emulsion is stable for 6 hours.

Example 5

The phenylethylphenol mixture characterized in Example 2 is oxyethylated at 135-145 ° C using an alkali catalyst to 25 moles of ethylene oxide. 396 g (0.3 mol) of the product is phosphated at 80-90 ° C with 15 g of P2O5 (0.1 mol). The acidic product contains 1.0% phosphorus by weight. Neutralization is carried out with cyclohexylamine to pH = 6.9. The emulsifier has a pasty substance having the following physicochemical constants. Density at 50 ° C (kg.m ^-3 ) = 1136, viscosity at 50 ° C (mPa.s) = 1607, refractive index at 70 degrees Celsius = 1.4847. 50 g of the emulsifier thus prepared is homogenized at 80 ° C with 900 g of the tri / 1-phenylethylphenylphosphite mixture characterized in Example 1 and 50 g of a mixture of aromatic-naphthenic-paraffinic hydrocarbons declared as aviation kerosene characterized as follows: aromatics content = max. 20% by weight, sulfur content = max. 0.1% by weight, acid number = 0.4 to 0.7 mg KOH / g, density at 20 ° C - = 775 kg. m ^-3 , kinematic viscosity at 20 ° C = min. 1.30 mm ² / s. After homogenization, 1000 g of a mixed self-emulsifiable phosphorus antioxidant suitable for rubber production are obtained. The product is water soluble to form a stable emulsion.

Example 6

Weigh 21 g of O, O-dimethyl-S-phthalimidomethyl-dithiophosphate of the formula

O-Cx o

and dissolved in 45 g xylene and 26 g cyclohexanone. Then, 3 g of calcium phenylsulfonate and 5 g of emulsifier prepared according to Example 5 are added. After homogenization, 100 g of an insecticidal composition intended for destroying the potato tape are obtained. The insecticidal composition dissolves in water to form a stable emulsion.

Example 7

Weigh 82 g of methyl 3- (4-chlorophenyl) -2-chloropropionate of the formula

and dissolved in 8 g of xylene. Then 4 g of calcium phenylsulfonate and 6 g of emulsifier prepared according to Example 2 are added. After homogenization, 100 g of a herbicidal composition intended for destroying deaf oats are obtained. The herbicidal composition dissolves in water to form a stable emulsion.

example

Weigh 21 g of N- (1-farmamido-2,2,2-trichloroethyl) morpholine of the formula

Ct CH-NH-CH-O

which is dissolved in 57 g of cyclohexanone. 5.5 g of calcium phenylsulfonate and 16 g of emulsifier prepared according to example 5 are added. After homogenization, 100 g of fungicidal composition intended for controlling powdery mildew in agricultural crops are obtained. The fungicidal composition dissolves in water to form a stable emulsion.

Claims (1)

SUBJECT We claim: An emulsifier or component thereof for organic compounds, in particular phosphorus, characterized in that it consists of a mixture of a monoester and a diester of phosphoric acid having a phosphorus content in its acid form of 1 to 2,5% by weight of the general formulas o II XO-P-O (C 2 H ₄ O) _x -R I OH ABOUT II XO (C 2 H 4 O) _y -O-P-O (C 2 H 4 O) is _from R x wherein X is hydrogen, sodium, potassium, an aliphatic and / or cyclic amine having a carbon number of 2 x, y, z are positive integers and have a total of 10 to 25, and n is Θ to 15.