DE1932299A1 - Phosphoric acid ester - Google Patents

Description

FARBEWFABRiKEN BAYER AG1932299

LEVERKUSEN-Biyeiwerk June 25, 1969 Patent department B / Li

Phosphoric acid ester

The invention relates to phosphoric acid esters of the general formula

^ 0-CH-C- (OH ₉ ) -XM I, R ₅ R ₄

in the

R ^ and R ₂ independently of one another for a C ₁ - CgQ

or C, _{-C 20} -alkenyl radical, with the proviso that the sum of the total of the carbon atoms contained in R .. and Rp is at least 12,

R, hydrogen or an oxymethyl group,

R. hydrogen, a hydroxyl group, a phenyl or a Cj - CjQ-alkyl radical optionally interrupted by oxygen atoms,

Rc hydrogen or a methyl group, η 0 or a number from 1-3, Σ the G groups -SO- "or -OSO, 'and M a cation

mean, and their use as wetting agents.

Pure r! | and R ₂ are, for example, the methyl, ethyl, iso-propyl, sec-butyl, 2-ethylhexyl, sodecyl, letradecyl, hexadeoyl and octadeoyl radicals _{as C 1 -C 20 -alkyl radicals} , mentioned as C- - C ₂₀ -Allcenylreste in particular the oleylrest.

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3932299 called methyl and ethyl but also the 2-oxa-decyl radical.

The alkali ions, such as the, come in particular as the cation M Sodium and potassium ions, also the magnesium ion and also ammonium ions, such as the ammonium, the mono-, di- and Triethanolammonium and cyclohexylammonium ions into consideration.

Representatives of the phosphoric esters according to the invention include, for example, the compounds of the formula I in which R ₁ , R ₂ , R-, R., R ₅ , X, M and η have the following meanings:

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^L 1

2 ^ ethyl-hexyl 2-ethyl-hexyl 2-ethyl-hexyl 2-ethyl-hexyl 2-ethylhexyl 2-ethylhexyl 2-ethylhexyl 2-ethylhexyl trimethylhexyl

_o trimethyl-hexyl cd n-octyl

oo n-decyl ^ n-dodecyl ^ ⁵ i-dodecyl

σ? n-dodecyl

2,2-dimethylhexyl

2-ethyl-hexyl 2-ethyl-hexyl 2-ethyl-hexyl 2-ethylhexyl 2-ethylhexyl 2-ethylhexyl 2-ethylhexyl 2-ethylhexyl trimethylhexyl Trimethyl-hexyl n-octyl n-decyl methyl ethyl n-butyl ■ (1) 2,2-dimethylhexyl- (1)

CHgOH CHgOH CH ₂ OH

C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅

CH, H *

H H H H H

H -OSO

H -OSO

H -OSO

H -OSO

H -OS '

H -SO ₃

H -OSO,

H -OSOj

η -oso;

H -OSO ^

H -, OSOj

H -OSO ^

H -OSO ^

H -OSOj

H -OSOj

H -OSOl

Well ^H

Ha

Ha"

Ha"

Ha ^H

Ha ¹

HH

O O

HH (C ₂ H ₄ OH) ₃ ⁺

2 O O O O O

HH (O ₂ H ₄ OH) ₃ ⁺ Ha ⁺

O O O

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CD OJ)

You can produce the phosphoric esters according to the invention be done in different ways; the production of those containing sulfate groups Ester e.g. B. by reaction of the oxyalkyl-containing dialkyl phosphoric acid esters of the formula

₃ O-CH-C- (CH ₉ V-OH II,

R R

R ₅ R ₄

in which Jl ^, R ₂ , R *, R ^ t ^R c "u && n have the meaning given under formula I, with sulfating agents such as chlorosulfonic acid, the preparation of the esters containing sulfonic acid groups, e.g. by reaction of the alkali metal salts of the dialkyl phosphorus- "acid esters with sultones or haloalkanesulfonic acids or by reacting the dialkylphosphoric esters with epihalohydrins and reacting the phosphorylhalohydrins or epoxy compounds obtained with bisulfite or by converting the oxy group in the oxygroup-containing dialkylphosphoric esters into esters of the hydrohalic acids, the sulfuric acid and the reaction of these esters with benzene or toluenesulfonic acid Sodium sulfite.

The preparation of the oxyalkylgruppenhaltigen dialkyl phosphates of the formula II is carried out by reacting the dialkyl phosphates with Spoxiden at temperatures between \ 50 and 120 ° C in the absence of catalysts. 1-3 moles of epoxide per mole of dialkyl phosphoric acid ester are added on. Particularly suitable epoxides for the addition reaction are ethylene oxide, propylene oxide and the butylene oxides; but styrene oxide, epichlorohydrin, 3-ethyl-3-oxymethyloxetane or epoxides which contain an alkyl chain interrupted by oxygen atoms can also be used successfully.

The compounds according to the invention are clear in water soluble or emulsifiable in water. You stand out e.g. T.

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characterized by an excellent wetting effect; some are esters good emulsifiers for natural or synthetic oils. The alkali resistance of the connections should be emphasized. In addition, the compounds according to the invention have a good one antistatic effectiveness.

example 1

In 322 g of di-2-ethylhe3yl-pihoephat at 80-85 ° C to Ethyleno ^ id introduced to saturation. After removing the Epoxy excess in vacuum is the yield of tertiary ester 379 g (acid content of the reaction product: 0.7) To 150 g of the tertiary eutor at 20 - 30 ° 0 46 g of chlorosulfonic acid are added dropwise. Then the split off hydrogen chloride is removed as completely as possible under reduced pressure. The sulfation mixture is then entered in the ice wall and with caustic soda neutralized. The amount of water is measured so that a 40 # paste is created. This dissolves clearly in water.

The ester is not only characterized by an excellent wetting effect but also by a very good antistatic effect the end. This can be seen from the table below, in which the surface resistances of various tissues that were treated with the aqueous solution of the ester, are compiled.

Surface resistance ISLJ _ (65 5 * relative humidity un3 30 ° C)

Poly- £ - Poly- polyethylene- caprolactam acrylonitrile terephthalate

untreated> 10 ¹⁵ > 10 ¹³ > 10 ¹³ treated with 5 g / l 1O ⁹ » ⁹ 10 ⁷ » ⁹ 1O ⁷ ' ⁷ treated with 10 g / l 10 ⁸ » ⁶ 10 ⁷ ' ⁵ 10 ⁷ » ⁶

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. 322 g of di-2-ethylhexyl phosphate are added at 80-90 ° C

130 g of butylene oxide (1.2 mol) were added dropwise. After the reaction has ended the excess epoxide is removed in vacuo (acid number of the ester: 0.4). 203 g of the tertiary ester are reacted with 63 g of chlorosulfonic acid as described in Example 1. After neutralization with 50% potassium hydroxide solution, a paste is obtained which dissolves clearly in water.

Example 3

180 g of 3-ethyl-3-hydroxymethyl-oxetane are added dropwise to 322 g of di-2-ethylhexyl phosphate at 80-90 °. Subsequently, ψ, the reaction mixture is stirred for 3 hours at 120 ° C. The acid number is then 0.6. As described in Example 1, 125 g of the tertiary ester are reacted with 29 g of chlorosulfonic acid. The sodium salt is a paste that is clearly soluble in water.

Example 4

In 64.4 g of di-2-ethylhexyl phosphate at 50-60 ° C. 10.6 g of anhydrous soda entered. The mixture is stirred until the cups develop. After that, that will The reaction mixture is slowly heated to 100 ° C. and 24 »4 g of butane sultone are added in portions. After the addition is complete the batch stirred for 5 hours at 150 ° C »After Cooling is made from the reaction product by diluting it with Water made a 40 pound paste that clears in Water dissolves. .

The superior wetting effect of the phosphoric acid esters according to the invention over the known, no anionic group having, water-soluble surface-active dialkylphosphoric acid ethoxylation products is based on the following Table in which the net effect of the examples

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1-4 described Este- * and the wetting effect of the water-soluble Esters (A) of the formula

(1O ₈ H _n O) ₂ P.

is put together. The ester A was through. Ethoxylate the according to Example 1 from di-2-äthyUiexyl-phosphate and Ethylene oxide obtained ester (acid number: 0.7) in glacial acetic acid in the presence of boron trifluoride.

The networks were according to DHJ 53 901 - determination of the sinking times of Baxuawollchen - depending on the Determines the concentration of the ester used in each case. The numbers in the 5 columns of the table mean the sinking times in seconds. These are mean values 5 measurements each.

Ester concentration in g per liter
0.2 0.4 0.6 0.8 1.0

A> 120.0> 120.0 100.0 75.0 50.0

of Example 1 103.0 26.0 10.7 5.7 4.0

of Example 2 84.4 29.8 15.3 7.0 4.1

of example 3> 120.0 48.2 26.4 15.9 9.9

of example 4> 120.0 87.6 39.3 22.2 13.4

Example 5

161 g of di-2-ethylhexyl phosphate are added at 110 ° C. with 114 g of the epoxides, which is produced by the reaction of 2-X.thylhexyl alcohol with epichlorohydrin. The reaction is continued until the acid number has dropped below 5. 138 g of the reaction product are, as described in Example 1, with 29 g of chlorosulfonic acid implemented. After neutralization with sodium hydroxide solution, a paste is obtained which dissolves in water in a cloudy manner.

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Claims (4)

Ea t relaxed \ ( 1) phosphoric acid ester of the general formula ^R °° in the R ₁ and R ₂ independently of one another for one or C * - CgQ-alfcenyl radical, with the proviso that the total of the total _{G atoms contained in R 1} and R _{2 is} at least 12, R- hydrogen or an oxymethyl group, R. Hydrogen, a hydroxyl group, a phenyl or an optionally interrupted G ^ * G ₁₀ -alkyl radical, R _{5 is} hydrogen or a methyl group, ή O or a number from 1-3, χ 'the groups ^ SO ₅ "or -OSÖ ^" and M mean a cation. 2) Phosphoric acid ester of the formula 7 2 3) Phosphoric acid esters of the formula 4) Use of the phobioric acid esters according to claims 1-3 Katsmittel. A 12 306 - 8 - 00908 2/2260