DE2412324A1 - DISPERSIONS OF 2-ALKYL-4,6-DINITROPENOL-ESTERS - Google Patents

Description

FARBWERKE HOECHST AG "formerly KeJscer Lucius & Brüning file number: HOE Hk / Υ 075

Date: 12-. March 1974. . Dr. Tg / br

D i s p ersions of 2-alkyI ~ 4,6 ~ dinitro-phenol-esters

The invention relates to stabilized aqueous dispersions of 2-alkyl-4,6-dinitro-phenol esters, which are used as fungicides and / or Acaricides or herbicides are known.

Known representatives of this class are, for example, the Dimethylacrylsäure- (4, o-dinitro-E-sec-butylpheiiyl) ester (binapacryl), and the Kohiensäure-Isopi ~ opyl- (4 _t 6-dinitro-2-sec »butylphenyl ) ester (dinobutone), a carbonic acid diester.

The heating of tron -aqueous dispersions of such esters was already described (see e.g. DT-OS 1.912.707). Such dispersions are stable for a short time, but show a considerable tendency towards crystal growth after longer storage. This is due to that the 2-alkyl-4,6-dinitro-phenol esters have a certain albeit very high have low solubility in water. Go there because of their higher Solution pressure favors the small particles, which are at the bottom of the size distribution curve, in solution. This creates a saturated solution from which the active ingredient gradually recrystallizes on the larger, undissolved crystals. In this way, in commercial dispersions, in

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in which the active ingredients originally had intrinsic grains in the order of magnitude of less than 10 microns, and crystals of up to 50 microns in length after storage for 2 to 3 months.

A coarsening of the active ingredient particles with a simultaneous decrease the number of particles inevitably has a reduction in quality the dispersion and a decrease in biological effectiveness result. So there was a considerable practical need to stabilize the active ingredient particles in such dispersions against undesired crystal growth.

Erfiiiduiigsgemäß this problem is solved in that such aqueous dispersions metal complex dyes to 3 »preferably 0.3-1 wt.% Is added from the series of the azo dyes and Phthalocyaninfarbstoffkomplexe in concentrations of _1-O I.

Suitable metal complex dyes are z.3. what serious Ii before sulforiamide groups 2: 1 monoazo metal complex dyes. With these acts they are coupling products of optionally substituted β-naphthols or substituted pyrazolones with sulfonaniid groups containing optionally substituted Hydroxyanilineii, which as Central atoms contain cobalt or chromium. Connections of this type are for example in DT-AS 1,015,866 and US-PS 2,610,175 described. An example of this is the dye known under the generic name Acid Blue 199, a 2j1 monoazo dye-chromium complex. * ''

Water-insoluble, laked-up sulfo-containing groups are also suitable Azo dyes obtained by coupling naphthols, which may be substituted by carboxylic acid and / or sulfonic acid groups, in particular of ß-naphthol, with optionally (preferably by -CH.J, -COOH and / or Cl) substituted anilinesulfonic acids or Naphthylamines and subsequent laking with metal salts are created, (see Venkataraman, "The Chemistry of Synthetic Dyes" (New York 1952), Vol. I, p. 486). They preferably contain barium, calcium and manganese as the central metal atom; particularly preferred are the Ba compounds. Examples of such sulfo groups Azo dyes that are loaded with metal salts are

the dyes listed in the Color Index Lake Pigment Red 53- (CI. No. 15 585) ,. Lake Pigment Red 68 (CI, No. 15 525), Lake Pigment Red 57 (CI No. 15 85O) and Lake Pigment Red 5> t

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(CI. No. Ik 830).

Finally, phthalocyanine dyes are also suitable, the phthalocyanine structure being either unsubstituted or substituted by chlorine or bromine. Such complexes preferably contain copper, cobalt and iron as central atoms. Examples are CI Pigment Blue 15 (CI No. 7 ¹ I 160), a copper phthalocyanine, pigment green "7 (CI. No. 7 ^ 260), a polyhalogenated copper, - 'phthalocyanine, and cobalt phthalocyanine.

Of course, the problem of crystal growth only occurs such 2-alkyl-4l ·, 6-dinitro-phenolesters at the temperatures grinding and storage are firm. This is generally the case with such 2-alkyl ~ * t, 6-dinitrophenol esters, which are above 30 °, preferably melt above 50 ° C. These include in particular Compounds of the general formula

in which ■

R (C ₁ -C ₅ ) -alkyl or (C -C _& ) -cycloalkyl, R «(C ₁ -C ^) -alkyl, (C ₂ -C ^) -alkenyl, (C -C,) -0 -Alkyl or the phenyl or cyclohexyl radical and R "denotes methyl or preferably hydrogen."

The radicals for R are straight-chain, in particular methyl, or, preferably branched ones such as sec-butyl- or tert-butyl-, for R ¹ methyl, ethyl, propyl, isopropyl, butyl, vinyl, dimethylvinyl -, methoxy, ethoxy, propyloxy, isopropyloxy in question.

Well-known examples of this are in particular the /5.6-Dinitro-2-sec.-7butylphenol7-dimethylacrylic acid ester (Binapacryl.), The corresponding isopropyl carbonic acid ester (dinobutone), the benzoic acid ester and the eexahydro-benzoic acid ester; also the / ~ k , 6-dinitro-2-tert. ~ butyl-phenol7-acetic acid ester, the / 5, 6-dinitro-2-tert. ~ butyl ~ 5-ffiethyl-phenol7-acetic acid ester, and furthermore, the

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/5,6~ Dinitro-2-sec.~ butyl-phciiol7-trimethylessigsäure- resp. (ethyl carbonic acid) ester.

The various dispersants are particularly suitable Cell pitch types (lignosulfonic acid sodium, calcium and ammonium salts) as well as sodium salts of dinaphthylmethane disulfonic acid as well as alkali and ammonium salts of polymeric alkyl sulfonic acids. The commercially available dispersants can be particularly advantageous Vanisperse CB (sodium lignin sulfate) and

(R)

Darvan No. 3 (sodium polyalkyl «■ * sulfonate) should be used. The proportion of dispersants is in the order of magnitude of 2-5 %.

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Example 1 ( Compare 3beispji.ejJ

In ο J only friction ball inülil e, in the quartz balls of 2 now Dtuch ~ inesäor'ala grinding media are contained, becomes a dispersion JO I - {V'iuJts i · Composition aiiJ "Koriii'uiuhci ton of unLoi · Ί micron vuiinah 1 en:

$ 0 Gt'W.ji Üinapacry1 techn.

2 Gow, # Vanisperse ClP ^R '

0.8 wt. '/ Darvan No. 3' ¹ ^

1.0 wt. ^ Acid Blue 199 ' k6.2 Gev ° yes water.

The dispersion has a relatively low viscosity and is easy to use. The grain distribution spectrum remains even after prolonged storage or under severe storage conditions at 50 C for more than three Months stable. The average grain size is after that on the order of ό microns.

Wild the dispersion according to Example 1 without the addition of a stabilizer If the viscosity increases at the same time, a crystal growth of the binapacryl occurs during storage a. Crystals appear after 6-8 weeks of storage from 30 - 50 microns, some technical binapacryl batches even tend to sedimentation.

Example 2:

According to Example 1, a dispersion of the following 'composition manufactured:

50 wt.% Binapacryl techn. 2 wt. $ Vanisperse CB ^ '0.8 wt. ^ Darvan No. 3' ^R * ■

1.0 wt.% CI, Pigment Blue (CI. No. 7 ^ 160)

hb, 2 wt. ^ water.

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Dei * Stabilisiuruiigseffekfc IhL the same as in Example 1 "

Hui Sj) LuI 3:

According to Example 1, a dispersion is made with the following composition is called; put fc:

50 GcW ₁ ^ lilnaxjacryl techn. 2 Gcw.'i Vunisperse CIi ^ ¹ ^ 0.8 wt. F Darvan No. 3 ' ¹ ^

0.5 wt. # CI, pigment song 5'j: l (Sa - salt) (Cl, No. 15 585: 1)

k6, J Gev. '. ^ water.

The ü tabi I ization sef J'elc t is the same as in Hei game

Be is pi ei

According to Example 1, a dispersion is made with the following composition made by J. t:

50 wt. $ Binapacryl techn. 2 wt. # Vanisperse C 0.8 wt. Ic Darvan No. 1, 0 wt. $ Cobalt phthalocyanine

k6,2 Gev.fi water.

The stabilization effect is the same as in example

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Example · 5 According to Example 1, a dispersion is made made of the following composition:

50 ,8th Ge w. - $> Binapacryl techn. 3 , 0 dd • p
Vanisperse CB 0 ti R.
Darvan Kr. 3 1 η Hostapermgriin GG η water

py

Cu phthalo cyanine)

Here, too, the crystal growth of the binapacryl can be prevented will.

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Example 6 (comparative example)

The Grind dispersion of the following composition to a grain size of less than "5 microns:

50 wt. 56 dinobutone tech. 3 "Vanisperse CB ^R

0.2 "sodium dinaphthylmethanedisulfonic acid (Taraol KHO) ^R

TJ

0.6 ⁿ Darvan # 3 46.2 "water

The dispersion obtained has good flowability, driving however, storage at 50 C occurs after 4-6 weeks considerable crystal growth a '

that is a decrease in physical properties and has a biological effect. -

Example 7 : '-

Crystal growth can be prevented if one of the dispersion before grinding 0.8 wt. CI. Pigment Blue 15 adds:

50 wt .- ^ dinobutone techn.

3 ". Vanisperse CB ^R

0.2 "Tamol NNO ^R

0.6 ^h Darvan No. 3

0.8 «· CI. Pigment Blue 15 (Cu phthalocyanine)

45.4 "water.

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Example 8:

If one proceeds according to Example (7), ab, he replaces Pigment Blue by Lake Pigment Red 57 (C.I. No. 15 850), the crystal growth of dinobutone in aqueous dispersions is reduced hinders. An aqueous dispersion of the following composition: -

'40 wt * $ dinobuton

5.5 wt. $ Vanisperse CB ^R

Op 3 Gew "$ Tamol NNO

0.6 wt. $ Darvan No. «3

1.0 wt. 5 ^ Lake Pigment Red 55 (Ba-SaIz)

54.6 wt. $ Water

shows a greatly slowed down crystal growth compared to Example (6).

Example 9, ·:

The 4,6-r-dinitro.2-tert-butylphenol-acetic acid ester also shows in the form of its aqueous dispersion a stronger crystal growth. It can be obtained by adding Cu-phthalocyanine strongly delay. With the following composition:

50 wt. # ■ 4,6-Dinitra-2-tert-butylphenol acetic acid ester

3 wt. # Vanisperse CB

0.8 wt. 1 ° Darvan No. 3

1.0 wt. ^ CI. Pigment Blue 15 (CI. No. 74160) 45.2 wt.% Water

a stabilized dispersion is obtained after grinding according to example (6).

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Claims (5)

Claims 1) Stabilized aqueous dispersions of 2-alkyl-4,6-dinitrophenol esters, characterized by a content of 0.1 to 3% by weight, preferably 0.3-1% by weight, of a metal complex dye from Series of azo dye and phthalocyanine dye complexes. 2) Stabilized aqueous dispersions according to claim 1, characterized in that the azo dye complex is a water-soluble 2: 1 monoazo metal complex containing sulfonamide groups or a water-insoluble one, optionally by coupling carboxylic acid or Naphthols containing sulfonic acid groups with optionally substituted anilinesulfonic acids or naphthylamines and then Is laked azo dye obtained by laking with metal salts. . 3) Stabilized aqueous dispersions according to claim 1 and 2, characterized in that the azo dye complex Acid Blue 199 (2: 1 monoazo dye-chromium complex). i
k) Stabilized aqueous dispersions according to claim 1 and 2, characterized in that the azo dye complex by laking Lake Pigment Red 53 (Color Index No. 15 505) ι Lake 'Pigment Red 68 (CI. No. 15.525), Lake Pigment Red 57 (CI No. 15,850) or Lake Pigment Red 5 ^; ± (CI. No. Ik 830) was obtained. 5) Stabilized aqueous dispersions according to claim 1, characterized in that the phthalocyanine dye complex is Pigment Blue 15 (CI. No. Tk I60), Pigment Green 7 (CI No. 7 ^l i 26o) or cobalt phthalocyanine. 509839/1036