DE4318539A1 - Anionic siloxanyl modified polyhydroxylated hydrocarbons - Google Patents

Description

The invention relates to anionic siloxanyl modified Compounds, their production and their use as interface-active and interface-modifying Fabrics.

It is known to use siloxanyl modified alkenols Maleic anhydride to implement half esters, which then by neutralizing the free carboxylic acid function in anionic surfactants can be converted (DD 2 55 346, DD 2 82 692).

After all, siloxanyl-modified alkyl are already gluconamides have become known (JP 62-68 820), however even when using a small siloxane block only have limited solubility in water.

It is also known to use siloxanyl-modified alkanols with amidosulfuric acid in polar aprotic solution  to implement the sulfates (Poster D. Schaefer, P. Lersch, K.-D. Small, "Anionic silicone surfactants", Munich Silicon Days, August 1992).

There is therefore no teaching to be found in the prior art take, according to which the benefits of anionic Siloxane surfactants, such as. B. sharp lowering of the upper surface tension with which of saccharide surfactants, e.g. B. good biodegradability and compatibility with native organic materials can.

The subject of the application are therefore anionic siloxanyl-modified compounds of the general Formula (I)

wherein
Z stands for a solid derived from a mono- or oligosaccharide with pentose and / or hexose units, or for cyclic or acyclic polyhydroxylated hydrocarbons having 4 or 5 carbon atoms, the cycle containing at least one oxygen atom and optionally by 1 to 10 mono- or oligosaccharides are substituted with 1 to 10 pentose and / or hexose units,
n is calculated as the maximum possible number of OH groups of Z, where n is at least 3 and at most 40,
v represents a number 1 to 10,
w stands for a number 0 to 10, with a maximum of one group per monosaccharide unit

is available,
D and E independently of one another represent H, alkyl, C₁-C₄ acyl or X,
nvw is a number from 0 to 39,
X for alkyl, C₁ to C₄ acyl, the group

or for X ', where
X 'is an anionic radical which is derived from a dicarboxylic acid derivative, sulfuric acid derivative, lactone, sultone or isocyanatoalkylcarbonic acid derivative,
k represents a number 0 to 10,
and
R¹, R² independently of one another are H or CH₃, at least one radical being H,
M for a group

stands in what
Q for the groups

stands in what
R¹² represents H, alkyl or X ′,
R¹⁵ represents H or alkyl,
the groups T independently of one another are optionally substituted alkylene, which may be by at least one of the groups

Arylene, in each case saturated or unsaturated cycloalkylene or R¹¹ together with the group (T) _e forms a preferably 5- or 6-membered heterocyclic ring, is interrupted,
where i stands for a number 0 to 3 and
R¹³ and R¹⁴ independently represent X ′, hydrogen or C₁-C₄-alkyl,
L for the groups

stands,
R¹¹ is X or H, alkyl, hydroxyalkyl or the groups

stands,
a to h independently of one another represent a number 0 or 1, at least one index being 1,
Sil for a silicon-containing radical of the formula

stands in the
A stands for a siloxane chain consisting of m structural elements of the formula

and an end group

consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are alkyl, cycloalkyl, cycloalkyl-alkyl or optionally substituted aryl or aralkyl,
the radicals R⁵, R⁷ and R⁸ also for the group

stand,
R¹⁰ represents alkyl and
where the sum of the structural elements m independently of one another stands for a number from 0 to 600, and
B and R³ have the same meaning as A,
or represent alkyl, cycloalkyl, cycloalkyl alkyl, optionally substituted aryl or aralkyl,
or A and B together form a siloxane cycle,
where the radicals R⁴ to R¹⁰ in the chains A, B and R³ can be different, and
where one or more anionic groups and a corresponding number of cationic counterions are present in the molecule.

Water is preferably used as the cationic counterion substance, alkali metals such as Na, K and / or alkaline earth metals such as Mg, Ca or ammonium (primary / secondary / ter tiary / quaternary, NH₄⊕) in question.

In the context of the present invention, the substituents generally have the following meaning:
Alkyl can represent a straight-chain or branched alkyl radical having 1 to about 6 carbon atoms. Examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, n-pentyl, iso-pentyl, n-hexyl and iso-hexyl. Preferred alkyl radicals are methyl and ethyl.

Halogen may be fluorine, chlorine, bromine or iodine Fluorine or chlorine.

Cycloalkyl can be cyclic, preferably mono cyclic, hydrocarbon residue with 5 to 7 carbons atoms stand. For example, cyclopentyl, Cyclohexyl and Cycloheptyl called. Are preferred Cyclopentyl and cyclohexyl.  

Cyclcalkyl-alkyl can for a radical with 6 to 13 Koh lenstoffatomen stand, with a straight-chain or ver branched alkyl radical (C₁ to C₆) by a cycloalkyl rest (C₅ to C₇) may be substituted. For example be cyclohexylmethyl, 2-cyclohexyl-1-ethyl, cyclo called heptylmethyl and 2-cycloheptyl-1-ethyl. Before Cyclohexylmethyl, 2-cyclohexyl-1-ethyl are added.

Aryl can be used for an aromatic hydrocarbon residue have 6 to 12 carbon atoms. For example phenyl, naphthyl and biphenyl may be mentioned. Prefers is phenyl.

Aralkyl can be for a 7 to 18 carbon residue atoms stand, being a straight chain or branched Alkyl radical (C₁ to C₆) by an aromatic radical (C₆ to C₁₂) can be substituted. For example Benzyl, phenyl-ethyl and phenyl-propyl called. Before is benzyl.

The aryl and aralkyl radicals can optionally substi be acted upon. Examples include substituents Lower alkyl (C₁ to about C₆), aryl (C₆ to C₁₂) and Halogen, preferably fluorine and chlorine.

C₁ to C₄ acyl can be for a formyl, acetyl, Propionyl, iso-propionyl radical are available. Is preferred Acetyl.

The siloxane chain (A) consists of m structural elements

and the end group

wherein the substituents R⁴ to R¹⁰ the above Be to have an interpretation.

The structural elements can be distributed statistically or combined into larger structural areas (blocks) his. It is also possible that the siloxane chain is only made of one type of structural elements.

In general, the siloxane chain consists of a total 0 to 600, preferably 0 to 200, particularly preferably 0 to 50, structural elements (m).

The alkylene chain (T) can, for example, by the Groups like

be interrupted.  

The term "maximum possible number of OH groups from Z "in the definition of n means that in the case of sugars e.g. B. a pentose or hexose unit in the cyclic Form not contain more than 3 or 4 OH groups can.

The number of substituents M per unit Z is preferably 1 (v = 1). In this case there are several Sugar units via a spacer to any one Sil unit bound. In the event that v <1, is preferably a monofunctional Sil unit under Sil to understand.

An alkylene chain (T) generally represents one double-bonded, straight-chain or branched coal water hydrogen residue with 1 to 10 carbon atoms. Prefers become alkylene chains with 2 to 6 carbon atoms.

For example, the following alkylene chains are ge named: methylene, ethylene, propylene, isopropylene, 1-methyl-propylene- (1,3), 1,2-dimethyl-propylene- (1,3).

In the event that z. B. the number (m) of structural elements is 0 and B and R³ are alkyl, there is Siloxane chain only from the end group (disiloxane).

In the event that z. B. the number (m) of structural elements is 0 and B is methyl and R³ is A, be the silox content is only from the unit

Compounds of the formula (I) in which
Sil for the groups

or

stands,
where p and q independently of one another have values from 1 to 100, and Y has the meaning of methyl or

has, and
the remaining symbols, radicals and groups have the meanings given above.

Compounds of the formula (I) in which
(T) _a , (T) _e and (T) _h independently of one another for the groups

stand,
and the remaining symbols, radicals and groups have the preferred meanings given above.

Compounds of the formula are very particularly preferred (I) in which Sil for the groups

or

stands,
p and q independently assume values from 1 to 50 and the other symbols, radicals and groups have the meanings given above.

Compounds of the formula (I) in which
Z stands for a residue which is derived from a sugar or sugar derivative such as glucose, mannose, fructose, maltose, sucrose, cellobiose, palatinose (glucopyranosyl-fructose), glucopyranosyloxymethyl furfural, aminoderivates such as derivatives being derived from derivatives. B. 2-amino-glucose, glucamine, N-methylclucamine, carboxylic acid derivatives such as. B. gluconic acid, glucopyranosyl arabonic acid, gluconol acton, ascorbic acid, glucopyranosyl arabic acid lactone, aldehydes and alkoxylation products of the above sugars are to be understood,
and wherein the remaining symbols, radicals and groups have the meanings given above, in particular the preferred, particularly preferred or very particularly preferred meanings.

It was also found that the new compounds of formula (I)

in which the symbols, residues and groups have the meaning given above,
by implementing
A) compounds of the formula (III)

in the
X '' for alkyl, C₁ to C₄ acyl or the group

stands
R¹¹ to R¹⁴ have the meaning given above, but do not represent X ′,
E ′, D ′ independently of one another represent H, alkyl, C₁-C₄-acyl, and the other symbols, radicals and groups have the meaning given above,
With
B) the derivative of a dicarboxylic acid, a lactone, a sultone or isocyanatoalkylcarboxylic acid (derivative) or sulfuric acid derivatives.

The reaction takes place in aprotic polar solution agents such as dioxane, ether, THF, acetonitrile if with the addition of esterification catalysts and optionally subsequent neutralization with alkali and / or Alkaline earth salts.

The compounds of formula (II) are known and will be described in a parallel application.

Depending on the output connection used extensions of formula (III) and especially at higher molecular starting compounds give products or product mixtures of compounds of formula (I) in where the individual molecules differ, i.e. i.e., on various reactive sites and / or where appropriate in different places with the derivatives of Di carboxylic acids, sulfuric acid, lactones, sultons or Have reacted isocyanatoalkyl carboxylic acids.

The pure ones can be obtained from the product mixtures obtained Connections are isolated. For use as surface-active or surface-modifying However, substances are preferably those from the manufacturer available product or product mixtures, if necessary after rough cleaning, used directly as technical goods.

Subject of the registration are therefore also those from the Process available products and product mixtures.  

The starting compounds of formula (III) are in generally 1 to 5 moles, preferably 1 to 2 moles Acid, lactone or sulton per equivalent of hydroxy or Amino groups implemented.

The new compounds of formula (I) have spoken good surface-active and interface-modifi decorative properties and are according to the invention e.g. B. as a film former, leveling agent, wetting agent, dis Pergiermittel, stabilizers and / or spreading agents or generally as formulating agents, additives or Adjuvants used where the properties of Formulations must be modified accordingly.

Because of the structure of the compounds of formula (I) from a siloxanyl part of a spacer to poly hydroxylated hydrocarbons can be bound the properties of the compounds of formula (I) Variation on the siloxanyl part, spacer and / or carbon hydrogen part easily according to requirements be adjusted.

For example, the chain length of the Siloxane's hydrophobicity and the nature of the sugar rest adjust the hydrophobicity. The solubility and the surfactant properties are also influenced by the spacer.

In addition, the compounds of formula (I) offer the Advantage of good biodegradability or one extremely good ecological compatibility.  

The compounds of formula (I) are therefore preferred as formulation aids, additives or adjuvants for Crop protection agents such as insecticides, herbicides, Fungicide agents used. They serve as emulsifiers for z. B. insecticides, herbicides, fungicides, growth regulating agents and / or solvents in solid and Liquid formulations, especially in emulsions concentrates of these active ingredients.

They serve as additives or adjuvants for effectiveness improvement by increasing spray adhesion or the penetration of the active ingredient into the plant can increase. This is connected, for. B. an increased Rainproof.

They are used as formulation aids with 0.5 to 50%, preferably 1 to 20% incorporated into the recipe. As an additive or adjuvant, they are used in one concentrate tration from 0.05 to 1%, preferably 0.1 to 0.5% of Spray liquor added.

The following examples serve to explain the Invention.  

example 1 1a) Acylation of an aminopropylsiloxane with glucono lactone

8 g (2.86 × 10 ^-2 mol) of the 3-aminopropyl-1,1,1-3- 5,5,5-heptamethyltrisiloxane and 5.12 g (2.86 × 10 ^-2 mol) of gluconic acid lactone are dissolved in 35 ml of methanol heated under reflux. After 6 hours the solvent is removed. The remaining syrup is taken up in 40 ml of pentane. The product precipitates and is dried after the solution has been separated off. 12.5 g of a white powder are obtained.

1b) Synthesis of maleic acid half ester from 1

6.9 g (1.5 · 10 ^-2 mol) of the gluconamide from Example 1a) and 10 mg of J₂ are dissolved in 30 ml of dioxane and heated to 90 ° C, the siloxanyl-modified gluconamide completely dissolving. After cooling to room temperature, 1.47 g (1.2 · 10 ^-2 ) maleic anhydride, dissolved in 5 ml of dioxane, are added.

The mixture is heated to 90 ° C. within 1 h and this Temperature held for 6 h. Then the solution withdrawn medium in vacuo and the mass in pentane (30 ml) added. With strong stirring one becomes white powdery appearance. The the supernatant solvent is decanted off and the process is repeated with 2 × 30 ml of pentane. To Vacuum drying gives 7.8 g of a white-yellow wax.

1c) Synthesis of the carboxylates by neutralization of the Acid function with appropriate bases

2 g of maleic acid half ester (3.6 · 10 ^-3 mol) according to example 1b) and 0.7 g of N-methylglucamine are taken up in 10 ml of methanol and heated under reflux for 1 h.

After removing the solvent, a remains white-yellow powder. Inclusion in 30 ml of pentane and decanting it after vigorous stirring Suspension leads after final drying a white-yellow powder (2.5 g).

1d) triethylammonium salt (M⁺ = HN⁺ (C₂H₅) ₃)

2 g of maleic acid semiesters according to Example 1b) and 0.36 g of triethylamine are mixed in 10 ml of methanol agrees and the one already described before Submitted procedure. You get 1.9 g of ge mixed connection.

1e) Na salt

3.0 g of the maleic acid half-ester (5.4 × 10 ^-3 mol) according to Example 1b) are dissolved in 10 ml of methanol.

There are 3 drops of a phenolphthalein solution in Ethanol / water added. One becomes agitated about 5 to 10% solution of NaOH in methanol until added dropwise to the envelope product. During the closing The salt drops out of solution. The final evaporation of the suspension results 2.9 g of a white powder.

Surface tension (σ) of a 1% aqueous Solution: 20.8 mN / m.

Example 2 2a) Acylation of aminopropyl-heptamethyltrisiloxane with glucopyranosylarabonic acid lactone

1.8 g 3-aminopropyl-1,1,1,3,5,5-heptamethyltrisoxoxane (6.45 · 10 ^-3 mol) and 2 g glucopyranosylaronic acid lactone (6.45 · 10 ^-3 mol)

are dry at room temperature in 20 ml Methanol mixed and reflux for 5 h heated. After the reaction is over, it will Stripped solvent and the residue in 10 ml Ether / 15 ml pentane added. By stirring like the product. The precipitant mixture is decanted and the sediment of a vacuum dry subjected. There remain 3.1 g of a pul verse.

Surface tension (σ) of a 0.1% aqueous Solution 19.0 mN / m.

2b) Synthesis of maleic acid half-ester, neutralization the carboxylic acid function

1.5 g of the amide according to Example 2a) (2.25 · 10 ^-3 mol) are dissolved in 20 ml of dioxane at 90 to 100 ° C. After cooling to about 50 ° C., 0.25 g of maleic anhydride, dissolved in 5 ml of dioxane, is added. Immediately afterwards, 0.1 ml of CS₂ is added dropwise and the mixture is heated under reflux for 5 hours. After cooling to 60 ° C., 0.14 g of KOH, dissolved in 15 ml of methanol, is added dropwise. The mixture is stirred at 60 ° C. for a further 20 minutes. Then the mixture is freed from the solvent mixture. 1.6 g of a colorless powder are obtained.

Surface tension (σ) of a 0.1% aqueous Solution: 19.9 mN / m.

Example 3

3 g of the product from Example 1a) (6.56 · 10 ^-3 mol) and 0.636 g of HOSO₂NH₂ (amidosulfuric acid, 6.56 · 10 ^-3 mol) are combined in 20 ml of N-methylpyrrolidone and at 90 ° C. for 7 h heated. After removal of the solvent by washing the reaction product several times with 30 ml of ether / 50 ml of hexane and then with 5 × 20 ml of ether, 2.6 g of a yellowish powder are obtained after vacuum drying.

Surface tension (σ) of a 1% aqueous solution: 20.1 mN / m.

Example 4 4a) Synthesis of the Schiff base

21.6 g (75 mmol) GMF (glucosyloxymethylfurfural), previously dissolved in 20 ml of dry methanol has been,

become 20.9 g of 3-aminopropyl-1,1,1,3,5,5,5- heptamethyl-trisiloxane added. The mixture is heated to reflux temperature for 10 h. The Solvent is removed and the residue in Vacuum dried. Yield: 35.5 g of powder Formula 4a.

4b) Reduction of the Schiff base from Example 4a)

32.8 g (60 mmol) of the product from Example 4a) are dissolved in methanol (200 ml) and in the presence Raney nickel at 110-120 ° C and 120-140 bar H₂ hydrated. After cooling, the catalyst filtered off and the filtrate was concentrated.

Yield: 28.2 g (84.7% of theory).
Mass spectrum (CI / isobutane, silylated sample) MH⊕ = 915 m / l.

4c) Synthesis of maleinamide and neutralization of the Carboxylic acid function

13.6 g of the secondary amine (2.7 × 10 ^-2 mol) prepared according to Example 4b) are dissolved in 150 ml of dioxane. Then 0.2 ml of CS₂ and 2.4 g (2.7 · 10 ^-2 mol) of maleic anhydride (dissolved in dioxane) are added. The mixture is heated to 90 ° C. for 5 hours and then left at room temperature for 24 hours.

2.1 g (0.027 mol) sodium acetate, dissolved in 30 ml absolute methanol become that at room temperature given the reaction product described above; one stir for 90 minutes. The solution above will decanted. The residue is mixed with n-hexane stirs and vacuumed. After drying in a vacuum 9.8 g of product are obtained. Become from the filtrate another 4 g of product isolated.

Mass spectrum: m / c 676 (MH⊕), m / c 698 (M⊕Na⊕).
Surface tension of a 0.5% aqueous solution: 26.0 mN / m.

Claims (10)

1. Anionic siloxanyl-modified compounds of the general formula (I) wherein
Z represents a radical which is derived from a mono- or oligosaccharide with pentose and / or hexose units, or stands for cyclic or acyclic polyhydroxylated hydrocarbons with 4 or 5 carbon atoms, the cycle containing at least one oxygen atom and, if appropriate, ge 1 to 10 mono- or oligosaccharides is substituted by 1 to 10 pentose and / or hexose units,
n is calculated as the maximum possible number of OH groups of Z, where n is at least 3 and at most 40,
v represents a number 1 to 10,
w represents a number from 0 to 10, with a maximum of one group per monosaccharide unit is available,
D and E independently of one another represent H, alkyl, C₁-C₄ acyl or X ′,
nvw is a number from 0 to 39,
X for alkyl, C₁ to C₄ acyl, the group or for X ', where
X 'is an anionic radical which is derived from a dicarboxylic acid derivative, sulfuric acid derivative, lactone, sultone or isocyanate toalkylcarboxylic acid derivative,
k represents a number 0 to 10,
and
R¹, R² independently of one another are H or CH₃, at least one radical being H,
M for a group stands in what stands in what
R¹² represents H, alkyl or X ′,
R¹⁵ represents H or alkyl,
the groups T independently of one another are optionally substituted alkylene, which may be by at least one of the groups Arylene, in each case saturated or unsaturated cycloalkylene or R¹¹ together with the group (T) _e forms a preferably 5- or 6-membered heterocyclic ring, is interrupted,
where i stands for a number 0 to 3 and
R¹³ and R¹⁴ independently represent X ′, hydrogen or C₁-C₄-alkyl,
L for the groups stands,
R¹¹ is X 'or H, alkyl, hydroxyalkyl or the groups stands,
a to h independently of one another represent a number 0 or 1, at least one index being 1,
Sil for a silicon-containing radical of the formula stands in the
A stands for a siloxane chain consisting of m structural elements of the formula and an end group consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are alkyl, cycloalkyl, cycloalkyl-alkyl or optionally substituted aryl or aralkyl,
the radicals R⁵, R⁷ and R⁸ also for the group stand,
R¹⁰ represents alkyl and
the sum of the structural elements in independently of one another stands for a number from 0 to 600, and
B and R³ have the same meaning as A,
or represent alkyl, cycloalkyl, cycloalkyl alkyl, optionally substituted aryl or aralkyl,
or A and B together form a siloxane cycle,
where the radicals R⁴ to R¹⁰ in the chains A, B and R³ can be different, and
where one or more anionic groups and a corresponding number of cationic counterions are present in the molecule. 2. Compounds of formula (I) according to claim 1, in which
Sil for the groups stands,
where p and q independently of one another have values from 1 to 100 and Y has the meaning of methyl or Has. 3. Compounds of formula (I) according to claim 1, wherein
(T) _a , (T) _e and (T) _h independently of one another for the groups stand. 4. Compounds of formula (I) according to claim 1, in which Sil for the groups or stands
where p and q independently take values from 1 to 5. 5. Compounds of formula (I) according to claim 1, in which
Z stands for a residue which is derived from a sugar or sugar derivative. 6. Process for the preparation of compounds of formula (I) in which M, Z, X, D, E, n, v and w have the meaning given in claim 1,
by reacting compounds of the formula (III) in the
X '' for alkyl, carbonylalkyl or the group stands,
R¹¹ to R¹⁴ have the meaning given in claim 1, but do not represent X ′,
E ′, D ′ independently of one another are H, lower alkyl, C₁-C₄-acyl,
and the other symbols, radicals and groups have the meaning given in claim 1,
With
the derivative of a dicarboxylic acid, a lactone, a sulfone, an isocyanatoalkylcarboxylic acid derivative or a sulfuric acid derivative. 7. The obtainable by the method of claim 6 Products and product mixtures. 8. Use of compounds of formula (I) according to Claim 1 as interfacial and interfacial modifying substances. 9. Use of those obtainable according to claim 6 Products and product mixtures as surface-active and interface-modifying substances. 10. Plant protection products containing compounds of Formula (I) according to claim 1 and / or products or Product mixtures according to claim 7.