DE3706795A1 - New applications for quaternary ammonium salts of acetylenediurea derivatives - Google Patents

Abstract

Use of compounds of the general formula (I) <IMAGE> in which X, Y and R<1> to R<4> are as defined in Claim 1, for stabilising organic material, especially plastics and coatings and also oils, textiles and paper, and also as an antistatic, a plasticiser for antimicrobial finishing, an agent for eliminating interfering substances and a fixative (fixing agent) for anionic dyes.

Description

The main patent P 36 43 889.8 deals with the use of Compounds of the general formula (I)

wherein
R¹ and R² independently of one another are hydrogen, C₁-C₈-alkyl, C₅-C₈-cycloalkyl, C₇-C₁₂-aralkyl, C₇-C₁₄-cycloalkylalkyl, aryl or carboxylic esters or together represent a tetra, penta- or hexamethylene group or one optionally methoxy or methyl substituted radical of the formula

represent
X and Y independently of one another represent oxygen, sulfur or NR⁸, where R₈ has the meanings hydrogen, C₁-C₈-alkyl or C₇-C₁₂-aralkyl, and
R³ and R⁴ independently of one another for C₁-C₂₂-alkyl, which can be interrupted by ether oxygen, sulfur or nitrogen, C₁-C₂₂-alkenyl, C₃-C₁₂-cycloalkyl, optionally substituted C₇-C₂₀-aralkyl, C₃-C₁₂-alkynyl, Hydroxy, a non-aromatic, optionally substituted heterocycle, a C₁-C₂₂-alkyl radical which is substituted by a heterocycle, a C₁-C₂₂-alkyl radical which has an amino or hydroxy group, chlorine, bromine, iodine, sulfonyl, sulfoxide, a urethane group , a urea group, carboxyl, carboxylic ester and / or optionally substituted carbamoyl, or for the group BA-, in which -A- represents a bridge member and B- a thiol or cyano radical or a group of the formulas

means what
R⁵ represents hydrogen, C₁-C₂₂-alkyl, C₅-C₈-cycloalkyl, C₇-C₁₂-cycloalkylalkyl, C₇-C₂₀-aralkyl, optionally substituted aryl, a heterocycle or a heterocycle-containing C₁-C₂₂- alkyl,
R⁶ and R⁷ independently of one another are hydrogen, C₁-C₂₂-alkyl, ether oxygen-containing C₂-C₉-alkyl, C₇-C₂₀-aralkyl, optionally substituted aryl, a heterocycle or a heterocycle-containing C₁-C₂₂-alkyl or together with that Atom to which they are attached form a 3- to 12-membered ring system,
and the compounds of formula I, insofar as they are new.

This additional application relates to a further embodiment of the Invention, according to which also quaternary derivatives of the compounds of Formula (I) of the main patent can be used according to the invention.

It is known that 2,2,6,6-tetraalkyl-piperidine derivatives are light stabilizers for organic polymers. In the older EP-8 61 11 624.2 Acetylenediourea derivatives with incorporated 2,2,6,6-tetraalkylpiperidine remains described. It is also known that urea and thiourine Material derivatives provide good heat stabilization in some plastics achieve. However, only 4-hydroxyphenyl or 4-alkoxyphenyl substituted (thio) ureas a general UV absorber effect (cf. J. Voigt, in K.A. Wolf (ed.), Chemistry, Physics and Technology of the Kunststoffe, Springer-Verlag, Berlin, Heidelberg, New York, 1966, Pp. 300-303).

FR-A-22 91 203 contains glycoluril derivatives of the formula

described, wherein R is an optionally substituted hydrocarbon residual material with up to 22 carbon atoms. These connections are used as surface active agents for the textile industry and as Corrosion inhibitors proposed.

The invention has for its object new or known, but so far compounds not yet proposed for this application as To provide stabilizers for organic material.

This problem is solved through the use of connections of the general formula (I)

wherein
R¹ and R² independently of one another are hydrogen, C₁-C₈-alkyl, C₅-C₈-cycloalkyl, C₇-C₁₂-aralkyl, C₇-C₁₄-cycloalkylalkyl, aryl or carboxylic esters or together represent a tetra, penta- or hexamethylene group or one optionally methoxy or methyl substituted radical of the formula

represent
X and Y independently of one another represent oxygen, sulfur or NR⁸, where R⁸ has the meanings hydrogen, C₁-C₈-alkyl or C₇-C₁₂-aralkyl, and
R³ and R⁴ independently of one another for C₁-C₂₂-alkyl, which can be interrupted by ether oxygen, sulfur or nitrogen, C₁-C₂₂- alkenyl, C₃-C₁₂-cycloalkyl, optionally substituted C₇-C₂₀- aralkyl, hydroxy, C₃-C₁₂- Alkynyl, a non-aromatic, optionally substituted heterocycle, a C₁-C₂₂-alkyl radical which is substituted by a heterocycle, a C₁-C₂₂-alkyl radical, the amino, hydroxy, chlorine, bromine, iodine, sulfonyl, sulfoxyl, a urethane group, contains a urea group, carboxyl, carboxylic ester and / or optionally substituted carbamoyl, or stands for the grouping BA-, in which -A- represents a bridge member and B- a thiol or cyano radical or a group of the formulas

means what
R⁵ represents hydrogen, C₁-C₂₂-alkyl, C₅-C₈-cycloalkyl, C₇-C₁₂-cycloalkylalkyl, C₇-C₂₀-aralkyl, optionally substituted aryl, a heterocycle or a heterocycle-containing C₁-C₂₂- alkyl,
R⁶ and R⁷ independently of one another are hydrogen, C₁-C₂₂-alkyl, ether oxygen-containing C₂-C₉-alkyl, C₇-C₂₀-aralkyl, optionally substituted aryl, a heterocycle or a heterocycle-containing C₁-C₂₂-alkyl or together with that or the atom (s) to which they are attached form a 3 to 12-membered ring system,
wherein at least one of the tertiary nitrogen atoms contained in the compounds of the general formula (I) is quaternized by an alkylating agent, and their use for stabilizing organic material, in particular urea and paints, as well as oils, textiles and paper, furthermore as an antistatic, plasticizer for antimicrobial finishing, as an agent for removing contaminants and as a fixative for anionic dyes.

The use of the compounds for stabilizing is preferred Polyolefins, polyamides and paints.

A particularly preferred use is for light and heat protection and as a metal ion deactivator, especially in plastics.

Individual radicals R¹ and R² are in addition to hydrogen z. B. methyl, ethyl, Propyl, butyl, pentyl, hexyl, benzyl, phenylethyl, phenylpropyl, Phenylbutyl, methylbenzyl, phenyl, tolyl, carbomethoxy, carboethoxy, Carbopropoxy or carbobutoxy.

Preferred for R 1 and R 2 are methyl, ethyl, benzyl, phenyl and especially hydrogen.

X and Y are, in particular, oxygen, independently of one another, in addition Sulfur or NR⁸, wherein R⁸ has the above meanings. Alkyl residues, for example R³ and R⁴, can be both unbranched and be branched.

Alkyl radicals in the compounds of the general formula (I) are examples as C₁-C₂₂ alkyl, especially C₁-C₈ alkyl, especially preferably C₁-C₄ alkyl radicals, e.g. B. methyl, ethyl, propyl, butyl, pentyl, Hexyl, heptyl and octyl.  

Examples of such residues are

where n = 0-20.

An alkyl radical interrupted by ether oxygen or nitrogen for R³ and R⁴ (in the case of oxygen also for R⁶ and R⁷) can for example to be wise:

Exemplary urea groups are the following:

Exemplary urethane groups or carbamoyl groups are the following:

Cycloalkyl radicals (including bicycloalkyl) for R³, R⁴ (partly also R⁵) can be, for example:

Aralkyl radicals R³, R⁴, R⁵, R⁶, R⁷ can be, for example:

Alkyl radicals R³, R⁴, R⁵, R⁶, R⁷, which contain heterocycles, can for example be:

Alkyl radicals R³, R⁴, the hydroxyl, thiol, carboxyl or cyano groups can include, for example:

So far in the compounds according to the invention non-aromatic heterocycles are present, for example, the following:

As far as hydroxy-substituted or in the compounds of the invention Carboxyl-substituted alkyl radicals are present, for example be the following:

Bridge members -A- are divalent aliphatic, araliphatic or aromatic groups, including heteroatoms, namely oxygen, nitrogen or sulfur.

In particular, alkylene, cycloalkylene, aralkylene, by CO or SO₂ to name substituted alkylene, aralkylene or aryl radicals.

Individual bridge links A are for example:

Preferred bridge members are - (CH₂) - _p , where p = 1 to 5, in particular 1, 2 and 5.

Further examples of bridge members -B- are the following:

The term "given in connection with the rest definitions" given if substituted "includes the meanings explained above keiten. It particularly includes substituents such as C₁-C₆-alkyl, C₁-C₆- Alkoxy, C₂-C₁₂-carbonic ester, C₁-C₁₂-acyl, halogen, nitro, carboxyl, amino, Hydroxy, -SH, -S-C₁-C₄-alkyl, phenyl, C₂-C₆-alkenyl, (poly) ethoxy.

The term "acyl" stands for example for C₁-C₂₀ acyl, in particular for Remains of the formula

The production of the starting materials by alkylation in the Compounds according to the invention can be transferred is the main registration P 36 43 889.8.

The alkylation can be carried out in a manner known per se using alkylating agents such as B. dialkyl sulfates, alkyl halides, phenalkyl halides, Epoxides, carbonates, sulfites, aromatic halogen or nitro compounds, or sulfonic acid esters.

Dialkyl sulfates are, for example, dimethyl or diethyl sulfate, alkyl Halides are organic chlorine as well as bromine and iodine links.

Examples include: methyl iodide, methyl bromide, methyl chloride, ethyl iodide, ethyl chloride, ethyl bromide, propyl bromide, isopropyl iodide, octyl bromide, benzyl chloride, benzyl bromide, bromoethanol, phenylethyl bromide, butyl iodide, pentyl iodide, hexyl iodide, heptyl propylene iodide, and furthermore ethylene and higher alkylating agents, ie CH₃- (CH₂) _r -X (with X = Cl, Br, I and r = 0-22). Sulfonic acid esters and alkyl methanesulfonic acid.

Examples include methyl benzenesulfonic acid, benzenesulfone Acid ethyl ester, benzenesulfonic acid propyl ester, benzenesulfonic acid isopropyl esters, butyl benzenesulfonate and the corresponding p-toluene to name sulfonic acid esters and methanesulfonic acid esters. Another The possibility of producing the compounds according to the invention is Implementation of non-quaternized compounds of formula (I), the contain at least one leaving group in the molecule, with tertiary amines.  

The compounds according to the invention are of ionic structure and contain mono- or polyvalent cations and monovalent anions such as B. Chloride, bromide, iodide, methosulfate, benzenesulfonate, p-toluenesulfonate or Methanesulfonate.

These anions can be exchanged by anion exchange in a suitable solvent against other mono- or polyvalent inorganic or organic anions be replaced. Examples of inorganic anions are: Fluoride, sulfate, tetrafluoroborate, hexafluorophosphate, phosphate or Rhodamide.

Examples of organic anions are carboxylic acid anions such as, for. B. the Anions of formic acid, acetic acid, propionic acid, hexanoic acid, cyclo hexane carboxylic acid, lactic acid, stearic acid, dodecylbenzenic acid, benzoin acid, acrylic acid, methacrylic acid, citric acid, malonic acid, maleic acid, Succinic acid, adipic acid, pimelic acid, suberic acid, oleic acid as well Anions of polycarboxylic acids with up to 3000 COOH groups to name.

The compounds of the invention have extraordinarily good ones stabilizing properties, have no inherent color, are good compatible with organic polymers and show a low Vapor pressure.

The compounds of the invention are suitable for stabilizing organic material, especially plastics, against degradation by Light and warmth. They are the plastics to be stabilized in one Concentration from 0.01 to 5% by weight, preferably 0.02 to 1% by weight, added during or after polymer formation.

For mixing the compounds of the invention with the Stabilizing plastics can all known devices and Methods for mixing stabilizers or other additives be applied in polymers.

Those stabilized by one of the compounds according to the invention If necessary, plastics can also contain other additives, for example antioxidants, light stabilizers, metal deactivators, antistatic agents, flame retardants, pigments and Fillers.  

Antioxidants and light stabilizers that hold the plastic in addition to the Compounds according to the invention can be added, for. B. Compounds based on sterically hindered phenols or sulfur or Phosphorus-containing costabilizers.

Examples of such phenolic antioxidants are 2,6-di-tert-butyl-4-methylphenol, n-octadecyl- β - (3,5-di-tert-butyl-4-hydroxyoxyphenyl) propionate, 1, 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert .-Butyl-4-hydroxybenzyl) benzene, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -iso cyanurate, 1,3,5-tris- [ β - (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl oxy-ethyl] -isocyanurate, 1,3,5-tris (2,6-di-methyl-3-hydroxy-4-tert .-Butyl benzyl) isocyanurate, pentaerythritol tetrakis [ β - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] mentioned.

Examples of phosphorus-containing antioxidants are tris (nonyl phenyl) phosphite, distearylpentaerythritol diphosphite, tris- (2,4-di-tert.- butylphenyl) phosphite, tris (2-tert-butyl-4-methylphenyl) phosphite, Bis- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di- tert-butylphenyl) -4,4'-biphenylene diphosphite mentioned.

Examples of sulfur-containing antioxidants are dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, pentaerythritol tetrakis ( b- laurylthiopropionate, pentaerythritol tetrakis ( β- hexylthiopropionate).

Other antioxidants and light stabilizers that can be used together with the compounds of the invention are e.g. B. 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, aryl esters of hydroxybenzoic acids, α- cyanocinnamic acid derivatives, nickel compounds or oxalic acid dianilides.

As organic polymers by the compounds of the invention can be stabilized, for example:

Polymers of mono- and diolefins, such as. B. lower polyethylene or high density, linear low density polyethylene, polypropylene, Polyisobutylene, polybutene-1, polyisoprene, polybutadiene as well Copolymers of mono- or diolefins or mixtures of the above Polymers;  

Copolymers of mono- or diolefins with other vinyl monomers such as e.g. B. ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, Ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers;

Polystyrene; Copolymers of styrene or α- methylstyrene with dienes or acrylic derivatives, such as. B. styrene-butadiene, styrene-acrylonitrile, styrene-ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene-acrylonitrile-methacrylate;

ABS, MBS or similar polymers;

Halogen-containing polymers, such as. B. polyvinyl chloride, polyvinyl fluoride, Polyvinylidene fluoride and its copolymers;

Polymers derived from α, β- unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles;

Polymers derived from unsaturated alcohols and amines or their Derive acrylic derivatives or acetals, such as polyvinyl alcohol or Polyvinyl acetate;

Polyurethanes, polyamides, polyureas, polyesters, polycarbonates, Polysulfones, polyether sulfones and polyether ketones.

Other organic polymers with the compounds of the invention Industrial paints can be stabilized. Below these are stove enamels, among them vehicle paints, preferably two-coat paints, especially to emphasize.

Again, the antioxidants and Sunscreen can be used.

The compounds according to the invention can be in solid or dissolved form Lacquer can be added. Their good solubility in coating systems is of special advantage.

The use of the compounds according to the invention is preferred in Polyolefins, preferably ethylene and propylene polymers.

The invention is further illustrated by the examples below.

Example 1

9.1 g of the compound of formula (II) were dissolved in 90 ml of dichloromethane. 5.7 g of methyl iodide were added to the solution. After 24 hours the precipitated precipitate filtered off, washed with petroleum ether and at the Air dried. 9.4 g of yellowish dye of mp. 212-213 ° C (dec.).

Example 2

6.6 g of the compound of formula (III) and 4.5 g of methyl iodide were in 70 ml of dichloromethane as in Example 1 implemented. 10.2 g were obtained yellowish dye with mp. 208-209 ° C (dec.).

Example 3

12.5 g of the compound of formula IV and 18.6 g of methyl p-toluenesulfonate esters were boiled in 175 ml of xylene for 2.5 h. After cooling to room temperature was suctioned off, washed with xylene and petroleum ether recrystallized from water. After drying in a water jet vacuum 80 ° C., 1 kg of colorless solid was isolated, with a melting point of 307 ° C. (decomp.).

Claims (12)

1. Use of compounds of the general formula (I) wherein
R¹ and R² independently of one another are hydrogen, C₁-C₈-alkyl, C₅-C₈-cycloalkyl, C₇-C₁₂-aralkyl, C₇-C₁₄-cycloalkylalkyl, aryl or carboxylic esters or together represent a tetra, penta- or hexamethylene group or optionally methoxy - or methyl-substituted radical of the formula represent
X and Y independently of one another represent oxygen, sulfur or NR⁸, where R⁸ has the meanings hydrogen, C₁-C₈-alkyl or C₇-C₁₂-aralkyl, and
R³ and R⁴ independently of one another for C₁-C₂₂-alkyl, which can be interrupted by ether oxygen, sulfur or nitrogen, C₁-C₂₂-alkenyl, C₃-C₁₂-cycloalkyl, optionally substituted C₇-C₂₀-aralkyl, C₃-C₁₂-alkynyl, Hydroxy, a non-aromatic, optionally substituted heterocycle, a C₁-C₂₂-alkyl radical which is substituted by a heterocycle, a C₁-C₂₂-alkyl radical which has an amino or hydroxy group, chlorine, bromine, iodine, sulfonyl, sulfoxide, a urethane group , a urea group, carboxyl, carboxylic ester and / or optionally substituted carbamoyl, or for the group BA-, in which -A- represents a bridge member and B- a thiol or cyano radical or a group of the formulas means what
R⁵ represents hydrogen, C₁-C₂₂-alkyl, C₅-C₈-cycloalkyl, C₇-C₁₂- cycloalkylalkyl, C₇-C₂₀-aralkyl, optionally substituted aryl, a heterocycle or a C₁-C₂₂-alkyl containing heterocycle,
R⁶ and ⁷ independently of one another are hydrogen, C₁-C₂₂-alkyl, ether oxygen-containing C₂-C₉-alkyl, C₇-C₂₀-aralkyl, optionally substituted aryl, a heterocycle or a heterocycle-containing C₁-C₂₂-alkyl or together with the atom that they are bound, form a 3 to 12-membered ring system,
wherein at least one of the tertiary nitrogen atoms contained in the compounds of the general formula (I) is quaternized, for stabilizing organic material. 2. Use of a compound of general formula I for stabilization of plastics and paints. 3. Use of a compound of general formula I for stabilization of oils. 4. Use of a compound of general formula I for stabilization of textiles. 5. Use of a compound of general formula I for stabilization of paper. 6. Use of a compound of general formula I for stabilization of polyolefins and polyamides. 7. Use of a compound of general formula I for light and Thermal protection or as a metal ion deactivator. 8. Use of a compound of general formula I as an antistatic. 9. Use of a compound of general formula I as a plasticizer. 10. Use of a compound of general formula I for antimicro biological equipment. 11. Use of a compound of general formula I for the impurity disposal. 12. Use of a compound of general formula I as a fixing agent for anionic dyes.