CS227302B2 - Method of inhibiting oxidative degradation of organic materials - Google Patents

Description

(54) A method of inhibiting the oxidative degradation of organic material

The invention relates to a method for inhibiting the oxidative degradation of organic material.

Many organic materials are susceptible to oxidative degradation under normal conditions. This leads to damage and, in some cases, destruction of such materials, which causes great economic damage. Therefore, ways to prevent oxidative degradation are sought. One method not yet described is made possible by the method of the present invention.

A method for inhibiting the oxidative degradation of an organic material according to the invention comprises adding to the organic material a weight of 0.001 to 10% by weight, based on the weight of the organic material, of a compound of formula (I) wherein:

A represents a C 2 -C 12 alkylene radical, a C 4 -C 8 cycloalkylene radical or a radical of the formula -CHg-C (GHg) p-, wherein β is an integer from 3 to 6, or

A represents a (C 2 -C 5) alkylene radical substituted with one or two groups of the formula -CHgOBOCCHg 1 R 2, wherein:

R 3 is a 3-W-5-Y-4-hydroxyphenyl radical wherein each of W and Y, which are the same or different, is an alkyl radical of 1 to 12 carbon atoms and m is 0, 1 or 2, is an alkyl radical or a radical of formula - (CH3) p in which

B and _m have the above-mentioned meaning and p represents a group of the formula -COR wherein 2

R represents an alkyl radical of 1 to 20 carbon atoms, an alkoxy group of 1 to 12 atoms

R, represents a group of the formula -BCONHAOCOR ¹ in which:

A and h 'have the meanings given above and

B represents a single bond, an alkylene radical having 1 to 10 carbon atoms, a phenylene radical, an oxydialkylene radical having 4 to 12 carbon atoms or a thiodialkylene radical having 4 to 12 carbon atoms, or

1 R has the same meaning as R above, with the proviso that at least one of A, R and M contains a 3-W-5-Y-4-hydroxyphenyl radical.

Particularly preferred is to add to the organic material a compound of formula (I) above wherein L is an alkylene radical having 2 to 4 carbon atoms or an ethylene radical substituted by two groups of the formula -CHgOCOCHgCHgR3, wherein:

R ^ is 3,5-di-tert-butyl-4-hydroxyphenyl, is C 14-C alkyl zbytek alkyl or -CHgCHgR ^ in which:

R ^ is as defined above, means a group of formula -COR in which

R represents an alkyl radical having 1 to 17 carbon atoms; a 3,5-di-tert-butyl-4-hydroxyphenyl group or a group of the formula -BCONHAOCOR in which:

A and R ¹ have the meaning indicated and výěe

B represents a single bond, an alkylene radical having 4 to 8 carbon atoms, a thiodiethylene or a phenylene radical, provided that at least one of A, R and U has a 3,5-di-tert-butyl-4-hydroxyphenyl group.

The terms alkyl and alkylene radicals include straight and branched groups.

The compounds of formula X exhibiting inhibitory activity used in the method of the invention can be prepared by the preparation of compounds of formula XX 'cooanh ₂ (II) wherein:

A and R ¹ have the výěe hereinbefore defined, reacting a compound of formula XXX

R ⁴ COX (XII), or with a compound of formula XV

B (COX) ₂ (IV) in which samples

B my meaning as above,

X is halogen, hydroxy or (C 1 -C 4) alkoxy;

R ⁴ snamené group of formula - ^(GH 2 ^ m ^R '▼ wherein m and IP eats defined above, an alkyl radical having 1 to 20 carbon atoms, a cycloalkyl radical having 4 to 8 carbon atoms, aryl radicals ee 6 to 10 carbon atoms or phenyl substituted with halogen, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, nitro or hydroxy, at temperatures ranging from 15 to 290 ° C at pressures ranging from 100 Pa to 10 kPa, wherein: in the case where X is a halogen halogen, the reaction is carried out in the presence of an acid acceptor.

. The compounds of the formula I used in the process according to the invention can also be prepared by the method of reacting a compound of the formula V

R ⁴ CO-NH-Q- (OH) _S (V) or a compound of formula VI

B--CONH-Q- (OH) _s / 2 (VI) in which formulas

R ⁴ is a radical of formula - (CH 2 R ⁵⁾ , in which

B and R ^ are as hereinbefore defined, C 1 -C 20 alkyl, C 5 -C 6 aryl or phenyl substituted by halogen, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, nitro or a hydroxyl group,

Q is a C 2 -C 12 alkylene radical, a C 4 -C 8 cycloalkylene radical or a radical of the formula -CH 8 -CCH 8), in which my meaning is as defined above, means an integer from 1 to 3, and

B, as hereinbefore defined, is reacted with a compound of formula Vil r'cox (VII), wherein r 'and X are as defined above, at a temperature in the range of from 5 to 250 ° C, at a pressure of from 100 Pa to 10 kPa, wherein when X is halogen, the reaction is carried out in the presence of an acid acceptor.

According to the invention, mixtures of the compounds of the general formula I can also be used together with organic materials subject to oxidative degradation.

In the compounds of formula (I), A is preferably an alkylene radical having CH ₂ - terminal groups.

Ί

Very preferably, ester and amide groups are bonded to the alkylene radical having terminal CHg groups in the alpha position, which does not have hydrogen bonded to the carbon atoms in the beta position.

The preferred meaning of R depends to some extent on the intended use of the product. If high solubility in hydrocarbons is required, the symbol R ^{2 should} mean a long hydrocarbon o

chain with 11 to 17 carbon atoms. In a particularly preferred compound, R is o

When low volatility is desired, R is preferably -HCONHAOCOr ', where B, A and r' are as defined above.

Particularly preferred are compounds wherein B is a single covalent bond. Particularly large molecular weight and low volatility can be achieved when the symbol R ² represents a group of formula -BCONHAOGOr 'wherein A is an alkylene radical substituted formula -CHgOCOXCHg) ^ ^3, where a and R ³ are as defined above. Preferred halogens are chlorine, fluorine, bromine and iodine.

The compounds of the invention are suitable for stabilizing organic materials which are susceptible to oxidative degradation under normal conditions. Materials that can be stabilized in this way include a variety of synthetic polymers. These polymers include various polyolefins such as polyethylene, polypropylene, polybutylene, polybutadiene, polymethylpentene. Other polymers that can be stabilized by the compounds of the invention include acetal resins, polyacrylates, polymethacrylates, polydialkylphthalates, cellulose derivative plastics, polyamides, polyesters, polyurethanes, polycarbonates, polystyrene, polyvinyl chloride and polyvinylidene chloride.

It is also possible to stabilize the copolymers with the compounds of the invention. Examples of such copolymers are copolymers of ethylene with propylene, copolymers of butadiene with styrene, copolymers of ethylene with vinyl acetate, and copolymers of ethylene with ethyl acrylate. These copolymers may also include tarpolymers such as ethylene-propylene-unconjugated dian terpolymers and acrylonitrile-butadiene-styrene interpolymers. Mixtures of polymers such as a mixture of polystyrene with polyphenylene oxide and a mixture of copolymers or terpolymers of ethylene propylene with polypropylene can also be stabilized by the compounds of the invention. Other materials that can be stabilized by the compounds of the invention include hot melt adhesives such as polyester based adhesives, polyamides, or mixtures of ethylene with vinyl acetate.

Petroleum products such as fuels, lubricating oils and greases, and natural products such as rubber, waxes, fats, tallow, linseed oil, corn oil, pheasant alley and cod liver oil can also be stabilized. This is a representative, but not exhaustive, list of products which can be advantageously protected against degradation by the compounds of the invention.

To achieve protection against oxidative degradation, the compounds of the invention are added to the above materials in the same amounts as used with other antioxidant agents that may have similar properties to achieve such protection. Depending on the material used, the antioxidant is added in an amount of from 0.001 to 10% by weight based on the weight of the material, with a typical range being from 0.05 to 2.0% by weight.

The compounds of the invention may be used either alone to stabilize organic materials or in combination with other stabilizers. Such other stabilizers may include other phenol-based compounds, various thio compounds, such as thiodipropionic esters, phosphites and phosphonates, antimicrobial chemicals such as oxalamides, various ultraviolet stabilizers, as well as other ingredients found to be beneficial in their addition. effect on the stability of said materials.

The compounds of the invention can generally be prepared from known starting materials by the amidification and esterification reactions described in the literature. Suitable aminoalcohols-NE used in preparing the compounds of this invention include ethanolamine, 2-aminopropanol, 2-amino-2 ^{1-methyl-1-propanol,} 3-amino-2-methyl-1-propanol, 2-amino-2- methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-1-butanol, tris (hydroxymethyl) aminomethane, 1-amino-15

1-aminomethyl-1-cyclohexanemethanol, 6-amino-1-hexanol, 2-amino-3-methyl-1-butanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 3 -amino-1-propanol,

2-aminocyclohexanol, 4-aminocyclohexanol, 3-amino-2-butanol, 1-amino-2-dodecanol, 2,2-dimethyl-3-amino-1-propanol, 2-aminomethyl-2-methyl- 1,3-propanediol, 2,2,2-tris (hydroxymethyl) aminoethane.

Many other amino alcohols can be readily prepared from the available starting materials by known methods.

A suitable synthesis of a compound of the invention will generally involve the preparation of an amide from one of the above alkanolamines followed by esterification of the resulting hydroxyalkylamide.

The amide used can be readily prepared by reacting an alkanolamine with an appropriate acid or acid chloride or ester. Suitable acids include C1-C21 aliphatic acids, benzoic acid, substituted benzoic acids such as alkylbenzoic acid, chlorobenzoic acid, dialkylbenzoic acid, 4-hydroxy-3,5-dlalkylbenzoic acid, 2- (4-hydroxy-3, 5-dialkylphenyl) acetic acid or 3- (4-hydroxy-3,5-dialkylphenyl) propionic acid.

If bis-amides are to be prepared, suitable acids include oxalic acid, phthalic acid, terephthalic acid, thiodialanoic acid and aliphatic diacids of the formula HO-CO-C _n H 2 _n -COOH, where a is an integer from 1 to 10 Examples of such acids are malonic, succinic, adipic, palmitic, azelaic, sebacic, and others.

Esters and chlorides of all the above acids are also suitable starting materials in the preparation of amides. It is known that some of the above acids may give rise to imides.

Appropriate measures, such as a large excess of amines and the use of milder conditions, are appropriate in such cases to maximize amide yield.

The usual starting material for esterification is 3,5-dialkyl-hydroxybenzoic acid, 2- (3,5-dialkyl-4-hydroxyphenyl) acetic acid or 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid, their chlorides or esters.

2

When an esteramide is prepared in which R and R are identical, esterification and amidification can be carried out in a single step.

When ethanolamine substituted with an alkyl or hydroxyalkyl group is used as the starting amine, a preferred alternative to the above procedures is possible. In this alternative, oxazoline is prepared by known methods from an acid or a derivative thereof and an aminoalcohol. The oxazoline formed can then be hydrolyzed to the aminoester, which can then be amidified by known methods.

The preparations described above are given as non-limiting examples of processes by which the compounds of the invention can be prepared. Those skilled in the art will be able to apply other appropriate procedures in the present case.

The following examples illustrate the invention in greater detail without limiting its scope.

Example 1

3- (3,5-di-tert-butyl-4-hydroxyphenyl) -N- (2-hydroxyethyl) propionamide

In a 3-liter, three-necked round-bottomed flask equipped with a thermometer, stirrer and a Dean-Stark trap with a condenser was charged 556 g (2.0 mol) of 3- (3,5-di-tert-butyl-) acid. 4-hydroxyphenyl) propionic acid, 135 g (2.2 mol) ethanolamine and 500 ml xylene. The mixture was heated at reflux for 11 hours and 79 ml of azeotropic mixture were collected. The xylene was distilled off under reduced pressure and the residue was dissolved in hot toluene. 211 g of an oily compound are obtained, which crystallizes on cooling. Melting point: 129-130 ° C.

Example 2

2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamido] ethyl laurate

A mixture of 44 g (0.22 mol) of lauric acid, 64 g (0.2 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -N- (2-hydroxyethyl) propionamide, 2 g of tetrabutyl titanate (Tyzor) as a catalyst and 100 ml of xylene were refluxed for 5 hours. Collect 3.8 ml of water in a Dean-Stark trap. The xylene was removed by distillation under reduced pressure and the residue was dissolved in acetonitrile. Cooling the solution in the refrigerator gave a white precipitate. Acetonitrile is removed by casting and the recrystallization is repeated. The last traces of acetonitrile were removed by heating the product under reduced pressure to give 66 g of the title compound as a tan oil at room temperature.

Example 3

2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamido] ethyl stearate

A mixture of 32.1 g (0.1 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -N- (2-hydroxyethyl) -propionamide, 28.5 g (0.1 mol) of acid stear, 1 g of tetrabutyl titanate (Tyzor) as a catalyst and 50 ml of xylene are heated to reflux at 140-170 ° C until water vapor is formed. 3.5 ml of water was collected in a Dean-Stark trap. The xylene was removed by distillation under reduced pressure and the residue was crystallized from acetonitrile. This gives 53 g of the title compound, m.p. 55-57 ° C.

Example 4

N- (2-hydroxyethyl) lauramide

To a solution of 24 g (0.4 mol) of ethanolamide in 100 ml of toluene at 50 ° C is added 40 g (0.2 mol) of lauric acid. The resulting mixture was heated at reflux for 6 hours.

The toluene is gradually removed to raise the resulting mixture temperature to 140 ° C. The distillate is collected in a Dean-Stark trap. The toluene was removed by distillation under reduced pressure and the residue was crystallized from n-hexane. 44 g of the title compound of m.p. 80 DEG-84 DEG C. are obtained.

Example 5

2- (lauramido) ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

A mixture of 13.9 g (0.055 mol) of N- (2-hydroxyethyl) -lauramide, 13.9 g (0.05 mol) of acid

3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 0.5 g of tetrabutyl titanate (Tyzor) as a catalyst a) 100 ml of xylene are heated under reflux until water is formed (3 hours). The xylene is then removed by distillation under reduced pressure and the residue is dissolved in acetonitrile. Cooling to about -10 ° C resulted in the formation of white crystals. The acetonitrile is decanted and the recrystallization is repeated. The last traces of acetonitrile were removed under reduced pressure to give the title compound as a yellow oil at room temperature.

Example 6

N- (2-hydroxyethyl) stearamide

To a solution of ethanolamine (24.4 g, 0.4 mol) in ethanol (500 ml) was added at 60 ° C

85 »2 g (0.3 mol) of stearic acid. Ethanol is removed by distillation until the temperature reaches 100 ° C, 300 ml of toluene are added and the water is distilled off as an azeotropic mixture. 6 ml of water was collected in a Dean-Stark trap over 5 hours at 110 ° C. To increase the temperature of the mixture to 135, a portion of toluene was removed. 7 ml of water was distilled off for another 4 hours. Upon cooling, 38.5 g of the title product crystallize, mp 96-99 ° C.

Example 7

2-stearamidoethyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

A mixture of 30.6 g (0.11 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid,

32.6 g (0.1 mol) of N- (2-hydroxyethyl) -stearamide, 0.8 g of tetrabutyl titanate (Tyzor) as catalyst and 100 ml of xylene are heated at reflux for 6 hours. 1.8 ml of water was collected in a Dean-Stark trap. The solution was filtered through synthetic calcium silicate (Microcel) and the solvent was removed by distillation under reduced pressure. The title compound (51 g) was recrystallized from acrylonitrile. Its melting point is in the range of 52 to 55 ° C.

Example 8

2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamido] ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

A mixture of 32 g (0.1 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -N- (2-hydroxyethyl) propionamide, 27 g (0.1 mol) of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 1 g of tetrabutyl titanate (Tyzor) as catalyst and 100 ml of xylene are heated to 150 ° C under reflux until the formation of water vapor has ceased. Within 4 hours, 2 ml of water was collected in a Dean-Stark trap. The xylene is removed by distillation under reduced pressure. The title compound is recrystallized from toluene / hexane (54 g). Its melting point ranges from 151 to 154 ° C.

Example 9

2- [2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethyl] -4,4-dimethyl-2-oxazoline

A mixture of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid (167 g, 0.6 mol), 2-amino-2-methylpropanol (65 g, 1.06 mol) and xylene (100 ml) was heated. 6 hours under reflux. Water is collected in Dean-Stark's tank. The mixture is poured into 300 ml of hexane and the resulting crystalline product is filtered off by cooling. 101 g of the title product of melting point 138 DEG-141 DEG C. are obtained.

He did

2-Amino-2-methylpropyl- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

In a 1-liter, three-necked round-bottomed flask equipped with a thermometer, stirrer and condenser was charged 66.2 g (0.2 mol) of 2- [2- (3,5-di-tert-butyl-4-). hydroxyphenyl) ethyl] -4,4-dimethyl-2-oxazoline, 400 mL isopropanol and 33 mL 6 N hydrochloric acid. The mixture was heated at 45 ° C for 2 hours and then cooled. 250 ml of water and 33 ml of 6N sodium hydroxide are added to this solution with stirring. The resulting product was filtered off and dried. 52 g of the title compound of melting point 97 DEG-99 DEG C. are thus obtained.

Example 11

3- (3,5-di-tert-butyl-4-hydroxyphenyl) -N- (1,1-dimethyl-2-hydroxyethyl) propionamide

In a 1-liter, three-necked, round-bottom flask equipped with a thermometer, stirrer and condenser was charged 34.9 g (0.1 mol) of 2-amino-2-methylpropyl- [3- (3,5-di) of tert-butyl-4-hydroxyphenyl) propionate] and 200 ml of isopropanol. The resulting mixture was heated to reflux for 15 hours. Then the solvent was distilled off and the residue was dissolved in hot hexane. On cooling, 20 g of the title compound and the like compound are obtained in similar crystals, which are filtered off and dried. Melting point: 120-122 ° C.

Example 12

2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamido] -2-methylpropyl laurate

To a solution of 70 g (0.2 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -N- (1,1-dimethyl-2-hydroxyethylpropionamide) in 60 ml of dimethylaniline and 50 ml of toluene is added dropwise A solution of 55 g (0.25 mol) of lauroyl chloride in 50 ml of toluene was heated at 50 DEG C. for 4.5 hours, then washed first with dilute hydrochloric acid, then brine, and the toluene was removed by distillation under reduced pressure. The residue is dissolved in acetonitrile, the solution is shaken with charcoal, filtered, and the filtrate is placed in the refrigerator, 20 g of the title compound crystallizes, and the crystals are collected by filtration, m.p. .

Example 13

2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamido] -2-methylpropyl palmitate

13 g (0.037 mole) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -N- (1,1-dimethyl-2-hydroxyethyl) propionamide, 10 g triethylamine and 250 ml benzene. To this mixture, 10.2 g (0.037 mol) of palmitic acid chloride was added with stirring, and the mixture was stirred for 3 hours, then filtered and distilled. The residue was dissolved in hot ecetonitrile. Some of the palmitic anhydride crystallizes and the crystals formed are filtered off. The acetonitrile solution was left in the refrigerator overnight to give 20 g of the title compound. The crystals formed are filtered off and dried. Their melting point ranges from 41 to 43 °.

Example 14

2-Palmitamido-2-methylpropyl-3- (3,5-di-tert-butyl-4-hydrophenyl) propionate

In a 1 liter three-necked round-bottomed flask equipped with a thermometer, stirrer and dropping funnel was added 17.5 g (0.05 mol) of 2-amino-2-methylpropyl-3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate, 500 ml of benzene and 10 g of trietnylamine. 14 g (0.05 mol) of palmitic acid chloride are added to this mixture with stirring and the resulting mixture is stirred for 4 hours, then filtered and distilled. The residue was dissolved in hot acetonitrile. The solution was stored at 5 ° C for 4 days to crystallize the product. Remove by filtration and dry. 14 g of the title compound of melting point 43-46 ° C are obtained.

Example 15

2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamido] -2-methylpropyl stearate

In a 1 liter three-necked round-bottom flask equipped with a thermometer, stirrer and dropping funnel was added 26.2 g (0.075 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -N9.

- (,, 1-dimethyl-2-hydroxyethyl) propionamide, 20 g of triethylamine and 400 ml of benzene. 22.5 g (0.075 mol) of stearic acid chloride were added with stirring, and the reaction mixture was stirred for 8 hours. The triethylamine hydrochloride was filtered off and the solvent was stripped off.

The residue was dissolved in hot hexane and 2.5 g of stearic anhydride was isolated, the hexane was stripped off and the residue dissolved in hot acetonitrile. Upon cooling, the title compound crystallizes out, which is filtered off and dried. Its melting point is in the range of 59 to 61 ° C.

Example 16

2-Stearamido-2-methylpropyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

In a 500 ml three-necked round bottom flask equipped with a thermometer, stirrer and dropping funnel was added 26 g (0.075 mol) of 2-amino-2-methyl-propyl-3- (3,5-di-tert). butyl 4-hydroxyphenyl) propionate, 200 ml benzene and 8.2 g triethylamine. 22.5 g (0.075 mol) of stearic acid chloride were added to this mixture with stirring and the resulting mixture was stirred for 4 hours. The triethylamine hydrochloride was filtered off and the solvent was stripped off. The residue was dissolved in hexane while hot. Crystallization, filtration and drying gave the title compound, m.p. 46-48 ° C.

Example, 7

2- (3,5-di-tert-butyl-4-hydroxy-benzamido) -2-methylpropyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

In a 1 liter three-necked round-bottomed flask equipped with a thermometer, stirrer and dropping funnel was added 34.9 g (0.1 mol) of 2-amino-2-methyl-propyl-3- (3,5-di). tert-butyl-4-hydroxyphenyl) propionate, 20 g triethylamine and 400 ml benzene. 26.8 g (0.094 mol) of 3,5-di-tert-butyl-4-hydroxybenzoic acid chloride were added with stirring and the resulting mixture was stirred overnight. The mixture was filtered and distilled, and the resulting residue was suspended in hexane. The product is filtered off and recrystallized from isopropanol. 30.5 g of the title compound of melting point 192 DEG-94 DEG C. are obtained.

Example 18

2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamido] isobutanetriyl tris [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

A solution of 85 g (0.27 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid chloride in 120 ml of toluene was added to 7.3 g (0.06 mol) of tris (hydroxymethyl). of aminomethane in 60 ml of pyridine and 30 ml of toluene. The mixture was stirred at 60 ° C for 42 hours. The mixture was then washed with dilute acid and then brine. Toluene was distilled off under reduced pressure and the residue was recrystallized from n-hexane. This yields the title compounds in the title. mp 118-122 ° C.

Elementary analysis:

H, 9.28; N, 1.21. Found: C, 74.19; H, 9.47; N, 1.11.

Example 19

2- (2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethyl) -2-oxazoline-4,4-dimethyl-bis (3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate]

A mixture of 167 g (0.6 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 24.2 g (0.2 mol) of tris (hydroxymethyl) aminomethane and 100 ml of xylene is heated under reflux for 6 hours. Water is collected in the Dean-Stark trap. The hot mixture was poured hot into 300 ml of hexane to give the title compound, which was recrystallized from benzene to give 166.9 g of the title compound, m.p. 173-175 ° C.

Elementary analysis:

H, 9.23; N, 1.58. Found: C, 74.53; H, 9.09; N, 1.34.

Example 20

2-stBramidoisobutantriyltrie [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

To 44.2 g (0.05 mol) 2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ethyl] -2-oxazoline-4,4-dimethylbis [3- (3) Of 5-di-tert-butyl-4-hydroxyphenyl) propionate] in 20 ml of toluene is added

8.2 ml of 6 M hydrochloric acid. The mixture was stirred for 4 hours and 8 g of sodium bicarbonate were added. The aqueous layer was separated and 40 ml of triethylamine was added to the organic layer, followed by 15.1 g (0.05 mol) of stearic acid chloride in 30 ml of toluene. The mixture was stirred at room temperature overnight and then stirred at 50 ° C for 1 hour.

After cooling, the mixture was washed first with dilute hydrochloric acid and then with brine. The toluene was distilled off under reduced pressure. The residue was purified by passing it through a column of silica, eluting with a toluene / hexane (50:50 by volume) mixture. Evaporation of the eluent gave 28 g of the title compound, mp 77-79 ° C.

Example 21

N, N'-bile (hydroxyethyl) oxamide

To a solution of 134 g (0.22 mol) of ethanolamine in 1 liter of ethanol was added 146 g (0.1 mol) of diethyl oxalate over 1 hour. The resulting mixture was heated at 50 ° C for 1 hour. On cooling, 162 g of the title compound precipitated, which was filtered off and dried.

Its melting point ranges from 166 to 168 ° C.

Example 22

2,2'-Oxplyldiamidobis [ethyl 1-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

A mixture of 55.6 g (0.2 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 17.6 g (0.1 mol) of N, H'-bis (2 -hydroxyethyl) oxamide, 1.5 g tetrabutyl titanate and 200 ml xylene are heated to reflux. Water and xylene are removed until the temperature of the reaction mixture reaches 200 ° C. After cooling, 54 g of the title compound crystallized. After recrystallization from toluene, its melting point is in the range of 128 to 131 ° C.

Example 23

2,2'-Oxalyldiamidobis [2-methylpropyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

In a 500 ml three-necked round bottom flask equipped with a thermometer, stirrer and dropping funnel was added 35 g (0.1 mol) of 2-amino-2-methylpropyl-3- (3,5-di-tert.). butyl 4-hydroxyphenyl) propionate, 250 ml benzene and 2.0 g triethylamine. To this mixture, 6.35 g (0.05 mole) of acetic acid chloride was added with stirring and the resulting mixture was stirred for 2 hours, then filtered and the solvent was distilled off. The residue was dissolved in a 2: 1 mixture of benzene and hexane and allowed to cool. 22 g of crystalline product are obtained, which after recrystallization from benzene / hexane (2: 1) melts at a temperature in the range from 169 to 171 ° C.

Example 24

2,2'-adipamidobis- [2-methylpropyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

In a 1 liter three necked round bottom flask equipped with a thermometer, stirrer and dropping funnel was added 29 g (0.083 mol) of 2-amino-2-methylpropyl- [3- (3,5-di-tert-butyl). 4-hydroxyphenyl) propionate], 20 g of triethylamine and 400 ml of benzene. To this mixture was added 7.6 g (0.0415 mol) of adipic acid chloride with stirring, and the resulting mixture was stirred for 4 hours.

The mixture was filtered and distilled to give a residue which was dissolved in hot hexane. Upon cooling, the product crystallized. Recrystallization from 400 ml isooctane with 125 ml toluene gave 21 g of the cross-linked product, m.p. 135-138 ° C.

Example 25

2,2'-sebacamldobis- [2-methylpropyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

To a 1-liter, 3-neck, round-bottom flask equipped with a thermometer, stirrer and dropping funnel was charged 34.9 (0.1 mol) of 2-amino-2-methylpropyl-3- (3,5-di-tert-butyl). butyl-4-hydroxyphenyl) propionate, 20 g triethylamine and 400 ml benzene. 11.9 g (0.05 mol) of sebacic acid chloride was added to this mixture with stirring and the resulting mixture was stirred for 5 hours. The mixture was filtered and distilled to give a residue which was dissolved in hot hexane. A solid is formed which is recrystallized from hexane / benzene (3: 1). This gives 32 g of the title compound, m.p. 13-13 ° C.

Example 26

2,2'-sebacamldobis [isobutanetriyl tris [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]]

To 44.2 g (0.05 mol) 2- [2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethyl] -2-oxazoline-4,4-dimethylbis (3- (3,5) of di-tert-butyl-4-hydroxyphenyl) propionate] in 200 ml of toluene is added

8.2 ml of 6 K hydrochloric acid. After stirring for 3 hours, 6 g of sodium bicarbonate were added. The mixture was stirred for 15 minutes and the layers were separated. To the organic layer (driven first with 40 ml of triethylamine, then 6 g (0.025 mol) of sebacic acid chloride in 30 ml of toluene) was stirred overnight at room temperature and stirred for 1 hour at 50 ° C. The mixture was washed first with dilute hydrochloric acid, then brine, the toluene was removed by distillation under reduced pressure, the residue was taken up in toluene / hexane (1 * 1) and the solution was passed through a fluorosil column to remove 11 g of the solvent. mp 134 DEG-14 DEG.

Example 27

Ν, Κ'-bis [1,1'-bis (hydroxymethyl) -2-hydroxyethyl] terephthalamide

In a 1-liter, 3-neck, round-bottom flask equipped with a thermometer, stirrer and condenser was charged 194 g (1.0 mole) of dimethyl terephthalate, 242 g (2.0 mole) of tris (hydroxymethyllaminomethane) and 1 liter of methanol. The title compound crystallizes out and is filtered off and dried, m.p. 188-190 ° C.

Example 28

2,2'-terephthalamidobis [isobutanetriyltris [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]]

To a 1-liter, 3-neck, round-bottom flask equipped with a thermometer, stirrer, dropping funnel and condenser was charged 18.6 g (0.05 mol) of Ν, Ν'-bis [1,1'-bis (hydroxymethyl) ) 227302

-2-hydroxyethyl] -tephthalamide and 200 ml of pyridine. To this suspension, 90 g (0.3 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid chloride are added from stirring at a temperature in the range of 20 to 30 ° C and the resulting mixture is stirred hours. The mixture was filtered and distilled and the resulting residue was dissolved in hot cyclohexane. Trace amounts of pyridine hydrochloride are filtered off and the solution is allowed to cool. Cooling gave 61 g of the title product as crystals which, after recrystallization from methanol, melted at 169-172 ° C.

Example 29

3,3'-thiobis [2-propionamidoethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

A solution of ethanolamine (26.8 g, 0.44 mol) and dimethyl 3,3'-thiopropionate (41.2 g, 0.2 mol) in ethanol (100 ml) was refluxed for 5 hours. 3,3'-thiobis- [N- (2-hydroxyethyl) propionemide], having a melting point after washing with acetone ranging from 130 to 32 ° C, is isolated as a crystalline white solid.

A mixture of 18 g (0.068 mol) of the above intermediate, 41.7 g (0.15 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl-propionic acid) and 1 g of tetrabutyl titanate in 100 ml of xylene is heated under 3.5 ml of water was collected in a Deans-Stark trap, after evaporation of xylene, 51 g of product were obtained as a viscous yellow oil.

Example 30

3'-thiobis [2-methyl-2-propionamidopropyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

A mixture of 40 g (0.44 mol) of 2-amino-2-methylpropenol, 3 g of potassium tert-butoxide and 41.2 g (0.2 mol) of dimethyl 3,3'-thlodipropionate was stirred at room temperature for 0.5 h. and then heated to 90 ° C for 0.5 hour under reduced pressure. Excess 2-amino-2-methylpropanol was removed by distillation under reduced pressure. Half (0.1 mol) of the resulting 3,3'-thiobis-N- (1'-dimethyl-2-hydroxyethyl) propionamide is heated for 2 hours under reduced pressure at a temperature between 100 and 1.0 ° C with 61 ° C. 2 g (0.2 mol) of ethyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 2 g of potassium tert-butoxide. The mixture was taken up in toluene, neutralized with acetic acid and washed with water. Removal of the toluene by distillation under reduced pressure afforded 79 g of the title compound as a yellow viscous oil liquid.

Example 31

N, N'-bis [2-hydroxyethyl] terephthalamide

A mixture of 194 g (1.0 mol) of dimethyl terephthalate, 150 ml (2.46 mol) of ethanolamine and 300 ml of ethanol was heated at reflux for 7 hours. On cooling, the title product precipitates, which is filtered off and washed with ethanol. After drying, it melts at 227-229 ° C.

Example 32

2,2'-terephthalamido-N, N'-bi8 [ethyl- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]]

To a mixture of 25.2 g (0.1 mol) of M, N'-bie- (2-hydroxyethyl) terephthalamide and 200 ml of pyridine was added 59.3 g (0.2 mol of 3- (3,5- di-tert-butyl-4-hydroxyphenyl) propionic acid in 300 ml of toluene, stirred for 2 hours, warmed to 90 ° C and filtered while hot. This gives 68 g of the title product which is filtered off and washed with hot water.

After drying, its melting point in the mixture is from 73 to 75 ° C.

Example 33

3-Oxalylamido-bis- [propyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

To a solution of 82.5 g (1.1 mol) of 3-amino-1-propanol in 500 ml of ethanol was added 73 g (0.5 mol) of diethyl oxalate over half an hour. The temperature is raised to 50 ° C. The mixture was stirred for an hour and the resulting precipitate (m.p. 156-158 ° C) was filtered off. a portion (20.4 g) of the thus obtained N, N '- (3-hydroxypropyl) oxamide was added to a mixture of 61.2 g (0.22 mol) of 3- (3,5-di-tert-butyl-4-) hydroxyphenyl) prionic, 100 ml xylene and 2 g tetrabutyl titanate (Tyzor) as catalyst. The resulting mixture was refluxed for 4 hours before being filtered through a Mycrooel filter. The xylene was removed by distillation under reduced pressure and the residue was taken up in hot hexane. Cooling gives the title compound, m.p. 120-123 ° C.

Elementary analysis:

H, 8.84; N, 3.87. Found: C, 69.96; H, 8.84; N, 4.02.

Example 34

3-Stearamidopropyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

To a hot (80 ° C) mixture of 30 g (0.4 mol) of 3-aminopropanol, 100 ml of xylene and 0.5 g of sodium methoxide was added 56.8 g (0.2 mol) of stearic acid. The mixture was heated at reflux for 2 hours to remove water, then poured into hexane, where N- (3-hydroxypropyl) stearamide crystallized and was filtered off. Its melting point is in the range of 83 to 89 ° C. After recrystallization from acetone, the melting point is increased to 94-96 ° C.

The read (34.1 g; 0.1 mol) of this intermediate was heated with 27.8 g (¢, 1 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 1 g of tetrabutyl titanate (Tyzor) as catalyst and 100 ml of xylene. The mixture was heated at reflux for 3 hours while 2 ml of water was collected in a Dean-Stark trap. The xylene was distilled off under reduced pressure and the residue was crystallized from acetonitrile. This gives 29 g of the title product, m.p. 50-52 ° C.

Example 35

N- (2,2-dimethyl-3-hydroxypropyl) stearamide

In a 500 ml three-necked, round-bottom flask equipped with a thermometer, stirrer and a Dean-Stark trap with a condenser was charged 119.4 g of methyl stearate, 41 g of 3-amino-2,2-dimethyl-propanol and 3 g of potassium ether. .butoxide. This mixture was heated to 190 ° C and methanol was distilled off. The reaction mixture was dissolved in hot isopropanol and filtered. Upon cooling, the product crystallized and after filtration and drying, its melting point was 44 ° C.

The IR spectrum shows an estercarbonyl group. Washing with hot hexane gave pure product, m.p. 68-69 ° C.

Example 36

2,2-Dimethyl-3-stearamidopropyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

In a 1-liter, 3-neck, round-bottom flask equipped with a thermometer, stirrer, dropping funnel and condenser was charged 36.9 g of N- (2,2-dimethyl-3-hydroxypropyl) stearamide, ml of triethylamine, and 250 ml of toluene. 29.6 g of 3- (3,5-di-tert-butyl-4-hydroxyphenylpropionic acid chloride) are added with stirring, the mixture is filtered, distilled and the residue is dissolved in hot methanol and 2,2-dimethyl is isolated. 3-Stearamidopropyl stearate, m.p. 60-62 DEG C. The methanolic solution was distilled off and the residue was dissolved in acetonitrile to give the title compound, m.p.

Example 37

N, N'-bis with [2,2-dimethyl-3-hydroxypropyl] oxamide

To a 0.1 L round bottom flask was added 12.0 g of 3-amino-2,2-dimethylpropanol and 20 mL of ethanol. 8.5 g of diethyl oxalate were added to the solution with stirring, and the resulting mixture was stirred while increasing the temperature of the reaction medium. On cooling, the title compound precipitates, which is filtered off and recrystallized from ethanol. Melting points range from 125 ° C to 126 ° C.

Example 38

3-Oxalyldiamidobis [2,2-dimethylpropyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

In a 1-liter, 3-neck, round-bottom flask equipped with a thermometer, stirrer, dropping funnel and condenser was added 13 g of N, N-bis (2,2-dimethyl-3-hydroxypropyl) oxamide, 25 ml of triethylamine and 250 ml of toluene. . To this solution was added, with stirring, 29.6 g of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid chloride. The resulting mixture was stirred for 4 hours, then filtered and distilled. The residue was heated with hot hexane. The title compound starts to precipitate immediately, which is then isolated by filtration. Melting point: 143-144 ° C.

Example 39

2-stearamidoethyl 3,4-di-tert-butyl-4-hydroxybenzoate

A mixture of 25 g (0.1 mol) of 3,5-di-tert-butyl-4-hydroxybenzoic acid, 50 ml of toluene and 8.5 ml of thionyl chloride was heated at reflux for 3 hours. Excess thionyl chloride and toluene were removed by rotary evaporation. The acid chloride was dissolved in 50 ml of toluene and added to a mixture of 29.4 g (0.09 mol) of N- (2-hydroxyethyl) stearamide, 20 ml of toluene and 15 ml of pyridine. The resulting mixture was heated at reflux for 2 hours, cooled, diluted with water, and washed with dilute hydrochloric acid and then with water. Toluene was removed by distillation and the residue was crystallized from hexane. This gives the title compound, m.p. 56-58 ° C.

Example 40

This example illustrates the convenience of using the compounds produced by the process of the invention with polypropylene. It also shows the beneficial effect of using these compounds together with another stabilizer. The respective compounds used in the experiments described in this and the following examples are indicated by the numbers in the above examples in which the procedures for their preparation have been described.

The stabilizers are admixed into the polypropylene resin in a mill at a temperature of 16 ° C. By pressing in a press at a pressure of 186 MPa at a temperature of 170 [deg.] C., disks having a diameter of approximately 2.5 cm and a thickness of 1.9 mm are produced. These samples shall be placed in a forced-air oven at 149 ° C and the number of days for which the samples must be heated before becoming brittle; When two of the three disks become brittle, ie become grainy due to thermal aging, this is considered a sample failure. The results are shown in Table I.

Compound / other stabilizer Concentration ^x Days to sample failure none 1 DSTDP ^XX 0.2 4 Example 3 0.2 41 Example 3 / DSTDP 0.1 / 0.1 36 Example 7 0.2 32 Example 7 / DSTDP 0.1 / 0.1 25 Example 8 0.2 34 Example 8 / DSTDP 0.1 / 0.1 61 example 13 0.2 42 Example 13 / DSTDP 0.1 / 0.1 59 Example 14 0.2 39 Example 14 / DSTDP 0.1 / 0.1 60 Example 15 0.2 34 Example 15 / DSTDP 0/1 / 0.1 55 Example 17 0.2 26 Example 17 / DSTDP 0.1 / 0.1 45 Example 18 0.2 43 Example 18 / DSTDP 0.1 / 0.1 69 Example 20 0.2 48 Example 20 / DSTDP 0.1 / 0.1 78 Example 22 0.2 62 Example 22 / DSTDP 0.1 / 0.1 82 ' Example 23 0.2 59 Example 23 / DSTDP 0.1 / 0.1 98 Example 24 0.2 28 Example 24 / DSTDP 0.1 / 0.1 45 Example 25 0.2 35 Example 25 / DSTDP 0.1 / 0.1 48 Example 26 0.2 55 Example 26 / DSTDP 0.1 / 0.1 76 Example 28 0.2 61 Example 28 / DSTDP 0.1 / 0.1 55 Example 32 0.2 40 Example 32 / DSTDP ο, ι / ο, ι 64 Example 33 0.2 56 Example 33 / DSTDP 0.1 / 0.1 84

^x parts by weight per 100 parts by weight of polypropylene ^xx distearyl thiodiproptonate

Example 41

This example demonstrates the advantageous use of the compounds produced by the process of the invention for terpolymers consisting of ethylene, propylene and 5-ethylidene-2-norbornene, wherein the ethylene / propylene weight ratio is 67/33, the iodine number is 10 and the Uooney viscosity is 57 (MW-4 at 120 ° C).

0.165 g of stabilizers are dissolved in rubber cement containing 110 g of the above terpolymers in 2000 g of hexane. Hexane is removed by slowly adding rubber cement to the boiling water. The solids were removed from the boiling water by filtration and dried on a calender for 5 minutes at a temperature ranging from 135 to 149 ° C.

The time required for 1 g of sample to absorb 20 cm @ 2 of oxygen (Tgo) at 150 DEG C. is then determined. The results are shown in Table II. This results in the excellent protection afforded to the above terpolymer by the presence of the compounds produced according to the invention.

Table II

Ingredient TgQ (minutes) none 30 from Example 15 560 from Example 16 260 from Example 23 405

Example 42

This example illustrates the advantageous use of the compounds produced by the known process of the invention with a dynamically cured elastomeric mixture of 20 parts by weight of polypropylene with 80 parts by weight of a terpolymer consisting of ethylene, propylene and dicyclopentadiene.

The compound produced by the process of the invention is added to the mixture in a mill to a concentration of 0.3 parts by weight per 100 parts by weight of the mixture. Then, 1.9 mm thick plates are pressed from the resulting mixture, from which the discs are punched out. These discs are placed in a 149 ° C forced air oven, and the time required to embrace three of the five discs is determined. The results are shown in Table III.

Table III

Ingredient Brittle Time (h) none 80 from Example 23 275

Example 43

This example demonstrates the advantageous use of the compounds produced by the process of the invention with high impact strength polystyrene.

The antioxidant (0.25 parts by weight per 100 parts by weight of polystyrene) is admixed to a high impact strength polystyrene at 138 ° C in the mill. Notched test rods (Iodine) are pressed from the mixture at 170 ° C. After the notch toughness is taught, the test rods are ground and pressed again. This procedure is repeated five times. The final notch toughness (in percent) after five repetitions is shown in Table IV.

«

Table IV

Antioxidant Preserved ultimate notch toughness (%) none 58.3 from Example 15 76.2 from Example 16 66.3 from Example 23 85.2

Example 44

This example demonstrates an unexpectedly higher potency of the compound of Example 32 compared to di-2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], prepared according to USSR 567 719, when used with polypropylene. Test samples were prepared and tested essentially as described in Example 35, with the results shown in Table V.

Claims (2)

SUBJECT OF THE INVENTION A method for inhibiting the oxidative degradation of an organic material, characterized in that 0.001 to 10% by weight, based on the weight of the organic material, of a compound of formula I r 'cooanhm (I) is added to said organic material wherein: A represents a C 2 -C 12 -alkylene radical, a C 4 -C 8 -cycloalkyl radical or a radical of the formula -CH ₂ -C (CH ₂ ) _p - in which p is an integer from 3 to 6 or A represents a (C 2 -C 5) alkylene radical substituted with one or two groups of the formula -CH ₂ CO (CH ₂ ) _m R - in which: R1 is a 3-W-5-Y-4-hydroxyphenyl radical wherein each of W and Y, which are the same or different, is an alkyl radical of 1 to 12 carbon atoms and m is 0, 1 or 2, R @ ¹ represents an alkyl radical having from 11 to 17 carbon atoms or a group of the formula - (CH3) R @ 6 wherein R @ 8 is as defined above, and 11 represents a group of formula -COS wherein o R is C 1 -C 20 alkyl, C 1 -C 12 alkoxy, nitro or hydroxy; or R ² is -BCONHAOCOr ', wherein: A and R are as defined above and B represents a single bond, an alkylene radical having 1 to 10 carbon atoms, a phenylene radical, an oxydialkylene radical having 4 to 12 carbon atoms or a thiodialkylene radical having 4 to 12 carbon atoms, or 2 I R is as defined above, with the proviso that at least one of A, R, and M contains a 3-W-5-Y-4-hydroxyphenyl radical. 2. A process according to claim 1 wherein the organic material is a compound of formula (1) above wherein: A represents a C2-C4 alkylene radical or an ethylene radical substituted by two groups of the formula -CHgOCOCHgCHgR4 _in which R1 represents a 3,5-di-tert-butyl-4-hydroxyphenyl radical; Or a radical of the formula -CHgCHgR3, wherein R1 is as defined above, rt M represents a group of the formula -COR in which R ² represents alkyl radicals having 11 to 17 carbon atoms, 3,5-di-tert.butyl-4-hydroxyphenyl group, or a group of formula -BCONHAOCOR wherein A and R ¹ are as defined above and B represents a single bond, an alkylene radical having 4 to 8 carbon atoms, a thiodiethylene or phenylene radical, provided that at least one of A, R and M contains 3,5-di-tert-butyl-4-hydroxyphenyl.