JPS6254298B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to novel phenolic esteramides that are useful in protecting organic materials such as synthetic and natural rubbers, petroleum products, and plastics from oxidative degradation. The present invention relates to compounds of formula R ¹ COOANHM, where A is C ₂ -C ₄ alkylene, or A is one or two -
CH ₂ OCO(CH ₂ ) _n C ₂ alkylene substituted with a R ³ group (wherein R ³ is 3,5-dithyabutyl-4-hydroxyphenyl and m is 2) R ¹ is -(CH ₂ ) _n R ³ (wherein m and R ³ are as defined above); M is -COR ² (wherein,
R ² is C ₁₀ -C ₂₀ alkyl, or R ²
is -BCONHAOCOR ¹ (where A and R ¹ are as defined above and B is a single bond, C ₁ -C ₁₀ alkylenephenylene or C ₄ thiodialkylene), or R ² is R ¹ defined above
). The terms alkyl and alkylene include straight chain and branched moieties. The compounds of the present invention and related matters will be explained in detail below. The present invention relates to a method for producing a compound having the formula R ¹ COOANHCOR ² , where A is C ₂
Alkylene of C ₁₂ to C 12, cycloalkylene of C ₄ to C ₈ , or -CH ₂ C (CH ₂ )- with p of 3 to 6
or A is an integer of one or two -
CH ₂ OCO(CH ₂ ) _n C 2 to C ⁵ alkylene substituted with the group R ₃ , m is 0, ₁ , or 2, and R ³ is 3-W-5-Y- In 4-hydroxyphenyl, W and Y may be the same or different and are C ₁ to C ₁₂ alkyl; R ¹ is -
(CH ₂ ) _n R ³ , where m and R ³ are as defined above; R ² is C ₁ to C ₂₀ alkyl, C ₅ to C ₆ cycloalkyl, C ₆ to C ₁₀ aryl , phenyl substituted with halogen, _C1 - _C12 alkyl, _C1 - _C12 alkoxy, nitro or hydroxy; or R ₁ and R ₂ are m and
R ³ is -(CH ₂ ) _n R ³ as defined above; B is one single bond, C ₁ to C ₁₀ alkylene, C ₄ to C ₈
cycloalkylene, phenylene, C ₄ to C ₁₂ oxydialkylene or C ₄ to C ₁₂ thiodialkylene;
Compounds of R ¹ COOANH ₂ with formula R ⁴ COX or B
(COX) ₂ in which A, R ¹ and B are as defined above and X
is halogen, hydroxy, or C ₁ to C ₄ alkoxy, R ₄ is m and R ³ are as defined above - (CH ₂ ) _n R ³ , C ₁ to C ₂₀ alkyl, C ₄ to C ₈ cycloalkyl, C ₆ to C ₁₀ aryl, or phenyl substituted with halogen, C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ alkoxy, nitro, or hydroxy; 15°C to 250°C, provided that an acid acceptor is employed in the reaction when X is a halogen.
℃ temperature and 100Pa to 10kPa. The present invention also relates to a process for the preparation of compounds having the formula R ¹ COOANHCOR ² ; where A is
C ₂ to C ₅ alkylene, one or two -
CH ₂ OCO(CH ₂ ) _n C ₂ to substituted with R ³ groups
C ₅ alkylene, R ³ is 3-W-5-Y-
In 4-hydroxyphenyl, W and Y may be the same or different and each is a C ₁ to C ₁₀ alkyl, and m is 0, 1, or 2; or A
is C ₄ to C ₈ cycloalkylene or p is an integer of 3 to 6 —CH ₂ C(CH ₂ ) _p —; R ¹
is - (CH ₂ ) _n R ³ ; R ² is C ₁ to C ₂₀ alkyl, C ₆ to C ₁₀ aryl, or halogen.
phenyl substituted with C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ alkoxy, nitro, or hydroxy; or R ² is BCONHAOCOR ¹
and A and R ¹ are as defined above,
B is one single bond, C ₁ to C ₁₀ alkylene,
Phenylene, C ₄ to C ₁₂ oxydialkylene,
or C ₄ to C ₁₂ thiodialkylene;
Its manufacturing method is the formula

[Formula] There is Yeah

consisting of reacting [formula] with a compound of formula R ¹ COX; Q is C ₂ to
C ₁₂ alkylene, C ₄ to C ₈ cycloalkylene,
C ₄ to C ₈ cycloalkylene or -CH ₂ -
(CH ₂ ) _p -, s is an integer from 1 to 3,
B, R ¹ , X and p are as defined above, R ⁴
is -(CH ₂ ) _n R ³ where m and R ³ are as defined above,
C ₁ to C ₂₀ alkyl, C ₅ to C ₆ aryl, or halogen, C ₁ to C ₁₂ alkyl, C ₁ to
phenyl substituted with _C12 alkoxy, nitro or hydroxy; the process is carried out at 15°C to 25°C, provided that when X is halogen, an acid acceptor is employed in the reaction. temperature and
It is carried out at a pressure of 100Pa to 10kPa. The invention also relates to compositions comprising the compounds of the invention and organic substances that are subject to oxidative degradation. A is preferably alkylene with a terminal CH ₂ group. Most preferably, the ester and amide groups are attached to an alpha-terminated alkylene that has no hydrogen on the beta carbon. The preferred definition of R ² depends in part on the intended use of the product. If high hydrocarbon solubility is desired, any of R ² should have a long hydrocarbon chain with 11 to 17 carbon atoms. In particularly useful compounds _, ^R2 is _C17H35 . If low volatility is desired, R ² is
BCONHAOCOR ¹ , where B, A, and R ¹ are as defined above. Particularly useful are compounds in which B is a single covalent bond. ^Particularly _{high molecular} ^{weight and} _low ^_ Volatility can be achieved. Preferred halogens are fluorine, chlorine, bromine, and iodine. The compounds of this invention are useful for stabilizing organic materials that normally undergo oxidative degradation. Materials stabilized in this manner include a number of synthetic polymers. Among these polymers are various polyolefins such as polyethylene, polypropylene, polybutylene, polybutadiene, and polymethylpentene. Other polymers stabilized by the compounds of this invention include acetal resins, polyacrylates, polymethacrylates, polydialkyl phthalates, cellulose materials, polyamides, polyesters, polyurethanes, polycarbonates, polystyrene, polyvinyl chloride, polyvinylidene chloride. ,
is included. Copolymers can also be stabilized by the compounds of the invention. Representative copolymers include ethylene/propylene copolymers, butadiene/styrene copolymers, ethylene/vinyl acetate copolymers, and ethylene/ethyl acetate copolymers. Copolymers also include ethylene/propylene/nonconjugated diene terpolymers and acrylonitrile/butadiene/styrene interpolymers. Polystyrene/polyphenylene oxide and ethylene propylene copolymers or terpolymers/styrene can also be stabilized by the compounds of the invention. Other materials stabilized by the compounds of this invention include polyester, polyamide, or hot melt adhesives such as those based on ethylene/vinyl acetate. For example, fuels, lubricating oils, petroleum products such as mineral oil jelly, natural products such as natural rubber, waxes, fats, tallow oil, linseed oil, corn oil, cottonseed oil, and cod liver oil are also stabilized. The above list is representative of those who may benefit from the compounds of the present invention, but is by no means exclusive. To achieve protection against oxidative degradation, the compounds of the invention are added in amounts generally known for known antioxidants possessing similar properties to achieve such protection. Depending on the substrate used, antioxidants are added in amounts of 0.001 to 10% by weight, based on the weight of the substrate, with a typical range of 0.05 to 2.0%. The compounds of the invention can be used on their own to stabilize organic materials or in combination with other stabilizers. Such other stabilizers include other phenolic substances, various thio compounds such as thiodipropionate esters, phosphites,
and phosphonates; such as oxalamide,
anti-copper drug
chemicals), various UV stabilizers, and other additives found useful. The compounds of this invention can be made from known starting materials by amidation and esterification reactions, which are generally well known in the literature. Common amino alcohols used in the preparation of the compounds of the invention include ethanolamine, 2-aminopropanol, 2-amino-2-methyl-1-propanol, 3-amino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, -amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-1-butanol,
Tris(hydroxymethyl)aminomethane, 1-
Amino-1-cyclopentane methanol, 1-aminomethyl-1-cyclohexane methanol, 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-amino-cyclohexanol, 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 are readily made by known methods from available starting materials. A conventional synthesis of the compounds of this invention involves making an amide from one of the aforementioned alkanolamines and then esterifying the hydroxyalkyl amide. Amides are easily prepared by reacting alkanolamines with appropriate acid chlorides or esters. Suitable acids are C ₁ to
_C12 fatty acids, benzoic acid, dialkylbenzoic acid,
4-hydroxy-3,5-dialkylbenzoic acid,
Contains 2-(4-hydroxy-3,5-dialkyl phenyl) acetic acid or 3-(4-hydroxy-dialkylphenyl) propionic acid. When a bisamide is desired, suitable acids include oxalic acid, phthalic acid, terephthalic acid, thiodialkanoic acid, and those with the structure HO--CO--C _o H ₂
Includes aliphatic diacids in which _o -COOH and n is an integer from 1 to 10. Examples of such acids are malonic acid,
These include succinic acid, adipic acid, palmitic acid, azelaic acid, sebacic acid, and others. All esters and acid chlorides of the aforementioned acids are likewise suitable starting materials for making amides. It is recognized that imides can be formed from some of the aforementioned acids. Appropriate precautions, such as using milder conditions and a large excess of amine to maximize amide formation, are recommended in such cases. Typical starting materials for esterification are 3,5-dialkyl-4-hydroxybenzoic acid, 2-(3,5
-dialkyl-4-hydroxyphenyl)acetic acid,
Alternatively, it is 3-(3,5-dialkyl-4-hydroxyphenyl)propionic acid, its acid chloride, or ester. When esteramides in which R ¹ and R ² are the same are desired, esterification and amidation can be carried out in one step. When the starting amine is an alkyl- and hydroxyalkyl-substituted ethanolamine,
A convenient alternative to the above method is available. This involves forming the oxazoline from the acid or its derivative and an amino alcohol according to known methods. This oxazoline can then be hydrolyzed to an amino ester, which can then be amidated according to known methods. The above manufacturing methods are presented as non-limiting examples of ways to carry out the objectives of the invention. Other methods will occur to those skilled in the art. The following non-limiting examples further illustrate the preparation and use of the compounds of the invention. Intermediate Preparation Example 1 3-(3,5-Dietashiabutyl-4-hydroxyphenyl)-N-(2-hydroxyethyl)propionamide Stark thermometer with thermometer, stirrer, and condenser
556 g (2.0 mol) of 3-
(3,5-ditertyabutyl-4-hydroxyphenyl)propionic acid, 135 g (2.2 moles) of ethanolamine and 500 ml of xylene were charged.
The mixture was refluxed for 11 hours and 79 ml of azeotrope was collected.
The xylene was removed under reduced pressure and the residue was dissolved in hot toluene. The title compound (211
g) melted at 129-130°C. Example 1 2-[3-(3,5-ditersiabutyl-4
-Hydroxyphenyl)propionamide]ethyl laurate 44 g (.22 mol) of lauric acid, 64 g (0.2 mol) of 3(3,5-dithyabutyl-4-hydroxyphenyl)-N-2(hydroxy ethyl) propionamide, 2g Tizer TBT
(trade name, tetrabutyl titanate) catalyst, and
The 100 ml xylene mixture was refluxed for 5 hours.
Water (3.8 ml) was collected in a Stark and Dean trap. The xylene was removed by vacuum stripping. The residue was taken up in acetonitrile. After cooling the solution in the freezer, a white precipitate formed. Acetonitrile was removed by decantation and recrystallization was repeated. Final traces of acetonitrile were removed by heating the product under vacuum and the title product (66 g) thus obtained was an amber oil at room temperature. Example 2 2-[3-(3,5-ditersiabutyl-4
-Hydroxyphenyl)propionamide]-
Ethyl stearate 32.1g (0.1 mol) of 3(3,5-ditertyabutyl-4-hydroxyphenyl)-N-(2
-Hydroxyethyl) propionamide, 28.5
g (0.1 mol) stearic acid, 1 g Tyser
A mixture of TBT catalyst and 50 ml of xylene was refluxed at 140-170° C. until water evolution ceased. The Stark and Deantrap collected 3.5 ml of water. The xylene was removed by vacuum stripping and the residue was crystallized from acetonitrile.
The title compound (53g) melted at 55-57°C. Intermediate production example 2 N-(2-hydroxyethyl)rauramide 24 g of ethanolamine (0.4 g in 100 ml of toluene)
40 g (0.2 mol) of lauric acid into a solution of
Added at 50°C. The mixture was refluxed for 6 hours. Gradually remove toluene to bring the final temperature inside the vessel to 140.
It was raised to ℃. The distillate was collected in a Stark and Dean trap. The toluene was removed by vacuum stripping and the residue was crystallized from n-hexane. The title compound (44 g) thus obtained melted at 80-84°C. Example 3 2-(rauramido)ethyl 3-(3,5-ditertyabutyl-4-hydroxyphenyl)
Propionate 13.9 g (0.55 mol) N-(2-hydroxyethyl)rauramide, 139 g (0.05 mol) 3
(3,5-ditertyabutyl-4-hydroxyphenyl)propionic acid, 0.5g Tizer-TBT
The mixture of catalyst and 100 ml of xylene was refluxed until water evolution ceased (3 hours). The residue was taken up in acetonitrile. White crystals separated upon cooling to about -10°C. Decant the acetonitrile,
Recrystallization was repeated. The last traces of acetonitrile were removed under vacuum and the title product thus obtained was a yellow oil at room temperature. Intermediate Preparation Example 3 N-(2-hydroxyethyl)stearamide 24.4 g (0.4 mol) in 500 ml ethanol at 60°C
85.2 g (0.3 mol) of stearic acid was added to a solution of ethanolamine. The internal temperature is 100
The ethanol was distilled off until this temperature was reached, at which time 300 ml of toluene was added and 6 ml of water was collected in the Stark and Dean trap. Remove some toluene and reduce the temperature inside the vessel.
The temperature was raised to 135℃. After another 4 hours, another 7
ml of water was collected. The title product (38.5 g) crystallized on cold and had a melting point of 96-99°C. Example 4 2-stearamidoethyl-3-(3,5-ditertyabutyl-4-hydroxyphenyl)
Propionate 30.6 g (0.11 mol) of 3-(3,5-dithyabutyl-4-hydroxyphenyl)propionic acid, 32.6 g (0.1 mol) of N-(2-hydroxyethyl) stearamide, 0.8 g Tizer of
TBT and 100 ml of xylene were refluxed for 6 hours. Water (1.8 ml) was collected in a Stark and Dean trap. The solution was passed through Microcell (trade name, synthetic calcium silicate) and the solvent was removed by vacuum stripping.
The title compound (51 g) was recrystallized from acetonitrile. It melted at 52-55°C. Example 5 2-[3-(3,5-ditersiabutyl-4
-Hydroxyphenyl)propion-amide]ethyl 3-(3,5-dithyabutyl-4-hydroxy-phenyl)propionate 32 g (0.1 mol) of 3-(3,5-dithyabutyl-4-hydroxy) phenyl)-N-(2
-Hydroxyethyl) propionamide, 27g
(0.1 mol) of 3(3,5-ditertyabutyl)
A mixture of 4-hydroxyphenyl)propionic acid, 1 g of Tizer TBT catalyst and 100 ml of xylene was refluxed at 150° C. until water evolution ceased. During the course of 4 hours, 2 ml of water was collected in the Stark and Dean trap. Xylene was removed by vacuum stripping. Title compound (54
g) was recrystallized from a toluene/hexane mixture. Its melting point was 151-154°C. Intermediate production example 4 2-[2-(3,5-ditertyabutyl-4
-Hydroxyphenyl)ethyl]-4,4-dimethyl-2-oxazoline 167 g (0.6 mol) of 3-(3,5-ditertyabutyl-4-hydroxyphenyl)propionic acid, 65 g (1.06 mol) of A mixture of 2-amino-methylpropanol and 100 ml of xylene was refluxed for 6 hours. Water was collected in a Stark and Dean trap. The mixture was poured into 300 ml of hexane and the crystalline product was separated off on cooling. The title product (101 g) thus obtained melted at 138-141°C. Intermediate production example 5 2-amino-2-methylpropyl [3-(3,
5-Ditertyabutyl-4-hydroxyphenyl)propionate] 66.2 g (0.2 mol) of 2
-[2-(3,5-ditertyabutyl-4-hydroxyphenyl)ethyl]-4,4'-dimethyl-2-oxazoline, 400 ml of isopropanol, and 33 ml of 6N hydrochloric acid were added. Mixture at 45℃
Heated for 2 hours and then cooled. to this stirred solution
250ml water and 33ml 6N sodium hydroxide were added. The product was filtered off and dried.
The title compound (52 g) thus obtained was heated to 97-99°C.
It melted. Intermediate production example 6 3-(3,5-dithyabutyl-4-hydroxyphenyl)-N-(1,1-dimethyl-
2-Hydroxyethyl)propionamide 34.9 g (0.1 mol) of 2
-amino-2-methylpropyl-[3-(3,5
- diterciabutyl-4-hydroxyphenyl) propionate] and 200 ml of isopropanol. The mixture was refluxed for 15 hours. The solvent was driven off and the residue was dissolved in hot hexane. The title compound (20 g) was filtered off and dried. It melted at 120-122°C. Example 6 2-[3-(3,5-ditersiabutyl-4
-Hydroxyphenyl)propionamide]-
2-Methylpropyl laurate 55 g (0.25 g) of lauroyl chloride in 50 ml of toluene
mol) solution dropwise with 60 ml of dimethylaniline.
70 g (0.2 mol) of 3- in 50 ml of toluene
It was added to a solution of (3,5-ditertyabutyl-4-hydroxyphenyl)-N-(1,1-dimethyl-2-hydroxyethyl)propionamide. The mixture was heated at 50°C for 41/2 hours. The mixture was washed with dilute hydrochloric acid and then with brine. Toluene was removed by vacuum stripping. The residue was taken up in acetonitrile. The solution was shaken with decolorizing charcoal, filtered, and then placed in a freezer. The title compound (20 g) crystallized and was removed by filtration. It melted at 24-27°C. Example 7 2-[3-(3,5-ditersiabutyl-4
-Hydroxyphenyl)propionamide]
-2-Methylpropyl palmitate 13 g (0.037 mol) of 3-necked round-bottomed flask equipped with a thermometer, stirrer, and addition funnel.
-(3,5-ditertyabutyl-4-hydroxyphenyl)-N-(1,1-dimethyl-2-hydroxyethyl)propionamide, 10 g of triethylamine and 250 ml of benzene were charged.
10.2 g (0.037 mol) of palmitoyl chloride was added to the stirred mixture and the mixture was stirred for 3 hours.
The mixture was per-distilled and the residue was dissolved in hot acetonitrile. Some palmitic anhydride crystallized and was separated. This acetonitrile solution was frozen overnight, and the title compound (20 g) crystallized.
This was filtered off and then dried. It melted at 41-43°C. Example 8 2-palmitamide-2-methylpropyl-3
-(3,5-Ditertyabutyl-4-hydroxyphenyl)-propionate 17.5 g (0.05 mol) of 2. -Amino-2-methylpropyl 3-(3,5-
diterciabutyl-4-hydroxyphenyl)
Propionate, 500ml benzene and 10g triethylamine were charged. 14g to this stirred mixture
(0.05 mol) of palmitoyl chloride was added and the mixture was stirred for 4 hours. The mixture is filter distilled and
The residue was dissolved in hot acetonitrile. Approximately 5℃
The product crystallized after about 4 days of storage at .
This was filtered out and dried. The title compound thus obtained melted at 43-46°C. Example 9 2-[3-(3,5-ditersiabutyl-4
-Hydroxyphenyl)propionamide]-
2-Methylpropyl stearate 26.2 g (0.075 mol) in 1 three-necked round-bottomed flask equipped with a thermometer, stirrer, and addition funnel.
3(3,5-ditertyabutyl-4-hydroxyphenyl)-N-(1,1-dimethyl-2-
Hydroxyethyl)-propionamide, 20g
of triethylamine and 400ml of benzene were added. 22.5 g (0.075 mol) of stearoyl chloride was added to the stirred mixture and the reaction was stirred for 18 hours. Remove triethylamine hydrochloride by filtration,
The solvent was distilled off. The residue was dissolved in hot hexane and 2.5 g of stearic anhydride was isolated. The hexane was distilled off and the residue was dissolved in hot acetonitrile. Upon cooling, the title compound crystallized. This was filtered out and dried. This is 59-61
Melted at °C. Example 10 2-stearamide-2-methylpropyl 3-
(3,5-Ditertyabutyl-4-hydroxyphenyl)propionate 500 ml with thermometer, stirrer, and addition funnel
26 g (0.075 mol) of 2-amino-2-methylpropyl 3-
(3,5-Butyl-4-hydroxyphenyl)propionate, 200 ml of benzene and 8.2 g of triethylamine were charged. 22.5g to this stirred mixture
(0.075 mol) of stearoyl chloride was added and the mixture was stirred for 4 hours. The triethylamine hydrochloride was removed by filtration and the solvent was driven off. The residue was dissolved in hot hexane. After crystallization, filtration and drying, the title compound melted at 46-48°C. Example 11 2-(3,5-ditertyabutyl-4-hydroxybenzamide)-2-methylpropyl 3
-(3,5-Ditertyabutyl-4-hydroxyphenyl)-propionate Into a three-necked round-bottomed flask equipped with a thermometer, stirrer, and addition funnel, 34.9 g (0.1 mole) of 2 -Amino-2-methylpropyl 3-(3,5-
diterciabutyl-4-hydroxyphenyl)
propionate, 20 g triethylamine and
Added 400ml of benzene. to this stirred mixture
26.8 g (0.094 mol) of (3,5-dithyabutyl-4-hydroxyphenyl)propionate, 20 g of triethylamine and 400 ml of benzene were charged. 26.8 g (0.094 mol) of 3,5-dithyabutyl-4-hydroxybenzoyl chloride was added to the stirred mixture and the mixture was stirred overnight. This mixture is filtered and distilled,
The residue was slurried with hexane. The product was separated and recrystallized from isopropanol.
The title compound (30.5g) thus obtained was 192
Melted at ~194°C. Example 12 2-[3-(3,5-ditersiabutyl-4
-Hydroxyphenyl)propionamide]
Isobutanetriyltris [3-(3,5-ditertyabutyl-4-hydroxyphenyl)]
-Propionate] 3 of 85 g (0.27 mol) in 120 ml of toluene
60ml of a solution of (3,5-ditertyabutyl-4-hydroxyphenyl)propionyl chloride
of pyridine and 7.3 g (0.06
mol) of tris(hydroxymethyl)aminomethane. The mixture was stirred at 60°C for 42 hours.
The mixture was washed with dilute acid and then brine. Toluene was removed by vacuum distillation and the residue was crystallized in n-hexane. The title compound thus obtained melted at 118-122°C. Elemental analysis: Calculated value Actual value C 74.37 74.19 H 9.28 9.47 N 1.21 1.11 Intermediate production example 7 2-[2-(3,5-ditertyabutyl-4
-Hydroxyphenyl)ethyl]-2-oxazoline-4,4-diethylbis[3-(3,5
167 g (0.6 mol) of 3-(3,5-ditertyabutyl-4-hydroxyphenyl)propionate, 24.2 g (0.2 mol) of tris(hydroxyphenyl)propionate A mixture of methyl)aminomethane and 100 ml of xylene was refluxed for 6 hours. Stark and water
Collected in a dean trap. heat the mixture
Hot poured into 300ml hexane. The title product precipitated. This is recrystallized from benzene and 173
The title compound (165.5 g) is obtained with a melting point of ~175°C. Elemental analysis: Calculated value Actual value C 74.70 74.53 H 9.23 9.09 N 1.58 1.34 Example 13 2-Stearamide isobutanetriyltris [3-(3,5-ditertyabutyl-4-hydroxyphenyl)propionate] 200ml of 44.2 g (0.05 mol) of 2-[3-(3,5-ditertyabutyl-4-) in triene.
8.2 ml of 6N hydrochloric acid was added to hydroxyphenyl)ethyl]-2-oxazoline-4,4-dimethylbis[3-(3,5-ditertyabutyl-4-hydroxyphenyl)-propionate]. The mixture was stirred for 4 hours and 8g of sodium bicarbonate was then added. Separate the aqueous layer and add 40ml of triethylamine to the organic layer, then 15.1g in 30ml
(0.05 mol) of stearoyl chloride was added. The mixture was stirred at room temperature overnight and then at 50° C. for 1 hour. Once cooled, the mixture was washed first with dilute hydrochloric acid and then with brine. Toluene was removed by vacuum distillation. The residue was passed through a silica column using a 50/50 (volume) mixture of toluene/hexane as the developer. The title compound (28 g) obtained after evaporation of the developing agent was heated to 77-79°C.
It melted. Intermediate Preparation Example 8 To a solution of 134 g (0.22 mol) of N,N'-bis(hydroxyethyl)oxamide 1 in ethanol was added 146 g (0.1 mol) of diethyl oxalate over the course of 1 hour. Mixture at 50℃
It was heated for 1 hour. The title compound (162g) precipitated on cooling. After over-drying, this is 166-168℃
It melted. Example 14 2,2′-oxalyldiamide bis[ethyl 3-
(3,5-ditertyabutyl-4-hydroxyphenyl)propionate] 55.6 g (0.2 mol) of 3-(3,5-ditertyabutyl-4-hydroxyphenyl)propionic acid, 17.6 g (0.1 mole) of N,N′-bis(2-
A mixture of hydroxyethyl)oxamide, 1.5 g of Tizer TBT, and 200 ml of toluene was brought to reflux. Water and xylene were removed until the temperature inside the vessel reached 200°C. Upon cooling, the title compound (54g)
crystallized. After recrystallization from toluene, this
It melted at 128-131°C. Example 15 2,2′-oxalyldiamide bis[2-methylpropyl 3-(3,5-ditertyabutyl-
4-Hydroxyphenyl)propionate] 500 ml with thermometer, stirrer, and addition funnel
35 g (0.1 mol) in a three-necked round bottom flask.
2-amino-2-methylpropyl 3-(3,5
- diterciabutyl-4-hydroxyphenyl)-propionate, 250 ml benzene and 20
g of triethylamine was added. To this stirred mixture was added 6.35 g (0.05 mole) of oxalyl chloride and the mixture was stirred for 2 hours. Strain the mixture;
The solvent was expelled. The residue was dissolved in a 2:1 mixture of benzene/hexane and allowed to cool. The crystalline product (22 g) was recrystallized from a 2:1 mixture of benzene/hexane and had a melting point of 169-171°C. Example 16 2,2'-Adipamidobis-[2-methylpropyl 3-(3,5-ditertyabutyl-4-hydroxyphenyl)propionate] 1 tripartite equipped with thermometer, stirrer, and addition funnel In a round-bottomed flask, 29 g (0.083 mol) of 2
-amino-2-methyl-propyl [3-(3,5
20 g of triethanolamine and 400 ml of benzene were added. To this stirred mixture was added 7.6 g (0.0415 moles) of adipoyl chloride and the mixture was stirred for 4 hours. The mixture was filter distilled and the residue was dissolved in hot hexane. The product crystallized and then was added with 400 ml of isooctane.
Recrystallized from a mixture of 125 ml of toluene. This purified product (21 g) melted at 135-138°C. Example 17 2,2′-Sebasamide bis-[2-methylpropyl 3-(3,5-ditertyabutyl-4-hydroxyphenyl)propionate] 1 tripartite equipped with thermometer, stirrer and addition funnel In a round-bottomed flask, 34.9 g (0.1 mol) of 2-amino-2-methylpropyl 3-(3,5-
diterciabutyl-4-hydroxyphenyl)
propionate, 20 g triethylamine and
Added 400ml of benzene. to this stirred mixture
11.9 g (0.05 mol) of sebasoyl chloride was added;
The mixture was stirred for 5 hours. The mixture was filter distilled and the residue was dissolved in hot hexane. The solid was separated and recrystallized from hexane/benzene (3:1). The title compound (32g) thus obtained was
It melted at 113-117°C. Example 18 2,2′-Sebasamide bis[isobutanetriyltris[3-(3,5-dithyabutyl-
4-Hydroxyphenyl)propionate] 44.2 g (0.05 mol) of 2- in 200 ml of toluene
[2-(3,5-ditertyabutyl-4-hydroxyphenyl)ethyl]-2-oxazoline-
8.2 ml of 6N hydrochloric acid was added to 4,4-dimethylbis[3-(3,5-dithyabutyl-4-hydroxyphenyl)propionate. 3 of the mixture
Stir for an hour and then add 6 g of sodium bicarbonate. The mixture was stirred for 15 minutes and the layers were separated.
Add 40 ml of triethylamine to the organic layer followed by
6 g of sebasoyl chloride in 30 ml of toluene was added. The mixture was stirred at room temperature overnight and then at 50 °C for 1
Stir for hours. After cooling, the mixture was washed first with dilute hydrochloric acid and then with brine. Toluene was removed by vacuum stripping. The residue is taken up in 1:1 toluene/hexane and passed through a fluosil column. Isolated after solvent removal, the title compound (11 g) melted at 134-141°C. Intermediate Production Example 9 N,N'-bis[1,1-bis(hydroxymethyl)-2-hydroxyethyl]-terephthalamide In a three-necked round-bottomed flask equipped with a thermometer, stirrer, and condenser. 194 g (1.0 mol) of dimethyl terephthalate, 242 g (2.0 mol) of tris(hydroxymethyl)aminomethane, and 1 part of methanol were placed therein. The mixture was refluxed for 8 hours,
Next, it was left to cool. The title compound crystallized and was dried separately. The melting point was 188-190°C. Example 19 2,2′-Terephthalamide bis[isobutanetriyltris[3-(3,5-ditertyabutyl-4-hydroxyphenyl)propionate]] Thermometer, stirrer, addition funnel and condenser 18.6 g (0.05 g
mol) of N,N'-bis[1,1-bis(hydroxymethyl)-2-hydroxyethyl]terephthalamide and 200 ml of pyridine were added. Add 90 g (0.3 mol) of 3-(3,5-) to this stirred slurry.
diterciabutyl-4-hydroxyphenyl)
Propionyl chloride was added at 20-30°C and the mixture was stirred for 18 hours. The mixture was filtered and distilled and the residue was dissolved in hot cyclohexane. Traces of pyridine hydrochloride were removed and the solution was allowed to cool. The title compound (61g) crystallized on cooling. After recrystallization from methanol, its melting point was 169-172°C. Example 20 3,3'-thiobis[2-propionamidoethyl-3-(3,5-ditertial-4-hydroxyphenyl)propionate] 26.8 g (0.44 mol) of ethanolamine and 41.2 g of ethanolamine in 100 ml of ethanol (0.2 mol) of dimethyl 3,3'-thiodipropionate was refluxed for 5 hours. 3,3'-Thiobis-[N-(2-hydroxyethyl)propionamide] precipitates as a white crystalline solid and upon washing with acetone, 130
Melted at ~132°C. 18g (0.068 mol) of the above intermediate, 41.7g
A mixture of (0.15 mol) of 3-(3,5-ditertyabutyl-4-hydroxyphenyl)propionic acid and 1 g of Tizer TBT catalyst in 100 ml of xylene was refluxed until no water evolution occurred. . 3.5 ml of water was collected in a Stark and Dean trap. After evaporation of xylene, the product (51 g) was obtained as a viscous yellow oil. Example 21 3,3'-Thiobis[2-methyl-2-propionamidopropyl-3-(3,5-ditertyabutyl-4-hydroxyphenyl)propionate] 40 g (0.44 mol) of 2-amino- 2-methylpropanol, 3 g potassium tertiarybutoxide, and 41.2 g (0.2 mole) dimethyl 3,
3′-thiodipropionate mixture at room temperature.
Stir for 1 hour and then heat to 90° C. in vacuo for 1/2 hour. Excess 2-amino-2-methyl-propanol was removed by vacuum stripping. The obtained 3,3′-thiobis-N-(1,1-dimethyl-2
-Hydroxyethyl)Half (0.1 mol) of propionamide is mixed with 61.2g (0.2 mol) of ethyl-3-
(3,5-ditertyabutyl-4-hydroxyphenyl)propionate and 2 g of potassium.
Vacuum for 2 hours with tarsia butoxide
Heated at 100-110°C. The mixture was taken up in toluene, neutralized with acetic acid and washed with water. Removal of the toluene by vacuum distillation gave the title compound (79g) as a viscous yellow oil. Intermediate production example 10 N,N'-bis[2-hydroxyethyl]terephthalamide 194 g (1.0 mol) of dimethyl terephthalate,
150 ml (2.46 moles) of ethanolamine and 300 ml
of ethanol was refluxed for 7 hours. Upon cooling, the title product separated. After this,
Washed with ethanol. After drying, it is 227-229
Melted at °C. Example 22 2,2'-terephthalamide-N,N'-bis[ethyl-[3-(3,5-ditertyabutyl-
4-Hydroxyphenyl)propionate] 59.3 in 300 ml toluene to a mixture of 25.2 g (0.1 mol) N,N'-bis(2-hydroxyethyl)-terephthalamide and 200 ml pyridine.
g (0.2 mol) of 3-(3,5-dithyabutyl-4-hydroxyphenyl)propionyl chloride was added. The mixture was stirred for 2 hours.
This was then heated to 90°C. The solvent was removed by distillation and the residue was crystallized from n-hexane. The title product thus obtained (68g)
and then washed with hot water. After drying, it melted at 173-175°C. Example 23 3-oxalylamide-bis-[propyl-3
-(3,5-ditertyabutyl-4-hydroxyphenyl)propionate] 500 g of diethyl oxalate (73 g; 0.5 mol)
It was added over half an hour to a solution of 82.5 g (1.1 mol) of 3-amino-1-propanol in ml of ethanol. The temperature rose to 50°C. 1 of the mixture
The mixture was stirred for an hour and the resulting precipitate (melting point 156-158°C) was separated by filtration. A portion (20.4 g) of N,N'-(3-hydroxypropyl)oxamide thus obtained was added to 61.2 g (0.22 mol) of 3
-(3,5-ditertyabutyl-4-hydroxyphenyl)propionic acid, 100 ml of xylene, and g of Tizer TBT catalyst were added to the mixture.
The mixture was refluxed for 4 hours and then passed through a microcell. Xylene was removed by vacuum distillation. The residue was taken up in hot hexane. Upon cooling, the title compound crystallized and melted at 120-123°C. Elemental analysis: Calculated value Actual value C 69.61 69.96 H 8.84 8.84 N 3.87 4.02 Example 24 3-stearamidopropyl 3 (3,5-di-
tertiarybutyl-4-hydroxyphenyl)
Propionate 30 g (0.4 mol) 3-aminopropanol,
Stearic acid (56.8
g; 0.2 mol) was added. The mixture was heated under reflux for 2 hours to remove water, then poured into hexane,
In it, N-(3-hydroxypropyl) stearamide was crystallized and obtained by filtration. The melting point was 83-89°C. After recrystallizing the product from acetone, the melting point rose to 94-96°C. 34.1g (1 mol) of this intermediate was converted into 27.8g (0.1 mol)
mole) of 3-(3,5-ditertyabutyl-4
-hydroxyphenyl)propionic acid, 1 g of Tizer TBT catalyst and 100 ml of xylene. After the mixture was refluxed for 3 hours, 2 ml of water was collected in a Stark and Dean trap. The xylene was distilled off under vacuum and the residue was crystallized from acetone. The title product (29 g) thus obtained melted at 50-52°C. Intermediate Preparation Example 11 N-(2,2-dimethyl-3-hydroxypropyl)stearamide In a 500 ml three-necked round bottom flask equipped with a Stark and Dean trap with thermometer, stirrer and condenser. 119.4 g of methyl stearate, 41 g of 3-amino-2,2-dimethylpropanol, and 3 g of potassium tertiarybutoxide were added to the solution. The mixture was heated to 190°C and methanol was distilled off. The reaction mixture was dissolved in hot isopropanol and filtered. On cooling, the product crystallized and after overdrying its melting point was 44°C. IR showed ester carbonyl. Pure product was obtained by washing with hot hexane. The pure product melted at 68-69°C. Example 25 2,2-dimethyl-3-stearamidopropyl-3-(3,5-ditertyabutyl-4-
Hydroxyphenyl)propionate 36.9 g of N- into a three-necked round-bottomed flask equipped with a thermometer, stirrer, addition funnel, and condenser.
(2,2-dimethyl-3-hydroxypropyl)
- stearamide, 25 ml triethylamine,
and 250ml of toluene. To this stirred mixture was added 29.6 g of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride. The mixture was filtered, distilled and the residue was dissolved in hot methanol. 2,2-dimethyl-3-stearamidopropyl stearate is isolated which melts at 60-62°C. The methanol solution was distilled and the residue was dissolved in acetonitrile. The title compound was isolated, which melted at 44°C. Intermediate production example 12 N,N'-bis[2,2-dimethyl-3-hydroxypropyl]oxamide In a 0.1 volume round bottom flask, 12.0 g of 3-amino-2,2-dimethylpropanol and 20 ml of ethanol. I put it in. 8.5 g of diethyl oxalate was added to this stirred solution and the mixture was stirred.
Fever was observed. Upon cooling, the title compound separated. This was removed by filtration and recrystallized from ethanol. The title product melted at 125-126°C. Example 26 3-Oxalyldiamide bis[2,2-dimethylpropyl 3-(3,5-ditertyabutyl-4-hydroxyphenyl)propionate] Equipped with thermometer, stirrer, addition funnel and condenser In a three-necked round bottom flask, 13g of N,
N'-bis-(2,2-dimethyl-3-hydroxypropyl)oxamide, 25 ml of triethylamine, and 250 ml of toluene were charged. To this stirred solution was added 29.6 g of 3-(3,5-ditertyabutyl-4-hydroxyphenyl)-propionyl chloride. Stir the mixture for 4 hours,
Distilled. The residue was heated with hot hexane.
The title compound separated immediately. It was filtered out and its melting point was 143-144°C. Example 27 2-Stearamidoethyl 3,4-ditertyabutyl-4-hydroxybenzoate 25 g (0.1 mol) of 3,5-ditertyabutyl-4-hydroxy-benzoic acid, 50 ml of toluene and 8.5 ml of thionyl chloride was refluxed for 3 hours. Excess thionyl chloride and toluene were removed on a rotary dryer. This acid chloride
It was dissolved in 50 ml toluene and added to a mixture of 29.4 g (0.09 mol) N-(2-hydroxyethyl)-stearamide, 20 ml toluene and 15 ml pyridine. The mixture was refluxed for 2 hours.
The reaction mixture was then cooled, quenched with water, and washed with dilute hydrochloric acid and water. The toluene was removed by distillation and the residue was crystallized from hexane. The title compound thus obtained melted at 56-58°C. Example 28 This example demonstrates the utility of compounds of the invention in polypropylene. This also demonstrates the beneficial effects observed by using the compounds of the invention together with co-stabilizers. The particular compound used in each experiment in this and subsequent examples is identified by the number of one of the examples above in which the compound is made. Stabilizer: Profax 6501 on mill at 165°C
(trademark) polypropylene. 75 mil platelet (approximately 1 inch in diameter and 75 mil thick (1.9
mm) by compression molding in a press at 27000 psi (186 MPa) and 177°C. These specimens were placed in a forced air bath at 149°C and the number of days required for embrittlement to occur was recorded. The coupon was considered to have failed when two of the three button coupons became brittle (ie, they became granular due to thermal aging). The results are shown in Table 1.

【table】

[Table] Example 29 This example uses EPDM (ethylene/propylene weight ratio 67/33, iodine number 10, Mooney viscosity (120°C
ML-4) is 57. Figure 2 illustrates the utility of the compounds of the present invention in ethylene/propylene/5-ethylidene-2-norbornene terpolymers. Stabilizer (0.165g) in 2000g hexane 110
g of EPDM was dissolved in rubber cement.
The hexane was removed by slowly adding the cement to boiling water. Remove solids from the boiling water by filtration and boil for 5 minutes on a mill at 275-300°C.
〓(135-149℃). The time required for 1 g of sample to absorb 20 cm of oxygen at 150° C. was then determined (T ₂₀ ). The results are shown in Table 2, and due to the presence of the compounds of the invention
It was shown that EPDM had an excellent protective effect. Table 2 Additives T ₂₀ (min) None 30 Example 9 560 Example 10 260 Example 15 405 Example 30 This example uses a terpolymer of polypropylene (20 parts by weight) and ethylene-propylene-dicyclopentadiene (80 parts by weight). (parts by weight) in dynamically cured elastomer blends. The compound was incorporated into the blend at a concentration of 0.3 parts by weight per 100 parts by weight of the blend. 75 mil (1.9
mm) platelets were compression molded and button-shaped coupons were punched out of these platelets. The buttons were placed in a forced air bath at 149°C and the time to brittleness of 3 out of 5 buttons was recorded. The results are shown in Table 3. Table 3 Additive Embrittlement Time None 80 Example 15 275 Example 31 This example demonstrates the utility of the compounds of this invention in high impact polystyrene. Antioxidant (per 100 parts by weight of polystyrene)
(0.25 parts by weight) was kneaded into high-impact polystyrene at 138°C. Izotsu rod with a notch
It was molded at 170℃. After measuring the impact strength,
The Izotsu rod was crushed and remolded. This process was repeated 5 times. Table 4 shows the impact strength retention rate after 5 moldings. Table 4 Antioxidant impact strength retention rate (%) None 58.3 Example 19 76.2 Example 10 66.3 Example 15 85.2 Example 32 This experiment was conducted under USSR Patent No. 567719 (Grushyukova)
The compound of Example 32 unexpectedly showed superior efficacy in polypropylene than di-2-[3-(3,5-ditertyabutyl-4-hydroxyphenyl)propionamide] made by This is to show that there is something to be done. Test specimens were prepared and tested essentially according to the process of Example 35, and the results are shown in Table 5.

【table】

Claims (1)

[Claims] 1 Formula R ¹ COOANHM [In the formula, A is C ₂ to C ₄ alkylene, or A is one or two -
CH ₂ OCO(CH ₂ ) _n C ₂ alkylene substituted with R ³ groups, where R ³ is 3,5-ditertyabutyl-4-hydroxyphenyl and m is 2 ); R ¹ is -(CH ₂ ) _n R ³ (where m and R ³ are as defined above); M is -
COR ² (wherein R ² is C ₁₀ -C ₂₀ alkyl, or R ² is -BCONHAOCOR ¹ (wherein A
and R ¹ are as defined above, B is a single bond, C ₁ to C ₁₀ alkylene, phenylene or C ₄
is a thiodialkylene) or
R ² is the same as R ¹ defined above. 2 One or two A-CH ₂ O-CO
(CH ₂ ) _n C ₂ alkylene substituted with a R ³ group, with the proviso that B is a single bond only when m and R ³ are as defined in claim 1; , B are as defined in claim 1. 3 Formula R ¹ COOANHM [In the formula, A is C ₂ to C ₄ alkylene, or A is one or two -
CH ₂ OCO(CH ₂ ) _n C ₂ alkylene substituted with a R ³ group (wherein R ³ is 3,5-dithyabutyl-4-hydroxyphenyl and m is 2) R ¹ is -(CH ₂ ) _n R ³ (where m and R ³ are as defined above); M is -
COR ² (wherein R ² is C ₁₀ -C ₂₀ alkyl, or R ² is -BCONHAOCOR ¹ (wherein A
and R ¹ are as defined above, B is a single bond, C ₁ to C ₁₀ alkylene, phenylene or C ₄
is a thiodialkylene) or
R ² is the same as R ¹ defined above.