DE2445345A1 - ESTERS AND AMIDES OF TRISUBSTITUTED HYDROXYPHENYLALCANIC CARBONIC ACIDS - Google Patents

Description

CSBA-GBGY

CLBA-GEIGY AG, CH-4002 Basel

DR. ERLEND DINN * PATENT ADVERTISER 28 BREMEN

UHLANDSTRASSE

Case 3-9006 / GC 639 / + Germany

Esters and amides of trisubstituted hydroxyphenylalkane -

carboxylic acids

The invention relates to esters and amides of the hindered
Hydroxyphenylalkanecarboxylic acids as well as organic material that normally undergoes oxidative, thermal and UV degradation
is subject and is stabilized with these esters or amides, in particular compounds of the formula

509813/1165

(A) -C-O

F-I

(A) -C-N

F-2

1 2
wherein R, R and R independently of one another are alkyl with 1-8 carbon atoms or cycloalkyl with 5-6 carbon atoms, with no more than 2 cycloalkyl groups being present, or

1 2

R and R together are butylene, which together with the phenyl ring forms a tetrahydronaphthyl group, and when η is 1, R is hydrogen, alkyl with 1-30 carbon atoms, cycloalkyl with 5-6 carbon atoms, phenyl, alkyl -substituted phenyl, where alkyl has 1-8 carbon atoms, or alkylthioethyI with 5-27 atoms in the chain, or, when η is 2, R ^{3 is} alkylene with 2-12 carbon atoms, cycloalkylene with 5-8 carbon atoms Atoms, alkylene with 7-10 carbon atoms and one cycloalkane group in the chain, thiobisalkylene with 5-9 atoms in the chain, alkyleneoxyalkylene with 5-9 atoms in the

5098 13/1165.

Chain, or polyoxyalkylene with 8-101 carbon atoms, or, when η is 3-6, a 3-6 valent cyclic or

acyclic hydrocarbon radical with 3-10 carbon atoms

3, where in formula F-I each carbon atom of the radical R is with

connected to only one heteroatom, R is hydrogen,

Alkyl with 1-8 carbon atoms or cycloalkyl with 5-6 carbon atoms

4 5
or R and R together form a piperazinyl ring

and include both N atoms, where m is 2, or the remainder

R 0 ^

■ - CH ₀ CH ₉ NHC- (A) - (O) - ^0H '

and when η is 1, R is hydrogen, alkyl of 1-24

C atoms, phenyl, alkylphenyl with 1-18 C atoms in the alkyl

3 is radical, or, when m is 2, R is alkylene with 2-18

Carbon atoms or polyoxyalkylene with 8-11 carbon atoms,

3
or, when m is 3 or 4, R is a 3- or 4-valent cyclic or acyclic hydrocarbon radical with 3-8 carbon atoms, where in formula F-2 each carbon atom of the radical R has only one carbon atom each is connected, A is branched or straight-chain alkylene with 1-8 carbon atoms, m is an integer from 1-4, and η is an integer from 1-6.

1 2 "■ ~ -

The radicals R, R and R can be straight-chain or branched Be alkyl with 1-8 carbon atoms, e.g. methyl, ethyl, propyl, butyl, pentyl, heptyl or octyl. R, R and R can be used as cycloalkyl with 5-6 carbon atoms, e.g. Be cyclopentyl or cyclohexyl.

Preferably, R is branched alkyl of 3-8, preferred

509813/116 5.

4-8 carbon atoms, such as isopropyl, sec-butyl, tert-butyl, see- and tert-aryl, see- and tert-hexyl, see- and tert-heptyl or sea- and tert-octyl, but especially tert-butyl.

1 2
R and R are preferably alkyl with 1-3 carbon atoms, such as methyl, ethyl and propyl, especially methyl.

3
R can be alkyl with 1-30 carbon atoms, such as methyl, η-butyl, n-octyl, n-dodecyl, n-octadecyl, n-tetracosanyl or n-triacontanyl, preferably alkyl with 1-18 carbon atoms, such as n-dodecyl or n-octadecyl.

R can also be cycloalkyl with 5-6 carbon atoms, preferably cyclohexyl.

R can also be phenyl or alkylphenyl, the alkyl groups having 1-18 carbon atoms. The substituents can be methyl, isopropyl, tert-butyl and tert-octyl. Substitution in the ortho or para position of the phenyl ring is particularly preferred. Preferably

3
R is alkylphenyl with alkyl groups of 1-12 carbon atoms, especially with 1-8 carbon atoms, such as two tert-butyl groups.

R can also be alkylthioethy1 with 5-27 carbon atoms in the chain, generally with the structure -CHLCHLSR ⁰ , where R ° is alkyl with 2-24 carbon atoms, such as n-octyl, n-dodecyl, n-octadecyl and n-tetracosanyl are preferred

3
R is alkylthioethyI with 5-21, in particular 21, carbon atoms in the chain, where R ° has 2-18 carbon atoms.

3
If η is 2, R can be alkylene with 2-12 C atoms, such as ethylene, tetramethylene, 2,2-dimethylpropylene,

5 0 9 8 13/1165.

3 hexamethylene, octamethylene or dodecamethylene. R is

in particular alkylene with 2-8 carbon atoms, preferably 2-6 and especially 5 or 6 carbon atoms.

R can be cycloalkylene with 5-8 carbon atoms, such as 1,3-cyclopentanediyl, 1,4-cyclohexanediyl and 2,2,4,4-tetramethyl-1,3-cyclobutanediyl. R is preferably 2,2,4,4-tetramethyl-1 , 3-cyclobutanediyl.

R can also be alkylene with 7-10 carbon atoms, the one Contains cycloalkane group in the chain, such as 1,4-cyclo-

hexanedimethylene and 1,5-cyclooctanedimethylene. Preferred

3
R is 1,4-cyclohexanedimethylene.

R can also be thiobisalkylene with 5-9 atoms in the

Be chain, like thiodiethylene and thiodibutylene.

3 3

Preferably R is thiodiethylene. R can also be alkyleneoxyalkylene with 5-9, preferably 7, carbon atoms in the chain

be like oxydiethylene, oxydibutylene and oxydi- (l, 2-

3
propylene). Preferably, R is oxydiethylene.

R can also be polyoxyalkylene with 8-101 carbon atoms,

of the general structure -R ⁰⁰ COR ⁰⁰ ), -, where R °° is straight-chain or branched alkylene with 2-4 C atoms and h is 2-33. R °° is, for example, ethylene, 1,2-pro

pylene, 1,2-butylene and tetramethylene. Is preferred

3
R polyoxyalkylene with 8-11 carbon atoms, in which R °° ethylene

3 is and h is 2-3. R is particularly preferably polyoxyethylene with 8 carbon atoms, e.g. ethyleneoxyethyleneoxyethylene. . >

3
If η is 3-6, then R is a 3-6 valent cyclic or

acyclic hydrocarbon radical with 3-10 carbon atoms,

509813/116 5.

e.g. derived from an alkane or cycloalkane, such as 1,2,3-propane triyl, neopentane triyl, neopentane tetrayl, 2,2-dimethyl-2,2-butanetriyl, 2,2-dimethyl-1,2,2-pentanetriyl, 1,2,3,4,5,6-Cyclohexanhexayl or 1,2,3,4,5,6-

3
Hexane hexayl. R is especially a 3-6 valent acyclic hydrocarbon radical with 3-7 carbon atoms, preferably with 5-7, especially 5 carbon atoms.

4th
R can be alkyl with 1-8 carbon atoms, such as methyl, ethyl,

4 butyl and octyl. R with 1-4 carbon atoms is preferred,

4th
especially methyl. R can also be cycloalkyl with 5-6

Be carbon atoms, especially cyclohexyl. If m is 2, then the rest can

It

- CH ₂ CH ₂ NHC- (A.

be when diethylenetriamine or triethylenetetramain can be used in the preparation of amides of Formula F-2.

R can be alkyl with 1-24 carbon atoms, such as methyl, octyl, n-dodecyl or n-tetracosanyl, preferably with 1-18 Carbon atoms, such as n-octadecyl.

R is also phenyl or alkylphenyl, where alkyl has 1-18 carbon atoms. Substituents can be methyl, isopropyl, be tert-butyl and tert-octyl, with one substitution is preferably in the ortho or para positions of the phenyl ring.

509813/1165.

If m is 2, then R can be alkylene with 2-18 carbon atoms, such as ethylene, octamethylene and octadecamethylene. Preferred R is alkylene with 2-12, in particular 2-6, carbon atoms, such as ethylene, hexamethylene and dodecamethylene.

R can also be polyoxyalkylene with 8-11 carbon atoms and the general formula -R ^oo (0R ⁰⁰ ) -, where R °° straight-chain or branched alkylene with 2-4 carbon atoms and k. 2-3 is. R is preferably polyoxyalkylene with 8 carbon atoms, where R °° is ethylene and k is 2.

If m is 3-4, then R is a 3- or 4-valent cyclic or acyclic hydrocarbon radical with 3-8 carbon atoms, such as neopentane tetrayl, neopentane triyl, 1,2,3-propane triyl and cyclohexane-l ^ -diyl-l ^ -dimethylene.

A is straight or branched alkylene of 1-8 C atoms, such as methylene, ethylene, 1,2-propylene, trimethylene, 1,1-butylidene, 2-methyl-l, 1-propylidene and 1,1-octylidene. A is preferably straight-chain alkylene with 1-3 carbon atoms, i.e. methylene, ethylene and trimethylene, and in particular A is alkylene with 1 or 2 carbon atoms, e.g. methylene or ethylene.

The integer m is 1-4, preferably 1 or 2. The integer η is 1-6, preferably 1-4.

The esters according to the invention are made by customary esterification processes from suitable alcohols and an acid of the formula

(A) -COOH

509813/1165

obtained, or an acid halide or anhydride thereof. The higher alkyl esters can also be prepared from lower esters, in particular from the methyl ester or the above-mentioned compounds by transesterification with higher alkanols. The above carboxylic acid derivatives, which are then used in the compounds according to the invention are converted, are obtained in a known manner according to the following chemical reaction

- (A) -C-OH + SOCl

(D

Other halogenating agents such as phosphorus trichloride and phosphorus pentachloride can be used in equation (1).

The lower alkyl esters of I, e.g., methyl, are suitably made by means of an acid catalyzed reaction in the presence of the lower alcohol such as methanol.

AC-OH + CH ₃ OH

R ¹ R ²

II

If A is ethylene, then lower alkyl esters, e.g. compounds II, are suitable by reaction of starting phenol (IV) with acrylate esters, e.g. prepared according to reaction (3):

509813/1 165.

+ CH

ι Q -y catalyst = CC-OR ^J :

IV

HO

R ¹ R ²

III

? 9

wherein R is hydrogen or alkyl with 1-6 carbon atoms and

3
R is alkyl with 1-30 C atoms. Methods of this type are described, for example, in U.S. Patent 3,247,240 (April 9, 1966) and U.S. Patent 3,364,250 (January 16, 1968).

Type III products can also be obtained by reaction IV with
Acrylonitrile or a substituted acrylonitrile followed by alcoholysis of the nitriles can be prepared according to reactions (4) and (4a):

IV

II]

509813 / 1165-

Reaction (4) is e.g. analogous to that according to the US patent No. 3,121,732 (February 18, 1964)

Carboxylic acids I with A as methylene are suitably prepared by the reaction sequence 5, 5a and 5b,

R ¹ R ²

IV

^HCH0

^H0

iV

^CH 2 ^N

VI

■ K

MCN—> H0

CH -CN 2

R ¹ R ²

(5a)

VI

VII

wherein M is an alkali metal, such as sodium and potassium and R ⁷ and R ^{8 are} alkyl with 1-8 carbon atoms or together with

the N atom form a morpholine or piperidine ring.

7 R R and R are preferably methyl.

CH ₂ -CN

C-

VII

hydrolysis
- ϊ HO- (OK CH ₂ C-OH (5b)

VIII

509813/1165.

VIII is then in the usual manner as described above in converted the ester stabilizers according to the invention. The synthesis of compounds of type VI and VII is described in the examples.

Replacement of higher aldehydes such as n-butanol and octanol instead of formaldehyde in reaction 5 leads to the preparation of acids of the formula I with A as 1,1-alkylidene.

Acids of formula I can also be prepared by a substituted phenolate anion with a corresponding halogenoalkane-carboxylic acid ester, -amide or -nitrile, where A is straight-chain or branched alkylene having 2-8 carbon atoms.

Amides according to the invention are produced in a manner known per se by reaction of the carboxylic acid of the formula I or an acid chloride or anhydride thereof with a corresponding one Amine produced. The higher alkanamides can also be obtained from the lower alkyl esters of the acid of the formula I known amidation can be produced.

Most of the 2,3,6-trialkylated phenols that are starting material for the compounds according to the invention are known and commercially available. If not commercially available, the synthesis of the starting phenols is described or shown in the examples. Such is the production of, for example, 2, ö-diisopropyl-S-methyl-phenol and 2,6-di-tert-butyl-3-methyl-phenol in Japanese Patent Application 70 15,491, that of 2,3-dimethyl-6-tert-butylphenol by G. Pare in Revue de L'Institut Francais du Petrole Vol. XV, page 693 (1960).

509813/1 165

The inventive hindered hydroxyphenyl alkanoates and -amides not only have superior stabilizer properties, but also prevent gas fading in polymer substrates, like polypropylene multifilament knitwear, all in one high mass, as other antioxidants do not show. In addition, the stabilizers according to the invention give polymers superior Processing properties, e.g. Polypropylene and besides are they badly extracted. This combination of properties is particularly useful for textile products made from synthetic polymers important.

The inventive hydroxyphenyl alkanoates and amides are stabilizers of organic material, which is normally thermal and subject to oxidative decomposition. Substances that are stabilized in this way are synthetic organic polymer substances, such as Vinyl resins from the polymerization of vinyl halides or from the co-polymerization of vinyl halides with unsaturated polymerizable Compounds, e.g. vinyl esters, oc, ß-unsaturated ketones, cc, β-unsaturated aldehydes and unsaturated hydrocarbons, such as butadienes and styrene, as well as poly-cc-olefins, including polybutylene Copolymers of oc-olefins such as ethylene-propylene copolymers, and dienes such as polybutadiene, polyisoprene and the like, including copolymers with other monomers, and polyurethanes and polyamides, such as polyhexamethylene adipamides and polycaprolactam, as well as polyesters, such as polyethylene terephthalate, as well Polycarbonates, as well as polyacetals, such as polyethylene terephthalate polyacetal, as well as polystyrene, polyethylene oxide and copolymers, such as those made from high-impact polystyrene containing copolymers of butadiene and styrene and those from copolymerization of acrylonitrile, budadiene and / or styrene, as well as natural and synthetic rubber, such as ethylene / propylene / diene copolymer (EPDM) and chlorinated rubber, as well as polyphenylene oxide and copo polymer.

Other substances that are stabilized by substances according to the invention are aliphatic ester type lubricants, e.g. di- (2-ethylene) azelate and other synthetic ester lubricants, Pentaerythritol tetracaproate and the like, animal and vegetable

509813/1165

Oils, e.g. linseed oil, fat, talc, lard, peanut oil, cod liver oil, Ricinusb'l, palm oil, corn oil, Baumwo Ils amenöl and the like, hydrocarbon materials, such as gasoline, mineral oil, heating oil, drying oil, cutting fluids, waxes, resins and the like, salts of fatty acids, such as soaps and the like, and alkylene glycols, e.g. ß-methoxyethylene glycol, Methoxytrimethylene glycol, triethylene glycol, octaethylene glycol, Dibutylene glycol, dipropylene glycol and the like.

Substrates of particular importance are olefin polymers such as polyethylene and polypropylene. According to the invention, polypropylene is used particularly well stabilized.

In general, the stabilizers of this invention are (the stabilized mixture by weight) used in amounts of about 0.01 to 5 ⁰ L, although it depends on the particular substrate and application. A range of _{about 0.05-2.7 O} , especially about 0.1-1%, is preferred.

The stabilizers can be added to polymeric substrates the polymerization or afterwards, during the usual manufacturing steps, e.g. by means of hot grinding, whereupon the Mixture extruded, pressed or the like. To films, fibers, threads, hollow bodies and the like. Is. The heat stabilization of this Substances protect the polymer advantageously against degradation during such processing at the usual high temperatures. the Stabilizers can also be dissolved in a suitable solvent and applied to the surface of films, fabrics, or fibers Like. To achieve effective stabilization.

These compounds may also be used in combination with other additives, such as sulfur-containing esters such as distearyl-ßthiodipropionat (DSTDP) in an amount of 0.01 - TL (weight) of the organic material or the like, pour point depressants, corrosion and rust protecting agent. , Dispersants, emulsifiers, antifoams, carbon black, accelerators and other chemicals that are used for rubber compounding, value uiacher, color stabilizers, surfactants, fillers, di- and trialkyl- and -alkylphenyl-phosphites, heat stabilizers, UV stabilizers, antiozonants , Paints, pigments, metal chelate

5098Ϊ3 / 11έ p

BAD ORIGfNAU

sculptors, dye sites and the like, often combinations like these especially sulfur-containing esters, phosphites and / or UV stabilizers give better results in certain applications than with the individual connections themselves.

The following formula shows co-stabilizers which, in certain applications, are very useful in combination with those according to the invention Stabilizers are:

C _n

^C O

where R is alkyl with 6-24 carbon atoms, η is an integer from 1-6. Particularly useful compounds of this type are Dilauryl-ß-thiodipropionate and distearyl-ß-thiodipropionate. The above co-stabilizers are used in an amount of 0.01-2% (weight) of the organic material, preferably of 0.1-1%.

In addition to the above additives which can be used in combination with the compounds according to the invention, it is often particularly advantageous to also use light stabilizers. The light stabilizers are used in an amount of 0.01-5 % (weight) of the organic material, in particular 0.1-170. Examples of light stabilizers are as follows.

UV absorbers and light stabilizers

2 - (2'-Hydroxyphenyl) -benztriazoles, such as 5'-methyl-, 3 ', 5'-di-tert-butyl-, 5'-tert-butyl-, 5 ^f - (1,1, 3,3-tetramethyl-butyl) -, 5-chloro-3 ', 5 ^f -di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-, 3'-sec .-Butyl-5'-tert-butyl-, 3 '- {cc-methylbenzylj -5' -methyl-, 3'- £ cc-methylbenzyl} -5 '-methyl-5-chloro-, 4'-hydroxy -, 4'-methoxy, 4'-octoxy, 3 ', 5'-di-tert.-amyl-, 3'-methyl-5'-carbomethoxyethyl

or 5-chloro-3 ', 5'-di-tert-amyl derivatives.

50981 3/1165

2,4-bis- (2'-hydroxyphenyl) -6-alkyl-s-triazines , such as the 6-ethyl, 6-undecyl or 6-heptadecyl derivative.

2-Hydroxy-benzophenones, such as 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy or 2 '-Hydroxy-4,4'-dimethoxy derivative.

1,3-bis- (2'-hydroxy-benzoyl) -benzenes, such as 1,3-bis- (2'-hydroxy-4 ^f hexyloxy-benzoyl) -benzene, 1,3-bis- (2'-hydroxy -4'-octoxy-benzoyl) -benzene, and 1,3-bis- (2'-hydroxy-4'-dodecyloxy-benzoyl) -benzene.

Esters of optionally substituted benzoic acids, such as phenyl salicylate, octylphenyl salicylate, di-benzoyl resorcinol, bis- (4-tert-butyl-benzoyl) -resorcinol, benzoyl-resorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2 , 4-di-tert-butylphenyl ester, octadecyl ester or -2-methyl-4,6-di-tert-butylphenyl ester.

Acrylates such as oc-cyano-ß, ß-diphenylacrylic acid ethyl ester or isooctyl ester, oc-carbomethoxy-cinnamate, cc-cyano-ßmethyl-p-methoxy-cinnamic acid methyl ester or -butyl ester and N- (ß-carbomethoxy-vinyl ) -2-methyl-indoline.

Nickel compounds, such as nickel complexes of 2,2'-thio-bis-4- (l, l, 3,3-tetramethylbutyl) -phenol, such as the 1: 1 and 1: 2 complex, optionally with other ligands, such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel complexes of bis- ^ 2-hydroxy-4- (l, l, 3,3-tetramethylbutyl) -phenyl} -sulphone, such as the 2: 1 complex, optionally with other ligands, such as 2-ethylcaproic acid, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as methyl, ethyl or butyl esters, the nickel complex of 2-hydroxy-4-methylphenyl) - undecyl ketone oxime and nickel 3,5-di-tert-butyl-4-hydroxy-benzoate.

Oxalic acid diamides , such as, for example, 4,4'-di-octyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert. -butyl-oxanilide, 2-ethoxy-5-tertiärybutyl-2'-ethyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, Ν, Ν'-bis- (3-dimethylaminopropyl) -oxalamide, mixtures of o- and p-methoxy- and o- and p-ethoxydi-substituted oxanilides and mixtures of 2-ethoxy-5-tert.-

50981 3/1165

butyl-2'-ethyl-oxanilide with 2-ethoxy-2 ^! -Aethyl-5,4'-di-tert-butyl-oxanilide.

Sterically hindered amines such as 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, bis- (2,2,6,6-tetramethylpiperidyl) sebacate and 3-n-octyl-7,7,9,9-tetramethy1-1,3-triaza-spiro [4.5] decane-2,4-dione.

Compounds according to the invention are given below as examples listed that are useful as stabilizers as described above:

Methyl 3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate, Ethyl 3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate, n-butyl 3- (2,3,5-tri-methy1-4-hydroxyphenyl) propionate, n-octyl 3- (5-t-butyl-2,3-diethyl-4-hydroxyphenyl) propionate, Methyl 3- (2,3-dimethyl-5-t-octyl-4-hydroxyphenyl) propionate,

Methyl 3- (5,6,7,8-tetrahydro ^ -hydroxy-S-butyl-naphthyl-1) propionate,

n-octadecyl 3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate,

2- (n-octadecylthio) -ethyl-3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) -propionate,

2- (ethylthio), - ethyl-3- (3, 5-di-t-butyl-2-methyl-4-hydroxyphenyl) propionate,

2- (n-octylthio) ethyl-5-t-butyl-2,3-dimethyl-4-hydroxyphenyl acetate,

Cyclohexyl 3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate,

Neopentanetetrayl-tetrakis- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) acetate,

Neopentanetetrayl tetrakis [3- (5-t-octyl-2,3-dimethyl-4-hydroxyphenyl) propionate],

Neopentanetetrayl tetrakis [4- (5-t-butyl-2,3-diethyl-4-hydroxyphenyl) butyrate],

50981 3/1165

2U5345.

1,2,3,4,5,6-hexane hexayl hexakis [3- (5-t-butyl-3-dimethyl-4-hydroxyphenyl) propionate ,

1,2,3-butanetriyl tris [3- (5,6,7,8-tetrahydro-4-hydroxy-3-t-butylnaphthyl-1) propionate],

Methyl-5-t-butyl-2,3-dimethyl-4-hydroxyphenyl acetate, n-octadecyl-5-t-butyl-2,3-dimethyl-4-hydroxyphenyl acetate, n-Butyl-S-t-butyl ^ jS-dimethyl ^ -hydroxyphenyl acetate, n-Octy1-5-t-butyl-2,3-dimethyl-4-hydroxyacetate, n-Dodecyl-5-t-butyl-2, S-dimethyl ^ -hydroxyphenyl acetate,

2,2-dimethylpropylene-bis- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl acetate),

1,6-hexamethylene-bis- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl acetate),

p-t-Octy! phenyl-3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate,

Phenyl 3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate,

o-methylphenyl 3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate,

o, p-Di-t-butylphenyl-3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate,

2-ethylhexyl 3- (5-t-butyl-2,3-dimethy1-4-hydroxyphenyl) propionate, n-octadecyl 3- (2,3-dimethyl-5-t-octyl-4-hydroxyphenyl) propionate,

n-octadecyl 3- (5,6,7,8-tetrahydro-4-hydroxy-3-t-butylnaphthyl-1) propionate,

2,2-dimethylpropylene-bis (5-t-octyl-2,3-dimethyl-4-hydroxyphenyl acetate),

1,6-hexamethylene bis [3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate],

1,2-propylene bis [3- (5-t-buty1-2,3-dimethyl-4-hydroxyphenyl) propionate] ,

Ethylene bis [3- (5-isopropyl-2,3-dimethyl-4-hydroxyphenyl) propionate] , 509813/1165

24453A5 -

2,2-dimethylpropylene-bis- (5-t-octyl-2,3-diSthyl-4-hydroxyphenyl) acetate,

2,2-dimethylpropylene bis [3- (5-cyclohexyl-2,3-dimethyl-4-hydroxyphenyl) propionate],

2-methyl-1,4-pentamethylene-bis [3- (2,3,5-triethyl-4-hydroxyphenyl) propionate],

1,8-0ctamethylene-bis- [4- (2,3,5-tri-t-butyl-4-hydroxyphenyl) butyrate] ,

2,4-dimethyl-2,4-pentamethylene-bis- [6- (5- t-butyl-2,3-dimethyl-4-hydroxyphenyl) -hexanoate] ,

1,5-pent amethylene-bis - [3 - (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate],

l, 12-dodecamethylene bis [3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate],

2,2-dimethyl-1,2,2-butanetriyl-tris- [3- (5-t-butyl-2,3-dimethyl-4- ' hydroxyphenyl) propionate],

1,2,3-propanetriyl-tris- [3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate],

2,2-dimethyl-1,2,2-pentanetriyl-tris- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) acetate,

Neopentanetetrayl tetrakis [3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate],

Phenyl (5-t-octyl-2,3-dimethyl-4-hydroxyphenyl) acetate,

Neopentanetriyl tris (5- t-butyl-2,3-dimethyl-4-hydroxyphenyl acetate),

Thiodiethylen-bis- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl acetate),

Thiodiethylene bis [3- (5-t-butyl-2,3-di-methy1-4-hydroxyphenyl) propionate],

Ethylene bis [3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate],

3,6-Dioxa-1,8-octamethylene-bis [3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate],

5098 13/1165

2U5345,

/ 9

2,2-dimethylpropylene bis [3- (5- t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate] ,

2,2-dimethyl-1,2,2-pentanetriyl tris [3- (5- t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate],

1,4-Cyclohexanedimethylene-bis- [3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate],

3- (5-tert-Buty1-2,3-dimethyl-4-hydroxyphenyl) propionamide, (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) acetamide,

N-methyl-N-n-tetracosanyl-S- (2,3-dimethyl-5-tert-butyl-4-hydroxyphenyl) propionate,

N-n-octyl-N-phenyl- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) acetamide,

N-Cyclohexyl-3- (5-tert-octyl-2,3-dimethyl-4-hydroxyphenyl) propionamide,

N, N-dibutyl-3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionamide,

N, N ^I. , N ", N '" - 1,4-Dimethylcyclohexane-1,4-dimethylcyclohexane-1,4-1,4-tetrayl-tetrakis- [3- (5-tert-butyl-2,3-dimethyl-4- hydroxyphenyl) propionamide],

N-o-tolyl-N-methyl- (5-tert-octyl-2,3-dimethyl-4-hydroxyphenyl) acetamide.

The following examples illustrate the invention. Are in it the parts are parts by weight, unless otherwise specified, and that The ratio of parts by weight to parts by volume is that of Grams to Kubi keen time tern.

509813/1165

Methyl 3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate

1:53 grams of sodium metal in small pieces to 240.6 g of 2-tert-butyl-5,6-dimethy! Phenol, which is heated to 60 ⁰ C, added. The reaction mixture is then heated to 120 ° for 2 hours with stirring, during which time the sodium metal reacts completely. 174 g of methyl acrylate are then gradually added over the course of one hour in such a way that the temperature remains at 120 °. The reaction mixture is then heated to 120 ° -130 ° for a further 4 hours. 3.9 ml of acetic acid are then added. The reaction mixture is diluted with 600 ml of toluene and heated to dissolve a precipitate. The toluene solution is washed successively with 2N sodium carbonate, saturated sodium chloride, water, dilute aqueous hydrochloric acid and finally with water until the wash water is almost neutral. After drying over sodium sulfate, the clear toluene solution is evaporated at 20 mm Hg, finally at 1 mm Hg for 2 hours. The red residue is crystallized from a mixture of 450 ml of isopropanol and 200 ml of water and kept at about 15 ° C. overnight. The thick crystal slurry is filtered, the filter cake is washed with a little cold isopropanol-water mixture. After drying and recrystallization, the desired product is obtained as white crystals, m.p. = 74-76 ⁰ C (compound 1).

Example 2 Methyl 3- (2,3-dimethyl-5-tert-octyl-4-hydroxyphenyl) propionate

a) 2,3-Dimethyl-6- (1,1,3,3-tetramethylbutyl) -pheno1

183 g of 2,3-dimethylphenol, 168 g of 2,4,4-trimethylpentene-1 and 28.5 g of p-toluic acid monohydrate are added together to 1 liter of toluene. The reaction mixture 9 is heated hours at 80 85 ° C and 23 hours at 70 ⁰ C. The reaction mixture is washed sequentially with water, saturated sodium bicarbonate and water until it is almost neutral. After drying over

509813/1165

2U5345

anhydrous sodium sulfate, the dry reaction mixture is concentrated under reduced pressure to give intermediate (a) as a crude product. Unreacted 2,3-dimethylphenol is obtained from the crude product by sublimation at 10 - 75 ⁰ C and 0.3 mm Hg. The remaining liquid is then distilled to pure 2,3-dimethyl-6- (1,1,3,3-tetramethylbutyl) -phenol, bp = 76-80 ° at 50 microns Hg.

b) The product is obtained by reacting 2,3-dimethyl-6- (1,1,3,3-tetramethylbutyl) phenol with methyl acrylate in the same way as described in Example 1. The desired product is obtained as white crystals, m.p. = 83-85 ⁰ C (compound 2).

Example 3

Methyl 3- (5,6,7,8-tetrahydro-4-hydroxy-3-tert-butylnaphthyl-1) propionate

a) 2-tert-butyl-5,6,7,8-tetrahydro-1-naphthol

To a solution of 60 g of 5,6,7,8-tetrahydro-1-naphthol and 5.7 g p-Toluenesulfonic acid monohydrate in 600 ml of toluene at 75 ° C initiated about 30 g of isobutylene within 3 hours. The reaction mixture is held at 75 ° C. for a further hour. After cooling to room temperature, the reaction mixture is successively mit.Wasser, saturated sodium bicarbonate and with Water washed. The toluene phase is then dried over anhydrous sodium sulfate. After distilling off the solvent the residue is distilled under reduced pressure to give 2-tert-butyl-5,6,7,8-tetrahydro-1-naphthol, a light yellow one viscous liquid, b.p. 97-98 ° G at 0.1 mm Hg.

b) methyl-3- (5,6,7,8-tetrahydro-4-hydroxy-3-tert-butyl-naphthyl-1) propionate

is made by reacting 5,6,7,8-tetrahydro-2-tert.-butyl-1-naphthol obtained with methyl acrylate in a manner analogous to that described in Example 1. The connection will be in the form of white

Crystals obtained, mp = 84-86 ° (compound 3).

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Example 4 λα

n-Octadecyl 3- (5-tert-butyl-2,3-dimethyl 1-4-hydroxyphenyl) propionate

37.9 g of n-octadecanol and 38.8 g of the compound from Example 1 are placed in a reaction vessel, dried and flushed with nitrogen, then 1 ml of dry dimethyl sulfoxide and 56 milligrams of lithium hydride are added. The system is flushed again with nitrogen and the reaction mixture heated to 120 ⁰ C. The melt is heated to 120-125 ° for 1 hour at 1 atmosphere pressure, to 130 ° for 50 minutes at 1 atmosphere and finally to 130-140 ° at 20 mm Hg for 1.25 hours. During this time, 5.6 ml of methanol is collected. The reaction mixture is dissolved in 200 ml of toluene and neutralized with 0.5 ml of glacial acetic acid. The toluene solution is then repeatedly dried with aqueous saturated sodium chloride solution and over anhydrous magnesium sulfate. After the drying agent has been separated off, the clear filtrate is concentrated under reduced pressure. The residue is kept at 50-60 ° C. and 0.3 mm Hg for 1 hour in order to remove all volatiles. A brown oil residue is obtained in this way. After two crystallizations from a methanol-isopropanol mixture, the desired product is obtained in the form of white crystals, mp = 55-57 ° (compound 4).

The compounds according to Table I are obtained in a manner analogous to that described in Example 4.

S09813 / 1165

Table I.

Other 3- (3-tert-alkyl-5,6-dialkyl-4-hydroxyphenyl) propionates

0 S-

CH.CH C-O

Rl

R "

link

CH,

CH

H, -C-

ch.-

• R ^J

• R

CH ₃ η-C ₁₈ H ₃₇ -S-CH ₂ CH ₂ -

-n

F. ⁰ C

49-5I

■ F ₃

CH ₃ -C-CH ₃

CH ₃ O- ³ CH ^

CH ₃ (CH ₂ ) ₃ CH-CH ₂ -

87.5-89.5

fluid

(1)

CH

—C-CHp ~

47-50

9. ■

R ₁ + R ₂

^[ 2 ^CH 2

^N CH ₂ -CH ₂

59-61 '

Table I (continued)

Connection no. 10 CH ₃ _R 11 CH ₃ CH ₃
-C-
L, 5 0 9 81 CHo
ο Ho co CH ₃ 12th CH ₃ ? ^H 3 σ>
cn CH ₃ -A-
CH ₃ CHo CH ₀
I 3 ι 3
-C-CH ₂ -C-
CHo CHo

R ^J

CH-

CH ₃

CH-

CH,

-CH ₂ -C-CHg-

- (CHg) ₆ -

CH ^ - I 2

-CH ₂ -C-CH ₂ -CH ₂ -

CH ₂ - -CHg-C-CHg-CH ₂ -

η F. ⁰ C

116-119

108-110

159-164

8l- $ 0

-C οι co

Note: (1) cleared from silica gel - pale yellow liquid

Example 5 Λς-

5-tert-butyl-2,3-dimethyl-4-hydroxyphenylacetic acid

a) 6-tert-Butyl-2,3-dimethyl-4- (dimethylaminomethyl) phenol

Tert 6 to 142.4 g, butyl-2,3-dimethy! Phenol dissolved in 270 ml of toluene 144.4 g of a 257 _o solution of dimethylamine added at about room temperature. 65.7 g of 36.5% strength aqueous formaldehyde are then added to the reaction mixture over the course of 10 minutes, initially at 15 °, the temperature at the end. rises to 30 °. The reaction mixture is then heated to 40 ° for 3 hours, finally under reflux (85 °) for 2 hours. The reaction mixture is diluted with about 1 liter of ether. The aqueous layer is separated. The upper layer of ether is washed 3 times with water. After drying over sodium sulfate, the organic phase is evaporated under reduced pressure and yields 176.3 g of crude product. This is crystallized from heptane to white crystals, F = 101 - 104 °.

b) 5-tert-butyl-2,3-dimethyl-4-hydroxyphenylacetonitrile

A solution of 153 g of the compound prepared under (a) dissolved in 200 ml of N, N-dimethylformamide is added to 48 g of sodium cyanide dispersed in 900 ml of N, N-dimethylformamide with vigorous stirring at 25-30 ° C. The reaction mixture is then heated to 70-75 ° for 5 hours while stirring. The reaction mixture is cooled to room temperature. About 1000 g of ice water are added. After inoculation with some product nitrile crystals to completely crystallize, the white crystals obtained are filtered off. The filter cake is washed with warm water and ^{dried in a vacuum oven at 70 °} C. and 15 mm Hg. The dried crystalline precipitate is slurried in hot hexane to remove dyes. The nitrile product is obtained as white crystals, mp = 126 ° -128 °.

c) 104 g of the nitrile according to (b) slowly become a mixture given by 115.2 g of 507 ° aqueous sodium hydroxide and 64 g of ethylene glycol at 80 °. The temperature is slowly increased by the To keep the reaction product stirrable. After about 1 hour it will

509813/1165

The reflux temperature is reached (12O ⁰ C) and the heating under reflux is continued for 6 hours. The reaction mixture is diluted with about 4 liters of water, heated to dissolve the sodium carboxylate salt, and then filtered to remove some insoluble. The clear filtrate is acidified with concentrated hydrochloric acid, the precipitated product is filtered off and the filter cake is ^{dried in vacuo at 80 °} C. and 15 mm Hg. The product is obtained as a white powder, m.p. = 213-217 ⁰ C. Crystallization from acetonitrile increases the melting range 214-218 ⁰ C (compound 26).

Example 6 Methyl 5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl acetate

11.8 g of 5-tert-butyl-2,3-dimethyl-4-hydroKyphenylessigsäure are added at 20 ⁰ C to 200 ml of methanol that was previously saturated with hydrogen chloride gas. The slightly pink solution is ^{heated under reflux (68 °} C.) for 3 hours. About half of the solvent is then removed under reduced pressure. The reaction mixture is then poured into about 500 ml of an ice / water mixture with stirring until all of the ice has melted. The precipitated crystals are filtered off, washed with water and dissolved in benzene. The benzene solution is washed successively with water, saturated sodium bicarbonate solution and finally with water to pH 7. The benzene solution is dried over anhydrous sodium. The clear benzene solution, freed from the drying agent by filtration, is concentrated under reduced pressure. The solid residue obtained is treated with hexane to remove dyes. After recrystallization from methanol, the desired product is obtained in the form of white crystals, mp = 117-119 ° C. (compound 14).

0 9 «13/1 165

Example 7 % r

n-Octadecyl-5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl acetate

8.85 g of 5-tert-butyr ^^ - dimethyl ^ -hydroxyphenylacetic acid, 9.45 g n-octadecanol and 0.665 g p-toluenesulfonic acid monohydrate are dispersed in 500ml toluene and refluxed for 7 hours. Something is added to the cooled reaction mixture Aether given to prevent failure. The reaction solution is then successively washed with water and saturated sodium bicarbonate solution and washed again with water until neutral. After drying over anhydrous sodium sulfate and filtering the clear filtrate is concentrated under reduced pressure. After washing with cold acetonitrile, the ground, dried The residue crystallizes from n-heptane and gives white crystals, melting point 79-81 ° (compound 15).

In the same way as in Example 7, other 5-tert-butyl-2,3 ■ dimethy1-4-hydroxyphenyl acetates obtained, which are contained in Table II are.

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Table II Other 5-tert-butyl- ^ B-dimethyl ^ -hydroxyphenyl acetates

link

fly.

16. 17th

19th

20th

tert-butyl ο

HO - //

CH ₃

-CH ₀ -C-CHj, -CH ₃

CH,

■ h-

η 1 1 1

JF ⁰ Jl

89-93 63-65 68-70

143-145 152-155

0 9 813/1165

Example 8

p-tert-octylphenyl-3- (5-tert-butyl- 2, 3-dimethyl-4-hydroxyphenyl) propionate

A stirred mixture of 3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionic acid (12.5 g, 0.05 mol) and thionyl chloride (7.5 g, 0.063 mol) in 250 ml of dry toluene with a few drops of N, N-dimethylformamide is heated to 75-85 ° for 1 hour. Moisture is excluded. p-tert-octylphenol (10.3 g, 0.05 mole) admitted. The mixture is stirred and refluxed for 18 hours. The solvent is under reduced pressure evaporated. The residue obtained in this way is dissolved in ether. The ether solution is with 107o sodium carbonate solution and then with Water washed. Evaporation of the sodium sulfate-dried ether solution results in an oily residue which is dissolved in petroleum ether will. A crystalline solid precipitates out on standing. Two recrystallizations from hexane give the product in the form of white crystals, F = 104.5 - 106.5 ° C (compound 21).

In a manner similar to that of Example 8, the compounds of Table III obtained.

5 0 9 813/1165

Table III

Others AryI-3- (5-tert-butyI-2,3-dimethyl · -4-hydroxyphenyl) ^ propionate

link
No.

22nd

tert-butyl

CH CH

Structure R

24 tert, butyl: - <f_ \

112-114

90-92 138-140

tert-butyl

509813/1

Example 9 Neopentanetriyl-tris- (5-tert .-

acetate)

24.2 g of 5-tert-butyl ^ jS-dimethyl ^ -hydroxyphenylacetic acid, 3.6 g 1,1,1-Trimethyloläthan and 0.746 g of dibutyltin oxide are in 35 ml dispersed dry xylene and 3 ml of dry dimethyl sulfoxide and heated to distill off XyIo! solvent until a Reflux temperature. Of 152-155 ° is reached. Then the The reaction mixture is homogeneous and is heated with stirring at this temperature for 18 hours, then for a further 6.5 hours 157-160 °. The reaction mixture is dissolved in 800 ml of chloroform and successively with water and saturated aqueous sodium bicarbonate solution and washed again with water until the pH of the wash water is neutral. The reaction solution is then over dried anhydrous sodium sulfate. The clear filtrate is evaporated under reduced pressure. A residue is obtained which becomes crystalline after treatment with a boiling mixture of 80 ml of hexane and 70 ml of toluene. After repeated crystallization from isopropanol and then from toluene, the product is obtained in the form of white crystals, temperature = 159 - 164 ° (compound 25)

In a manner similar to that of Example 9, the compounds of Table IV.

509813/1 165

24453 45 Tabel IV

-Tert
HOY η Butyl X 0
ir
(CHg) _x CO X r3 F o _c /
^CH 3 1 \
CH- 2 118-124 link
No. 2 2 R. ) ₂ s viscous syrup (1) 27 1 4th (1-CHgCHg 186-189 28 (-CH ₂ CH ₂ ), p- 29 CH ₂ -
-CHo-C-CH,
• 1 '
CH ₂ -

Note: (1) Purified by silica gel column chromatography,

which makes a slightly yellow syrup.

50981 3/1165

Example 10 W

2,2-dimethyl-1,2,2-pentanetriyl-tris- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl acetate)

A mixture of 2.54 g of 1,1,1-TrimethyIo! Butane together with 13.5 g of methyl 5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl acetate and 13.7 milligrams of lithium hydride are put together under nitrogen. 115 ° heated for 20 minutes, then to 140 ° for 30 minutes, at 170 ° for 1 hour. The mixture is then held at 190-195 ° for 4 hours. During this heating, the resulting Methanol is distilled off. After removing unreacted methyl 5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl acetate through The residue is dissolved in benzene by distillation under reduced pressure. The benzene solution is acidified with 1 ml of acetic acid and freed from little insolubles by filtration. The benzene solution, which contains the product, is then with 57oigem washed aqueous sodium carbonate and dried over sodium sulfate. The product appears in crude form as a glassy residue obtain. After purification by dry column chromatography with silica gel, the product turns white Crystals obtained, F = 73-75 ° C after crystallization a mixed solvent of benzene-hexane (compound 30).

Example 11

3,6-Dioxa-1,8-octamethylene-bis-3- (5-tert-butyl-2,3-dimethyl-4-hydrocyphenyl) propionate

a) 3- (5-tert-Butyl-2,3-dimethyl-4-hydroxyphenyl) propionic acid

A solution of methyl 1-3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate is added under nitrogen (71.5 g) in 150 ml of ethanol with a solution of 987o sodium hydroxide (12.1 g) in Treated 15 ml of water. The mixture is refluxed for 3 hours heated. The cold solution is diluted to about 1200 ml with water and then acidified with concentrated hydrochloric acid. Of the precipitated solid is filtered off and washed with water. Recrystallization * from 600 ml of acetonitrile gives the acid, ■ F = 191-193 ° C. 5098 13/1165

b) A stirred mixture of 12.0 g of 3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionic acid, 3.0 g of triethylene glycol and 0.6 milliliter of titanium tetraisopropoxide in 200 ml of dry Xylene is refluxed for 18 hours, during which time it evolves Water is removed by azeotropic distillation. The xylene is removed by distillation under reduced pressure. The residue obtained is taken up in ether. The ethereal solution is clarified by filtration and over sodium sulfate dried, after removing the desiccant, distilled off under reduced pressure. The product is analyzed by dry column chromatography Purified on silica gel as an absorbent and obtained as a colorless glass (compound 31).

Example 12

Ethylene bis {3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate}

This compound is made in a similar manner to Example 11, whereas ethylene glycol is replaced by triethylene glycol. After crystallization from a solvent mixture of Benzo1-Heptane becomes the product in the form of white crystals obtained, F = 148-150 ° (compound 32).

Unstabilized polypropylene powder (Hercules Profax 6501) is carefully mixed with 0.2 7 _O (weight) of the respective stabilizer. There also be prepared samples of polypropylene, 0.1 ° / o (weight) containing the same stabilizer, and 0.3 ° L (weight) of distearyl-beta-thiodipropionate (DSTDP). The mixed material is then milled on a two roll mill at 182 ° C for 10 minutes. The stabilized polypropylene is then removed from the mill to form films and allowed to cool.

The ground polypropylene films are cut into pieces

2 and 7 minutes in a hydraulic press at 218 ° C, 19.25 kg / cm pressed. The platelets obtained with a thickness of 0.635 mm are tested for their resistance to accelerated aging in one Oven tested at 150 ° C. As soon as the platelets show the first signs show signs of decomposition (e.g. cracks or brown corners)

509813/1165

they were considered decomposed. The results are shown in Table V.

Table V

Oven aging of polypropylene flakes containing 2,3,5-trialkyl-4-hydroxyphenyl alkanolates

Example% stabilizer

• Hours to decompose

Unstabilized Ver
binding
It 16
16 + 0 .3g DSTDP ■ .3g DSTDP 3 13th 0.2g
0.1g Il 17th <20
205 14th
15th 0.2g H 17 + 0 .3g DSTDP 3g DSTDP <20 16 0.1g It 18th * 220 17th 0.2g It 18 + 0 .3g DSTDP 3g DSTDP <20 18th 0.1g II 15th 250 19th '0.2g It 15 + 0 3g DSTDP 45 20th 0.1g It 4th 215 21 0.2g Il 4 + 0. 3g DSTDP 55 * 22nd 0.1g Il 2 1070 23 0.2g II 2 + 0. 3g DSTDP . <20 '24 0.1g Il 8th .155 25th 0.2g Il 8 + 0. 3g DSTDP 25th 26th 0.1g Il 3 1110 27 0.2g Il 3 + 0. <20 28 - 0.1g It 9 200 29 0.2g Il 9 + 0. 175 30th 0.1g Il 7th 795 31 0.2g ti 7+ 0. <20 32 0.1g 115 33

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2445345
36
Table V (continued) Ver
binding
It 6th
6 + 0.3 $ DSTDP Hours to zero
settlement example
No. % Stabilizer It 21 <20
110 34
35. 0.2 $
0.1 $ ti 21 + 0.3 $ DSTDP 25th 36 0.2 $ It 24 205 37 0.1 $ It 24 + 0.3 $ DSTDP <20 38 0.2 $ Il 23 125 39 0.1 $ It 23 + 0.3 $ DSTDP <20 40 0.2 $ Il 22nd 150 41 0.1 $ It 22 + 0.3 $ DSTDP . <20 42 0.2 $ It 124 43 0.1 $ Il 19 + 0.3 $ DSTDP 45 44 0.2 $ Il 10 250 45 0.1 $ ti 10 + 0.3 $ DSTDP 190 46 0.2 $ Il 20th 1590 47 0.1 $ It 20 + 0.3 $ DSTDP 25th 48 0.2 $ Il 11 II30 49 0.1 $ Il 11 + 0.3 $ DSTDP 240 50 - 0.2 $ ti ² 5 2270 51 0.1 $ ti 25 + 0.3 $ DSTDP 75 52 0.2 $ ti 29 2520 53 0.1 $ It 29 + 0.3 $ DSTDP 75 54 0.2 $ H 12th 2100 55 • 0.1 $ It 12 + 0.3 $ DSTDP 105 56 0.2 $ I5IO 57 0.1 $

50981 3/1165

Table V (continued)

Example “q ^ mh ,,, ^ 'hours to

N _{0 #} ι » ötaoiiizer decomposition

140

965 480 1225 190

58
59 0.2 * Ver
binding
0.1 * " ti 27
27 + 0.3 * DSTDP + 0.3 * DSTDP 60 0.2 * Il 28 • 61 0.1 * Il 28 + 0.3 * DSTDP + 0.3 * DSTDP 62 0.2 * Il 13th 63 0.1 * Il 13th + 0.3 * DSTDP + 0.3 * DSTDP 64 0.2 * Il 5 65 0.1 * Il '5 + 0.3 * DSTDP 66 0.2 * Il 30th 67 0.1 * Il 30th 68 0.2 * II 31 '69 0.1 * II 31 70 0.2 * Il 32 71 0.1 * 32

1005

1750 80

1530

215

1195

110

590

The stabilizers are particularly useful in the presence of a thioester co-stabilizer, effective as DSTDP.

5 0 9 813/1165

Example 72 £ 3

Cookies (500 g) of unstabilized nylon-6,6 (Zytel 101, DuFont) are placed in a household mixer. While mixing, a solution of 0.5 7 _O (based on the weight of nylon n-octadecyl-3- (5-t-butyl-2,3-diethyl-4-hydroxyphenyl) propionate in 20 ml of methylene chloride is slowly added. Sodium hypophosphite (0.5 g 0.1 %) is dissolved in 20 ml of water and added slowly to the nylon cookies while mixing, after the antioxidant solution has been added and most of the methylene chloride has evaporated The stabilized cookies are at 80 ^° C. and 1 mm Hg dried for 4 hours.

The polyamide formulation is extruded at 315.6 ° C. through a 0.635 cm nozzle to form a rod which is cooled in water and cut into flakes. A 1,905 cm Brabender extruder with a nylon screw is used. The platelets are ^{dried at 80 °} C. and 1 mm for 4 hours.

The dried platelets are pressure-pressed into 0.127 mm thick films at 290 ° C. for 4 minutes at 57.75 kg / cm. The films are oven aged at 150 ⁰ C. Samples are taken periodically. The viscosity of the samples is determined using a 1% formic acid solution at 25 ° C. The sample stabilized with the above stabilizer required a longer aging time to reduce its viscosity to half that of the unstabilized sample.

Example 73

Unstabilized high-impact polystyrene resin is mixed dry with 0.01% (weight) of the resin 2- (n-octylthio) -ethyl-5-t-butyl-2,3-dimethyl-4-hydroxyphenyl acetate. The resin is then compounded extruding in a 2.54 CM 24 / l = L / D extruder, melting temperature of 26O ° C and 7 minutes at a temperature of 163 ⁰ C and a pressure of 140 kg / cm uniform in film thickness of 2.54 mm is pressed . The foils are cut into pieces measuring 5.08 5.08 cm. These are oven aged at 80 ⁰ C.

Periodically, the color is determined using a Hunter Color Difference

509813/1 165

Meter model D25 measured. The polystyrene samples stabilized with the above stabilizer show the undesirable yellow . Discoloration much later than the unstabilized samples.

Example 74

Unstabilized linear polyethylene (HiFax 4401) is dissolved in methylene chloride with 0.2% (weight) of the substrate ethylene bis [3- (5-isopropyl-2,3-dimethyl-4-hydroxyphenyl) propionate] Solvent mixed and then vacuum dried. The resin is then at 232.2 ° C in a 1.905 cm extruder with a 24: 1 L / D Ratio extruded. The melt flow rate of the resin is determined after each extrusion according to ASTM test D-1238. Polyethylene stabilized with the above compound shows less change in melt flow rate than the unstabilized one Polyethylene.

Example 75

A lot of SBR emulsion with 100 g gum (500 ml of a 20% Texas U.S. SBR emulsion as Synpol 1500) under nitrogen is placed in a beaker and stirred vigorously. The pH of the emulsion is adjusted to 10.5 with a 0.5N NaOH solution adjusted.

50 ml of 257% NaCl solution are added to the emulsion. A 67.

• The solution, which has been adjusted to pH 1.5 with hydrochloric acid, is added to the thin stream while stirring vigorously. Is j_cht pH 6.5 ± ER, the rubber begins to coagulate and the addition is slowed aufrechtzuhälten to uniform motion. The addition of the acidic 6% NaCl solution is ended when pH 3.5 is reached. The coagulated lump of gum slurry is stirred at pH 3.5 for 1/2 hour.

The coagulated gum is isolated by filtration through a cloth and washed with distilled water. After washing three times with freshly distilled water, the coagulated Gum dried, first at 25 mm Hg and finally up to

Constant weight under high vacuum (<1 mm) at 40 - 45 ° C.

5 0 9 8 13/1165

The dried gum (25 g) is heated under nitrogen to shear 125 ⁰ C in a Br off-going-mi. 0.1 ° L 1,8-octamethylene-bis- [4- (2,3,5-trimethyl-4-hydroxyphenyl) butyrate are mixed in.

Portions of the rubber are ^{aged at 100 °} C. in the oven. The gel content of the gum is determined at various intervals. The gum stabilized with the above stabilizer shows much less gel formation than the unstabilized sample.

Example 76 .

In 50 g of polyacetal resin with 0.17 _o of an acid binder, dicyandiamide, are added 0.2% (weight) phenyl (5-t-octyl-2,3-dimethy1-4-hydroxyphenyl) -ac et al and 7 Minutes at 200 ⁰ C in a Brabender Piastirecorder ground. The ground formulation is on top

ο in a 1.016 mm film at 215 ⁰ C and 24.5 kg / cm 90 seconds

Pressed for a long time, then quickly cooled in a cold press at 24.5 kg / cm. The stabilized films are then pressed for 2 minutes at contact pressure and 3 minutes at 21 kg / cm ² and 215 ° C. to give platelets of 3.81 × m × 5.715 cm × 3.175 mm. The platelets are aged in an oven at 60 ° C. The weight loss of the samples is determined periodically until a 4% weight loss is reached. The stabilized sample takes much longer to achieve this 47o weight loss than the unstabilized sample.

Example 77

Unstabilized, carefully dried polyethylene terephthalate chips are dry mixed with _{1.07 o} Sjö-dioxa-ljS-octamethylene-bis- [3- (5-t-butyl-2,3-dimethy1-4-hydroxypheny1) propionate]. 60/10 denier multifilament is melt spun at a melt temperature of 29O ° C and cold oriented 3 to 1. The oriented threads are spun into yarn and ^{aged at 140 °} C. in the oven. The stabilized material retains its elasticity better than the unstabilized material after 24 hours.

509813/1165

Example 78 rf

A stabilized high-temperature lubricating oil is made by incorporating 0.05% (by weight) 2,2-dimethyl-1,2,2-pentanetriyl-tris- [3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate] in the lubricating oil, which contains diisoamyl adipate. The stabilized mixture is compared with the unstabilized lubricating oil by heating it to 175 ^° C. in the presence of air and metallic catalysts, according to the test method from Military Specification Mil-I-78O8c. After 72 hours the sample without stabilizer contains more sediment and has a higher viscosity than the stabilized lubricating oil.

Example 79

N-Methyl-3- (2,3-dimethyl-5-tert-butyl-4-hydroxyphenyl) propionamide ■

A mixture of 450 ml of dimethyl sulfoxide, 29.4 g of methylamine and 5.04 g of a 57% strength oil dispersion of sodium hydride (= 0.1197 mol) is stirred at 25 ° C. for 3 1/4 hours. 15.1 g of methyl 3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate are added and the mixture obtained is stirred at 25 ° C. for 18 hours. The reaction mixture is then neutralized with glacial acetic acid, diluted with water and extracted with ether. The ether extracts are added together and with sodium hydroxide and water washed and dried over anhydrous sodium sulfate. After removing the ether by distillation, crystallization results of the residue from toluene white crystals, mp = 125 ° 129 ° (compound 33).

Example 80

N-methyl-N-n-octadecyl- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) acetamide

A mixture of 8.76 g of methyl 2,3-dimethyl-5-t-butyl-4-hydroxyphenyl acetate and 11.87 g of N-methyl-N-n-octadecylamine is heated to 165 ° -180 ° for 5 hours and then to 180 ° -187 ° under nitrogen heated for another 3 hours. The reaction methanol is continuously distilled off. The "product would benefit from two crystalline

ions purified from ethanol and obtained as a white solid, F = 99 - 102 ° (connection 34).

N- n -dodecyl- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) acetamide is obtained in an analogous manner, with n-dodecylamine being N-methyl-N-n-octadecylamine replaced.

Example 81

N-n-octadecyl-3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionamide

A mixture of 10.6 g of methyl 3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate and 11.9 g of n-octadecylamine is heated to 160-165 ° for 1 hour and then to 175-180 ° for 4 hours. The reaction methanol is continuously distilled off. Crystallization from methanol gives white crystals, mp = 85 ° 87 ° (Compound 35).

Example 82

Ν, Ν'-Aethylenbis | 3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl ^ propionamide ^

A mixture of 22.21 g of methyl 3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate and 2.4 g of ethylenediamine is melted together and gradually from 91 ° to 172 ° within Heated for 18.5 hours and then held at 172 ° for a further 2 hours. Reaction methanol is removed by distillation. That The product is repeated from a solvent mixture of ethanol-water and then from acetonitrile to form white crystals crystallized, m.p. 214-217 ° (compound 36).

N, N'-1,2-propylenebis- (3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) Propionamide} is produced in a similar way by adding 1,2-propylenediamine to ethylenediamine in the above process replaced.

50981 3/1165

Example 83

Ν, Ν'-hexamethylene bis-j3- (5-tert-butyl ^^ - dimethyl ^ -hydroxyphenyl) propionamide) .

This product is made in a manner similar to that of Example 82 produced by 1,6-hexanediamine replacing the ethylenediamine. After repeated crystallization from a solvent mixture of carbon tetrachloride and 1,2-dichloroethane, methanol-water and finally from chloroform the product is obtained in the form of white crystals, F = 176 ° - 178 ° (compound 37)

NjN'-dodecamethylene bis- 3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) Propionamide is made in a manner similar to that in the example 82 obtained by 1,2-dodecamethylenediamine the ethylenediamine replaced.

Example 84

N, N'-bis- {3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl ·) propionyl} piperazine

A mixture of 20.0 g of methyl 3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate and 3.1 g of piperazine is gradually heated from 120 ° to 175 ° within 6.5 hours and at 175 ° -180 ° held under nitrogen for a further 4 hours. Reaction methanol is removed by distillation. The reaction product is made hot by repeated extractions with fresh Toluene and finally purified with 95% ethanol. The purified product is a white solid, F = 221 ° - 224 ° (compound 38).

509813/1165

Example 85

N, N'-3,6-dioxa-1,8-oetamethyleribis- [3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionamidj

A mixture of 18.9 g of methyl 3- (5-t-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate and 5.0 g (0.034 mol) of 3,6-dioxa-1,8-octanediamine is heated under nitrogen for 7 1/2 hours. Meanwhile, the temperature increases gradually from 135 ° to 175 °. Heating is continued for another 6 1/2 hours at 175 ° -180 ° continued. The methanol by-product weighs 20.53 g. The product is purified by extractions with 5% hydrochloric acid and water. The final purification is carried out using chromatography Alumina and chloroform achieved. 4.9 g of a white glass, F «72 ° -95 ° (compound 39) are obtained.

Oven aging tests are carried out on compounds 33 - 39, whereby the sample preparation and implementation are as per Table V can be performed. The results are shown in Table VI.

509813/1 1 65

Table VI

Oven aging of polypropylene platelets containing 2,3,5-trialkyl-A-hydroxyphenylalkanamide

example
No. % Stabilizer Verr
binding 33
33 H. hours DSTDP until decomposition . 86 Unstabilized Il 34 3 87
• 88 0.2%
0.1% 'Il 34 · \ DSTDP <20
165 89 0.2% Il 35 105 90 0.1% Il 35 - \ DSTDP > 520 91 0.2% Il 36 175 92 0.1% Il 36 H. DSTDP 950 93 0.2% Il 37 105 94 0.1% Il 37 H. DSTDP 590 95 0.2% Il 38 90 96 0.1% Il 38 H. DSTDP 780 97 0.2% Il 39 65 98 0.1% Il 39 - \ DSTDP > 1530 99 0.2% 100 ^: 100 0.1% 415 h 0.3% h 0.3% h 0.3% 1- 0.3% h 0.3% h 0.3% l 0.3%

50981 3/1165

Claims (22)

Claims 1 2
wherein R, R and R independently of one another are alkyl with 1-8 carbon atoms or cycloalkyl with 5-6 carbon atoms, with no more than 2 cycloalkyl groups being present, or. 1 2 R and R together are butylene which together with the phenyl ring forms a tetrahydronaphthyl group, and if η is 1, R is hydrogen, alkyl with 1-30 C atoms, cycloalkyl with 5-6 carbon atoms, phenyl, alkyl-substituted phenyl, where alkyl has 1-8 carbon atoms, or Alk'yl thioä thy I with 5-27 atoms in the chain, or, when η is 2, R is alkylene with 2-12 C atoms, cycloalkylene with 5-8 C atoms, alkylene with 7-10 C atoms and a cycloalkane group in the chain, thiobisalkylene with 5-9 atoms in the chain, alkyleneoxyalkylene with 5-9 atoms in the Chain, or polyoxyalkylene with 8-101 atoms, or, if η 3-6 is a 3-6 valent cyclic or acyclic hydrocarbon radical with 3-10 carbon atoms, where in formula F-I 3
each carbon atom of the radical R is bonded to only one heteroatom, R is hydrogen, alkyl with 1-8 carbon atoms or cycloalkyl with 5-6 carbon atoms, or R and R together form a piperazinyl ring and include both N atoms if m is 2, or the Rest " R P
-CH ₂ CH ₂ NHC- (A) and, when η is 1, R is hydrogen, alkyl with 1-24 carbon atoms, phenyl, alkylphenyl with 1-18 carbon atoms in the alkyl part, or, 3
when m is 2, R is alkylene having 2-18 carbon atoms or polyoxyalkylene 3 with 8-11 carbon atoms, or, when m is 3 or 4, R is a 3 or Is tetravalent cyclic or acyclic hydrocarbon radical with 3-8 carbon atoms, where in formula F-2 each carbon atom of the radical R is connected to only one carbon atom, A is branched or straight-chain alkylene with 1-8 carbon atoms, m is an integer from 1-4 and η is an integer from 1-6. 2. Compounds according to claim 1, wherein R is branched alkyl with 3-8 carbon atoms, R ¹ and R ^{2 are} alkyl with 1-3 carbon atoms, R ^{3 is} alkyl with 1-18 carbon atoms, cyclohexyl, alkylene with 2-8 carbon atoms, 2,2,4,4-tetramethyl-1,3-cyciobutanediyl, 1,4-cyclohexanedimethylene, alkylphenyl with 1-12 carbon atoms in the alkyl part, alkylthio methyl with 5-21 atoms in the chain, Thiodiethylene, oxydiethylene, polyoxyalkylene with 8-11 C-atoms or a 3-6-valent acyclic hydrocarbon radical with 3-7 C-atoms, R ^{4 is} alkyl with 1-4 C-atoms, R ^{5 is} alkyl with 1-18 C- Atoms, alkylene with 2-12 carbon atoms, or polyoxymethylene with 8 atoms, A is straight-chain alkylene with 1-3 carbon atoms, m is 1 or 2, and η is an integer from 1-4. 509813/1165 3. Compounds according to claim 1, wherein R is tert-butyl, R ¹ and R are methyl, R is alkylene with 2-6 carbon atoms, alkylphenyl with 1-8 carbon atoms in the alkyl part, polyoxyethylene with 8 atoms or a 3 -6-valent acyclic hydrocarbon radical with 5-7 carbon atoms, R is methyl, and A is methylene or ethylene. 4. Compounds according to claim 1, wherein R is alkyl with 4-8 C- 12 1 2 Is atoms, R and R are methyl, or R and R together Butylene, which together with the phenyl ring form a tetrahydro- 3 forms naphthyl radical, and, when η is 1, R is alkyl with 1-18 C- Atoms, phenyl, alkylphenyl with 1-8 carbon atoms in the alkyl part, Is alkylthioethyl with 21 atoms or cyclohexyl, or if 3
η is 2, R is alkylene with 5 or 6 carbon atoms, thiobisethylene, Alkyleneoxyalkylene with 7 atoms or Aethyleneoxyäthylenoxyäthylen 3
or, when η is 3, R is alkanetriyl with 5 carbon atoms, or, when η is 4, R is alkanetrayl with 5 carbon atoms, R is hydrogen or methyl, and when m is 1, R is alkyl with 1-18 carbon atoms, or, if m is 2, R is alkylene with 2-6 carbon atoms, or R and R together form a piperazine ring including both N atoms, A straight-chain alkylene with 1 or 2 carbon atoms Atoms, m is 1 or 2, and η is 1-4. 5. A compound according to claim 1, methyl 3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate. 6. A compound according to claim 1, n-octadecyl 3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate. 7. A compound according to claim 1, 2- (n-octadecylthio) ethyl 3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate. 8. A compound according to claim 1, N-n-octadecyl-3- (5-tert. - butyl-2,3-dimethyl-4-hydroxyphenyl) propionamide. 5 0B8 13/1 16 5 9. A compound according to claim 1, N, N'-bis [3- (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionyl] piperazine. 10. Use of a compound according to claim 1 for stabilizing organic material. 11. Use according to claim 10, characterized in that a compound according to claim 2 is used. 12. Use according to claim 10, characterized in that a compound according to claim 3 is used. 13. Use according to claim 10, characterized in that that a compound according to claim 4 is used. 14. Use according to claim 10, characterized in that a compound according to claim 5 is used. 15. Use according to claim 10, characterized in that that a compound according to claim 6 is used. 16. Use according to claim 10, characterized in that that a compound according to claim 7 is used. 17. Use according to claim 10, characterized in that that a compound according to claim 8 is used. 18. Use according to claim 10, characterized in that that a compound according to claim 9 is used. 509813/1165 19. Use according to any one of claims 10-18, characterized in that that the organic material is a polyolefin. 20. Use according to claim 19, characterized in that that the polyolefin is polypropylene. 21. Use according to one of claims 10-20, characterized in that in addition 0.01-2 % (weight) of a thio-costabilizer of the formula _ used, wherein R is alkyl with 6-24 carbon atoms and η 1-6. 22. Use according to one of claims 10-20, characterized in that in addition 0.01-5% (weight) of one Light stabilizer used. 509813/1165