JPS6118592B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates to stabilized organic material compositions. More specifically, the stabilizer compound according to the invention has the following formula: [In the formula, when R ₁ and X represent a sulfur atom,
R ₂ is each independently an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkylthioethyl group having 4 to 27 atoms in the chain, or an alkyl group having 4 to 27 atoms in the chain. represents a polyoxyalkylene group, Z and X represent an oxygen atom or a sulfur atom, R ₂ has the same meaning as R ₃ when X is an oxygen atom, and R ₃ has the following formula: (In the formula, R ₄ is an alkyl group having 1 to 4 carbon atoms, R ₅ is an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms, and R ₆ is a hydrogen atom. or a lower alkyl group having 1 to 4 carbon atoms, and A represents a covalent carbon bond or a linear or branched lower alkylene or alkylidene group having 1 to 8 carbon atoms] It is an ester represented by In the above, R ₁ and R ₂ have 1 carbon atom
~30 alkyl groups, such as methyl, n-butyl,
It may also be an n-octyl, tertiary-dodecyl, n-octadecyl, n-tetracosanyl or n-triacontanyl group. Preferably, R ₁ and R ₂ are each independently an alkyl group having 1 to 18 carbon atoms, such as methyl, n-butyl, n-dodecyl or n
-It is an octadecyl group. Most preferably, for use in stabilizing polyolefins, such as polypropylene, polyethylene and olefin copolymers, R ₁ and R ₂ are each independently alkyl having from 8 to 18 carbon atoms, especially from 12 to 18 carbon atoms. It is the basis. R ₁ and R ₂ may be cycloalkyl groups having 5 to 12 carbon atoms, such as cyclopentyl, cyclohexyl or cyclododecyl groups. R ₁ and R ₂ can also be alkylthioethyl groups with 4 to 27 atoms in the chain, such as 2-methylthioethyl, 2-(n-octylthio)ethyl and 2-
(Tetracosanylthio)ethyl. R ₁ and R ₂ are as follows: R ⁰ (OCnH ₂ n)h or R ⁰
(OCH ₂ CHR′) h (wherein R ⁰ is a carbon atom number of 1 to 18
, n is 2 to 4, R' is a hydrogen atom, a methyl group, or an ethyl group, and h is 1 to 3), and has 4 to 27 atoms in the chain. It may be an alkyl polyoxyalkylene group. R ₅ is a straight-chain or branched lower alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl,
Isopropyl, n-butyl, tert-butyl, tertiary
-amyl or n-octyl group. R ₄ and
R ₅ may also be a cycloalkyl group having 5 to 6 carbon atoms, such as a cyclopentyl or cyclohexyl group. Preferably, R ₅ is a branched alkyl group having 3 to 8 carbon atoms, such as isopropyl, 2-butyl, 3-butyl, 2-amyl, 3-amyl, 2-octyl or 3-octyl. It is an octyl group. Most preferably R ₅ is a tert-butyl group. R ₄ is a straight-chain or branched alkyl group having 1 to 4 carbon atoms, such as a methyl, ethyl, isopropyl or tert-butyl group. Most preferably R ₄ is a methyl group or a tert-butyl group. Preferably R ₆ is a hydrogen atom or has 1 carbon atom
~3 alkyl groups, such as methyl, ethyl or n-propyl groups. Most preferably R ₆ is a hydrogen atom or a methyl group. A is a linear or branched lower alkylene or alkylidene group having 1 to 8 carbon atoms, such as methylene, ethylene, 2,3-propylene, trimethylene, 1,1-dimethylethylene, 1,1-butylidene, 2 -Methyl-1,1-propylidene or 1,1-octylidene group. Preferably A is a straight chain alkylene group having 1 to 3 carbon atoms, ie a methylene, ethylene or trimethylene group. Most preferably A is a methylene or ethylene group. A may also be a covalent carbon bond. The ester as a stabilizer in the present invention is an appropriately substituted propanol and the following formula: It is produced from the acid represented by, its acid halide or acid anhydride, or the corresponding lower alkyl, preferably methyl ether, by a general esterification production method. The reaction may be carried out in the presence or absence of a solvent, under normal or reduced pressure and at elevated temperatures, e.g. 50-200°C, using known catalysts for esterification or transesterification reactions. Occurs in the presence of Acid halide derivatives of the aforementioned acids are prepared by conventional methods using standard halogenating agents such as thionyl chloride, phosphorus trichloride and phosphorus oxychloride. Lower alkyl esters, generally methyl esters, are conveniently obtained by acid-catalyzed reaction of the aforementioned acids with lower alcohols such as methanol. When A is an ethylene group or a substituted ethylene group, a lower alkyl ester is obtained by reacting a substituted phenol () with an acrylic ester as shown below: (In the formula, R ₄ , R ₅ , R ₆ have the meanings expressed above, R ₇ represents a hydrogen atom, a carbon atom, or a lower alkyl group having 1 to 6 carbon atoms, and R represents a carbon atom number. 1 to 4 alkyl groups).
Methods of this type are described, for example, in US Pat. No. 3,247,240 (April 9, 1966) and US Pat.
It is stated in the No. 1 specification (January 16, 1968). The ester intermediates shown above can also be obtained by reacting substituted phenols with acrylonitrile as shown below: The reaction is similar to that described in US Pat. No. 3,121,732 (February 18, 1964). For acids where A is a methylene group, the reaction formula follows: (In the formula, M is an alkali metal, such as sodium or potassium, and R ₈ and R ₉ are lower alkyl groups having 1 to 8 carbon atoms, or the above two groups taken together with a nitrogen atom form a morpholine or hyperidine ring. forming). Preferably R ₈ and R ₉ are methyl groups. In the reaction outlined in the previous section, formaldehyde is replaced by a higher aldehyde, e.g.
With butanal or n-octanal,
This results in the preparation of acids of the formula where A is 1,1-alkylidene. Acids of the formula can also be prepared by reacting a substituted phenolate anion with a suitable halogenoalkane carboxylic ester, amide or nitrile in which A is a straight or branched alkylene of 2 to 8 carbon atoms. You can get it. Many of the di- and trialkylated phenols () intended for use as starting materials for making the compounds of this invention are known compounds that are commercially available. The preparation of 2,6-diisopropyl-3-methyl-phenol and 2,6-c-tert-butyl-3-methylphenol is described in Japanese Patent No. 7015491. The method for producing 2,3-dimethyl-6-tert-butylphenol is described in the book by J. Parc, Reveilleux de l'Instituil Française.
Revue de LInstitut
Francais du Pelrole), 1960 edition, No. XV, page 693. Other substituted phenols are
It is obtained by selective alkylation of the phenolic starting material using an acidic catalyst such as p-toluenesulfonic acid and selected olefins such as propylene, isobutylene and 2,4,4-trimethylpentene-1. Particularly in the ester according to the invention, R ₅ is preferably in the ortho position to the hydroxyl group. The substituted propanol intermediate was reacted with the sterically hindered phenoalkanoic acid derivative according to the following reaction scheme to produce the ester according to the invention: The key atom-substituted propanol intermediates required to make the esters according to the invention are made by several methods. Most conveniently substituted 2-propanols are obtained by first reacting epichlorohydrin with an alcohol or mercaptan in the presence of a base, followed by a second stage reaction with the mercaptan in alkaline conditions. When Z is an oxygen atom, the other reaction sequence is to produce the allyl ether, oxidize the allyl moiety to the corresponding ethylene oxide, and open the ethylene oxide ring with a mercaptide to form the substituted 2-propanol. Consisting of (In the above formula, R ₁ , R ₂ have the meanings already given above, X is a halogen atom, M is a cation, such as lithium, sodium, potassium or ammonium, and A is an anion, e.g. chlorine, bromine or acetate ions, the solvent may be suitable and the oxidizing agent is a peracid, e.g. It is a novel compound which is useful in itself as a chemical intermediate in the production of synergists, extreme pressure additives for lubricants, pest control agents, combustion improvers and the like.Stabilizers in the present invention The vicinal glycol intermediate in which Z is substituted with a key atom, which is an oxygen atom, required when producing an ester, is produced by producing an allyl ether, then oxidizing the allyl group moiety, and converting it into a vicinal glycol via the corresponding ethylene oxide. Narglycol is obtained through the following series of reactions. (In the above formula, X is a halogen atom, M is a cation such as lithium, sodium, potassium or ammonium, the solvent may be suitable and the oxidizing agent is a peracid such as peracetic acid.) Another method for the production of these vicinal glycols that are oxygen atoms involves reacting glycidol with an alcohol or mercaptan in the presence of a base. These substituted vicinal glycols can be used as stabilizers and many other products according to the invention, such as synergists, extreme pressure additives for lubricants, pest control agents, combustion modifiers and the like. It is useful as a chemical intermediate in manufacturing. The esters according to the invention exhibit an excellent stabilizing effect in polypropylene even in the absence of thioester co-stabilizers, such as distearyl β-thiodipropionate (DSTDP). With the addition of the DSTDP co-stabilizer, the stabilizing action of the esters of the invention to protect polypropylene is surprisingly higher than in any case with similar preparations made with previous commercial stabilizer selections. is also excellent. This is very surprising and the economic importance of the esters according to the invention is such that even if the molar concentration of the active sterically hindered phenol from the ester stabilizer according to the invention in polypropylene is
Approximately 2/2 of the molar concentration of sterically hindered phenolic moieties in polypropylene when using commercially available stabilizers.
3 shows an excellent stabilizing effect. It is of great economic importance that small amounts of relatively expensive sterically hindered phenolic moieties are required due to their excellent stabilizing action. The scope of the invention is not limited to the examples that follow, and the effects of the stabilizing action of the esters according to the invention are not necessarily those stated in the explanations or overviews proposed herein. . Although the reasons for the particularly effective stabilizing action of the esters according to the invention are unknown, the molecular structure of these esters allows in some cases an effective utilization of the sterically hindered phenolic moiety of the molecule in polypropylene systems; It is theorized that less sterically hindered phenols must serve an effective stabilizing function. The liquid physical nature of these esters sufficiently facilitates their addition and compatibility with polypropylene systems in the amorphous region where stabilizing action is most needed, while the molecular structure of the esters is It has been found that this structural difference is the reason for the superior action of the esters of the present invention, unlike the stabilizers of the present invention. The ester is preferably a substituted isopropanol having one long alkyloxy group and one long alkylthio group in positions 1 and 3 respectively or two long alkylthio groups in positions 1 and 3 for use in stabilizing polyolefins. derived from. The esters have a centrally active sterically hindered phenol moiety with soluble hydrocarbon substituents pointing in opposite directions, resulting in particularly efficient and effective stabilization of the polypropylene. The esters are also derived from substituted vicinal 2,3-propanediols having a long chain alkyloxy or alkylthio group at the first carbon atom. Such esters connect each of two adjacent carbon atoms with one sterically hindered phenol moiety and provide a particularly good concentration of active groups leading to very good stability of the polypropylene. Has one soluble hydrocarbon group. There are four types of stabilizers according to the prior art that are strictly different from the esters of the present invention. In the first type, many of the sterically hindered phenolic moieties are surrounded by groups to which small hydrocarbons are attached.
These materials are generally solid materials with relatively high melting points and correspondingly limited solubility in aliphatic hydrocarbon solvents. One type of this group is 1,1,1-butanetolyltris[3-(3,5-di-tert-butyl-4-hydroxyphenyl)probionate] (U.S. Pat.
No. 3,285,855, Example 7) has a high molar concentration of sterically hindered phenol moieties and small soluble hydrocarbon chains (e.g. showed excellent stabilizing effect. The above compounds exhibit an even better stabilizing effect at low molar concentrations. See U.S. Pat. No. 3,644,482. In the second type, a sterically hindered phenol moiety is attached to a single bonded long chain hydrocarbon group, optionally containing a foreign atom such as a sulfur atom.
(See US Pat. Nos. 3,330,859 and 3,441,575.) In the third type, two sterically hindered phenol moieties are attached to an alkylene group, optionally containing a foreign atom such as a sulfur atom. (U.S. Pat. No. 3,644,482) In a fourth type, mixed esters derived from a mixture having a sterically hindered phenolic alkanoic acid and an alkyl group substituted with an alkanediol are substituted with an alkylene chain as an adjunct to a lower alkyl group. resulting in a liquid stabilizer with two sterically hindered phenol moieties attached to. (U.S. Patent No. 3779945) The best ester compounds of types 1 to 4 above and U.S. Patent Nos. 3285855 and 3758549
Example 12, No.
Shown in the table. The Estes according to the invention exhibits a better stabilizing effect in polypropylene at a concentration of only 40% of the best esters according to the prior art. In plastics, the lower the amount of additive required, the better in order to maintain their physical properties. These types of stabilizers are represented schematically as follows. However, in the formula represents a sterically hindered phenolic moiety, - represents a short bonded chain or branched group, and 〓 represents a long solubility which may optionally contain an oxygen or sulfur atom as a heteroatom. represents a hydrocarbon group. Comparing these schematic diagrams, it is clear that the esters according to the invention are structurally and sterically different and cannot be easily deduced or predicted from compounds according to the prior art. Esters according to the invention

[Formula] and

Substrate materials of particular interest are olefin polymers such as polyethylene, polypropylene, olefin copolymers and mixtures thereof. Polypropylene is particularly well stabilized with the compounds according to the invention. Stabilizers according to the present invention are particularly useful in high temperature end uses as well as in the protection of polymeric compositions that are processed at high temperatures. These stabilizers (wherein R ₄
is a methyl group, R ₅ is a tertiary butyl group, and R ₆ is a hydrogen atom or a methyl group). They tend to be particularly resistant. Polymer compositions, especially polypropylene, containing esters according to the invention, where Z is a sulfur atom, are surprisingly stable to light compared to compositions with high performance prior art antioxidants. This remarkable observation allows for the identification of the esters according to the invention and further provides them with special uses. The esters have an excellent stabilizing effect not only on polymerized supports, such as polyolefins, polyacetals, polyesters and polyamides, but also on non-polymerized supports, such as thermally decomposed and actinically decomposed oils. For many purposes, it is advantageous and necessary for the stabilizer additive to be a solid, preferably white, and somewhat high melting material.
This is especially true for polymerization substrates where small amounts of additives are isolated and then precisely weighed and added to each of the polymer systems to be stabilized. The compounds according to the invention also show that an equally good physical form for the stabilizers is an essentially colorless, high-boiling liquid. These substances are stable, have the necessary structural formula to increase their solubility and compatibility with the support to be stabilized, and have a high melting point solid or a low melting semi-solid. Their completely liquid nature provides a particularly convenient method for adding them to support systems. Thus, the compound can be precisely metered and controlled using standard liquid pumping equipment into the substance to be stabilized. The esters of the invention find particular application in the stabilization of liquid substrates, such as oils, and in the stabilization of polymerizable substances where liquid pumping equipment can be readily used when adding the stabilizer during the polymerization process. is expected to do so. The sterically hindered hydroxyphenyl alkanoates according to the invention are stabilizers for organic substances that are normally subject to thermal and oxidative decomposition. Materials so stabilized include the synthetic organic polymers shown below. Poly-α-olefins (including copolymers of α1-olefins such as ethylene/propylene copolymers): polyethylene, polypropylene, cross-linked polyethylene, polybutylene Dienes: polybutadiene, polyisoprene and other monomers such as polyurethanes and polyamides: polyhexamethylene adipamide and polycaprolactam polyesters: polyethylene terephthalate polycarbonates, polyacetals, unsaturated polyesters, polystyrene, polyethylene oxide and their copolymers: copolymers of ptadiene and styrene High impact polystyrene and acrylonitrile, including coalescing, putadiene and/or styrene (ABS),
Copolymers formed by copolymerization of SAN Natural or synthetic rubber: ethylene/propylene/diene copolymer (EPDM) and chlorinated rubber Polyphenylene oxide and its copolymers, formed by polymerization of vinyl halides or unsaturated and polymerizable compounds with vinyl halides (e.g. vinyl esters, α,β-unsaturated ketones,
and plasticized polyvinyl chloride. Other substances stabilized by the compounds of the invention are listed below. That is, aliphatic ester type lubricants: di(ethylhexyl) azelate and synthetic ester lubricants, pentaerythritate tetracabroate, etc. Polyester type spinning lubricants, oils derived from animals and plants: linseed oil, Fat, beef tallow, lard, peanut oil, cod liver oil, castor oil, palm oil, corn oil, cottonseed oil, etc. Hydrocarbon substances: gasoline, mineral oil, fuel oil, drying oil, inorganic lubricating oil, cutting fluid, wax, resin etc. Fatty acid salts: Soap, etc. Alkylene glycol: β-methoxyethylene glycol, methoxytriethylene glycol,
Triethylene glycol, octaethylene glycol, dibutylene glycol, dipropylene glycol, etc. Materials of particular interest are olefin polymers such as polyethylene, polypropylene, polybutylene and ethylene/vinyl acetate. Polypropylene is particularly well stabilized with the esters according to the invention. Generally, the stabilizers of the present invention are used in an amount of about 0.01 to about 5% by weight of the composition to be stabilized, although the proportions will vary depending on the particular substrate material and application. An advantageous range is about 0.05 to about 2%, especially about 0.1 to about 1%.
It is. To be added to the polymerized substrate, the stabilizer may also be incorporated before or after polymerization by conventional processing operations such as dry blending, using a compounding extruder, or using a hot roll mill. The composition may then be extruded, compressed, injected, molded or otherwise fabricated into films, fibers, filaments, molded articles, and the like. The thermally stable nature of these compounds is advantageous in stabilizing the polymer against degradation at the high temperatures encountered during such processing. However, the useful life of polymerizable materials is also extended beyond processing by these stabilizers. Stabilizers may also be dissolved in a suitable solvent and sprayed onto the surface of films, textiles, filaments, etc. to provide effective stabilization. These compounds can also be used in combination with other additives listed below. For example, sulfur-containing esters such as distearyl β-thiodipropionate (DSTDP) in an amount of 0.01 to 2% by weight of the organic material, pour point depressants, corrosion and rust inhibitors, dispersants, emulsifiers, antifoaming agents. agents, carbon black, accelerators and other chemicals used in rubber compounds, plasticizers, color stabilizers, antistatic agents, antiblocking agents, antislip agents, surfactants, fillers, organophosphites, organothio Phosphites, heat stabilizers, UV stabilizers, antiozonants, dyes, pigments, metal deactivators, metal chelating agents, dysites, etc. combination of these substances,
In particular, combinations of sulfur-containing esters, phosphites and/or UV stabilizers often yield better results for certain purposes than would be expected due to the properties of the individual compositions. The following formula: (wherein R is an alkyl group having from 6 to 24 carbon atoms, and n is an integer from 1 to 6), when combined with the stabilizer of the present invention, exhibits significant effects in certain respects. It is a useful co-stabilizer. Particularly advantageous compounds of this type are dilauryl β-thiodipropionate and distearyl β-thiodipropionate. The aforementioned co-stabilizers are present in an amount of 0.01 to 2% by weight of the organic substance, and preferably
0.1-1% by weight is used. In addition to the abovementioned additives which can be used in combination with the compounds according to the invention, it is particularly advantageous to also use light stabilizers. Light stabilizers are organic substances
It is used in amounts of 0.01 to 5% by weight, preferably 0.1 to 1% by weight. Examples of light stabilizers are shown below for illustrative purposes. Ultraviolet absorbers and photoprotectants Examples of 2-(2'-hydroxyphenyl)-2H-benztriazole derivatives include those having the following substituents. That is, 5′-
Methyl, 3',5'-di-tert-butyl-, 5'-tert-butyl-, 5'(1,1,3,3,-tetramethyl-
butyl)-, 5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-, 3'-sec-butyl-5'-tert Butyl-, 3′-
(α-methylpenzyl)-5′-methyl-, 3′-
(α-Methylbenzyl)-5'-methyl-5-chloro-, 4'-hydroxy-, 4'-methoxy-, 4'-
Octoxy, 3′,5′-di-tertiary amyl, 3′-
Methyl-5'-carbomethoxyethyl- or 5-
Chlor-3',5'-di-tertiary amyl- or 4'-tertiary octyl derivative. 2,4-bis-(2'-hydroxyphenyl)-
Examples of derivatives of 6-alkyl-s-nariazine include 6-ethyl-, 6-undecyl- or 6-
Examples include heptadecyl derivatives. As derivatives of 2-hydroxy-penzophenone, 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-penzyloxy-4,2',4'-trihydroxy- or 2′-hydroxy-4,4′-
Dimethoxy derivatives can be exemplified. As a derivative of 1,3-bis-(2'-hydroxy-penzoyl)-benzene, 1,3-bis-
(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1,3-bis-(2'-hydroxy-4'-octoxy-benzoyl)-benzene and 1,3-bis-(2'-hydroxy -4'-dodecyloxy-benzoyl)-benzene can be exemplified. Optionally substituted esters of benzoic acid include phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-
(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butyl phenyl ester, octadecyl ester or 2-methyl- of 3,5-di-tert-butyl-4-hydroxybenzoic acid. 4,6-di-tert-butyl phenyl ester and 4-(3,5-di-tert-butyl phenyl ester)
Butyl-4-hydroxybenzoyloxy-3,
Examples include alkyl esters of 5-di-tert-butylbenzoic acid. As an acrylic ester, α-cyano-
β,β-Diphenyl acrylic acid ethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-β-
Examples include methyl or butyl ester of methyl-p-methoxy-cinnamic acid and N-(β-carbomethoxy-vinyl)-2-methyl-indoline. As nickel compounds, 2,2'-thio-
Nickel complexes such as the 1:1 and 1:2 complexes of bis-4-(1,1,3,3-tetramethylbutyl)-phenol; bis optionally with other ligands such as 2-ethylcaproic acid. -{2-hydroxy-4-(1,1,3,3-tetramethyl-
nickel complexes such as the 2:1 complex of (butyl)-phenyl}-sulfone; nickel dibutyl-dithiocarbamate, 4-hydroxy-3,5-di-tert-butyl-benzylphosphonic acid monoalkyl esters such as methyl, ethyl or butyl Examples include nickel salts of esters, nickel complexes of (2-hydroxy-4-methylphenyl)-undecyl-ketone oxime and nickel 3,5-tert-butyl-4-hydroxy-benzoate. Examples of oxalic acid diamide include 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,
2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-5-tert-butyl-2'-ethyl-oxanilide, 2-ethoxy-
2′-ethyl-oxanilide, N,N′-bis-(3
-dimethylaminopropyl)oxalamide, o
- and p-methoxy and o- and p-ethoxy-di-substituted oxanilides, and 2
-Ethoxy-5-tert-butyl-2'-ethyl-oxanilide and 2-ethoxy-2'-ethyl-5,4'-
A mixture with di-tert-butyl-oxanilide can be exemplified. Examples of sterically hindered amines include 4-benzoyloxy-2,2,6,6-tetramethylbiveridine, 4-stearoyloxy-2,2,6,6
-tetramethylpiperidine, bis-(2,2,
6,6-tetramethylpiperidyl) sebacic acid and 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazase spiro[4,
5] Decane-2,4-dione can be exemplified. The objects listed below by way of example are the compounds according to the invention useful as stabilizers that have been discussed so far. 1-n-hexadecyloxy-3-n-octadecylthio-2-propyl-3-(3,5-di-
Tertiary-butyl-4-hydroxyphenyl)propionate 1,3-bis(n-octadecylthio)-2-
Propyl (3,5-di-tert-butyl-4-hydroxyphenyl) acetate 1-n-dodecyloxy-3-n-hexadecylthio-2-propyl-(2,3-dimethyl-4
-Tertiary butyl-4-hydroxyphenyl) acetate 1,3-bis(cyclohexylthio)-2-propyl-3-(3-methyl-5-tert-butyl-
4-Hydroxyphenyl)propionate 1-[2-(2-octadecylthio)ethyloxy]-3-n-octadecylthio-2-propyl-3-(3-methyl-5-tert-butyl-4-hydroxyphenyl ) Propionate 1,3-bis(n-hexadecylthio)-2-
Propyl-3-(2-methyl-5-tert-butyl-
4-Hydroxyphenyl)propionate 1-n-octadecyloxy-3-n-octadecylthio-2-propyl-3,5-di-tert-butyl-4-hydroxybenzoate 1-n-dodecyloxy-3-n- Dodecylthio-2-propyl-3,5-di-tert-butyl-4
-Hydroxyphenyl acetate 1-n-dodecylthio-3-n-octadecyloxy-2-propyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate 1-methylthio-3-n-dodecylthio -2-
Propyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-methylpropionate 1-n-octyloxy-3-n-octadecylthio-2-propyl 3-(3-methyl -5-tert-butyl-4-hydroxyphenyl)-2,2-
Dimethylpropionate 1-n-hexadecyloxy-2,3-bis(3,5-di-tert-butyl-4-hydroxyphenylacetoxy)propane 1-[2-(n-octadecylthio)ethylthio]- 2,3-bis(2,3-dimethyl-5-tertiary amyl-4-hydroxyhydrocinnamoyloxy)propane 1-cyclohexylthio-2,3-bis[4-
(3-Methyl-5-tert-butyl-4-hydroxyphninyl)butyloxy]propane 1-n-dodecyloxy-2,3-bis(3,
5-di-tert-butyl-4-hydroxybenzooxy)propane 1-n-dodecylthio-2,3-bis(3,5
-di-tert-octyl-4-hydroxyhydrocinnamoyloxy)propane 1-n-octadecyloxy-2,3-bis[6-(3,5-di-tert-butyl-4-hydroxyphenyl)caproyloxy] Propane 1-cyclododecyloxy-2,3-bis(2
-Methyl-5-tert-butyl-4-hydroxyhydrocinnamoyloxy)propane The present invention will be explained in more detail by the examples that follow, but are not intended to limit the invention in any way. Temperatures are expressed in degrees Celsius unless otherwise noted. In addition, among the following Examples, Examples 1 to 11 are methods for producing esters, which are stabilizers in the present invention, and Examples 13 to 21 are related to the stabilized compositions of the present invention. Example 1 1-n-hexadecyloxy-3-n-dodecylthio-2-propyl-3-(3-methyl-5
-Tertiary butyl-4-hydroxyphenyl)-
Propionate (a) Methyl-3-(3-methyl-5-tert-butyl-4-hydroxyphenyl)-propionate 13.8g, 1-n-hexadecyloxy-3-
A mixture of 25.0 g of n-dodecylthio-2-propanol and 0.045 g of lithium hydride was heated to 135 g under normal pressure.
Heated at a temperature of ~160°C for a total of 10.5 hours and then an additional 8 hours at 150°C and 4 mm Hg vacuum. Cool the reaction mixture and add 0.5 g of glacial acetic acid.
ml to neutralize the catalyst. The resulting crude product was clarified by filtration and chromatographed sequentially through silica gel and alumina using a mixture of benzene and heptane to elute the product to obtain the final purified product. The pure product fractions were combined, the solvent removed and dried at 125° C. and 0.3 mm Hg vacuum to constant weight. The ester product was obtained as a colorless liquid (Stabilizer No. 1). C ₄₅ H ₈₂ O ₄ S: C H S (%) Theoretical value 75.15 11.49 4.46 Actual value 75.10 11.61 4.44 Example 2 1-n-dodecyloxy-3-n-dodecylthio-2-propyl-3-(3-methyl -5-Tertiary butyl-4-hydroxyphenyl)-propionate (a) The same amount of 1-n-dodecyloxy-3-n-dodecylthio-2-propanol was added to the 1-n-hexane described in Example 1. When used in place of decyloxy-3-n-dodecylthio-2-propanol, the ester of the above product is obtained as a colorless oil. (Stabilizer No. 2) C ₄₁ H ₇₄ O ₄ S: C H S (%) Theoretical value 74.25 11.27 4.83 Actual value 74.54 11.47 5.02 (b) n-dodecyl glycidyl ether and 1-n
-dodecyloxy-3-ndodecylthio-2-
Preparation of Propanol 186.3 g (1.0 mol) of n-dodecanol and 323.8 g (3.49 mol) of epichlorohydrin were placed in a flask connected to a vacuum azeotrope collector. To the stirred and reacted mixture was then added 2.45 g (22.4 mmol) of tetramethylammonium chloride catalyst. While applying a vacuum to the mixture using a water pump,
Heat to 40-50℃ and add sodium hydroxide 50.9%
88 g (1.1 mol) of the aqueous solution were added over 2 hours. A distillate consisting of water and epichlorohydrin was collected over a period of 5 hours until no more water distilled out. cool the reaction mixture, and
The desired glycidyl ether was initially formed when fed in VPC. The crude product was further purified by treatment with 15 g of filter cell. The mixture was filtered and the solid residue was washed once with 120 ml of epichlorohydrin. Pour the clear yellow liquid into 50ml of saturated sodium sulfate, 50ml of sodium dihydrogen phosphate 10w/v% and ethanol.
Extracted with a solution consisting of 100 ml. The aqueous layer was discarded and the organic layer was stripped of volatile components in a rotary film evaporator, first at a water pump vacuum and finally at high vacuum until no epichlorohydrin remained. The desired glycidyl ether was obtained containing a small amount of unreacted n-dodecanol. n-dodecyl glycidyl ether 50.0g (0.21
mole) and n-dodecyl mercaptan 41.7g
(0.21 mol) were mixed in a nitrogen atmosphere. Add 50.9% sodium hydroxide to the mixture while stirring and cooling.
% aqueous solution (0.21 mol) were added dropwise. This reaction was highly exothermic. After stirring for 3 hours, the reaction mixture became a solid mass. The solid crude product was washed with 500 ml of water and dried under vacuum to give an off-white solid. This substituted isopropanol was further purified by recrystallization with ethanol to obtain a white solid having a melting point of 39-43°C. Example 3 1,3-bis(n-dodecylthio)-2-propyl 3-(3-methyl-5-tert-butyl-4-
Hydroxyphenyl)propionate (a) Methyl 3-(3-methyl-5-tert-butyl-
4-Hydroxyphenyl)propionate
20.5g, 1,3-bis(n-dodecylthio)-
2-propanol 34.1g and lithium hydride
0.059g of the mixture was heated at 120-150°C for 12.5 hours at normal pressure and then heated for a further 3 hours at 150°C and 0.1
Heated under reduced pressure. The reaction mixture was cooled and treated with 0.5 g of glacial acetic acid to neutralize the catalyst. When the crude product is purified by chromatography, the product ester is obtained as a colorless oil.
The compound was then dried at 100° C. and 0.2 mm vacuum to a constant weight (stabilizer No. 3). C ₄₁ H ₇₄ O ₃ S ₂ : C H S (%) Theoretical value 72.50 10.98 9.44 Actual value 72.57 11.04 9.48 (b) Preparation of 1,3-bis(n-dodecylthio)-2-propanol 85.8% potassium hydroxide solution 137.3g (2.1mol)
was prepared in a mixture of 200 ml water and 200 ml ethanol with cooling. Add n-dodecyl mercaptan to the stirred solution over 30 minutes with continued cooling.
404.8g (2.0mol) was added dropwise. 92.5 g (1.0 mol) of epichlorohydrin was added to the resulting gelatinous material at 0-5°C, and stirring was continued at this temperature for an additional 5 hours. The resulting product was collected by filtration and washed with water until neutral. The product was further washed or recrystallized from methanol. Dry substituted isopropanol: melting point 50-55℃. Example 4 1,3-bis(n-dodecylthio)-2-propyl 3-(2,3-dimethyl-5-tert-butyl-4-hydroxyphenyl)-propionate 1-n-hexadecyl in Example 1 The same amount of 1,3-bis(n-dodecylthio) instead of oxy-3-n-dodecylthio-2-propanol
-2-propanol and methyl 3-(3-methyl-5-tert-butyl-4-hydroxyphenyl)
Instead of propionate, the same amount of methyl 3-
Using (2,3-dimethyl-5-tert-butyl-4-hydroxyphenyl)propionate, the above-mentioned ester was obtained as a viscous oil (stabilizer No. 4). C ₄₆ H ₇₆ O ₃ S ₂ : C H S (%) Theoretical value 72.76 11.07 9.25 Calculated value 73.01 11.27 9.45 Example 5 1,3-bis(n-dodecylthio)-2-propyl 3-(3,5-di -Tertiary butyl-4-hydroxyphenyl)propionate Methyl 3-(3-methyl-5 in Example 1)
-tert-butyl-4-hydroxyphenyl)propionate in place of the same amount of methyl 3-(3,5-
Using di-tert-butyl-hydroxyphenyl) propionate, the above ester was obtained as a light yellow oil (stabilizer No. 5). C ₄₄ H ₈₀ O ₃ S ₂ : C H S (%) Theoretical value 73.27 11.18 8.89 Calculated value 73.21 11.42 8.90 Example 6 1,3-bis(n-dodecylthio)-2-propyl 3,5-di-3 Butyl-4-hydroxyphenylacetate Methyl 3-(3-methyl-5 in Example 1)
If the same amount of methyl 3,5-di-tert-butyl-4-hydroxyphenyl acetate is used in place of tert-butyl-4-hydroxyphenyl) propionate, the above ester is obtained as a pale yellow liquid. (Stabilizer No. 6). C ₄₃ H ₇₈ O ₃ S ₂ : C H S (%) Theoretical value 73.03 11.12 9.07 Calculated value 72.99 11.61 9.07 Example 7 1-n-octadecyloxy-2,3-bis(3-methyl-5-tert-butyl -4-Hydroxyhydrocinnamoyloxy)propane (a) A mixture of 27.6 g (0.08 mol) of 1-n-octadecyloxy-2,3-propanediol and 0.144 g (0.018 mol) of lithium hydride was placed in a flask under a nitrogen atmosphere. and heated to about 90° C. with stirring. 44.6 g (0.176 mol) of methyl 3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate is then added and the reaction is stirred and heated at atmospheric pressure at 125-140° C. for about 5 hours; Heating was continued for an additional 3.5 hours at 130-135° C. under 2 mm vacuum. The reaction mixture was then cooled and acidified by adding 2.4 g (0.04 mol) of glacial acetic acid. A 21.3 g aliquot of the crude product was placed in a Hickman molecular still and heated at 160-180° C. with a 20 micron vacuum to remove unreacted starting ester. The final product was obtained by dissolving 17 g of the residue in 25 ml of benzene and passing the solution through a bed of 340 g of alumina. The pure product fractions were combined, stripped of solvent and dried at 80° C. and 0.1 mm vacuum to constant weight. The product obtained was a clear viscous liquid (Stabilizer No. 7). C ₄₉ H ₈₀ O ₇ : C H (%) Theoretical value 75.34 10.32 Calculated value 75.53 10.27 (b) 1-n-octadecyloxy-2,3-propanediol Pour n-octadecyl into a 500 ml three-necked flask equipped with a distillation collector. 54.1 g (0.20 mol) of decanol and 200 ml of toluene were added. The mixture was heated under reflux and the distillate was collected until it was clear. Cool the mixture and add 10.8 g (0.20 g) of sodium methoxide
mol) was added. Distillation was carried out again and continued until the distillation temperature reached 110°C. 137 ml of distillate was collected. An additional 150 ml of fresh toluene was added. Heat the mixture under reflux and add 14.8 g of glycidol
(0.20 mol, 13 ml) was added over 30 minutes. The reaction mixture immediately became a clear orange solution and was heated at reflux for an additional 2 hours. The reaction mixture was cooled to room temperature and neutralized with glacial acetic acid. After removing the precipitated sodium acetate, the toluene solvent was evaporated and the desired product was obtained in a crude yield of 68 g.
(quantitative yield) as a residue. Further purification of 1-n-octadecyloxy-2,3-propanediol by vacuum distillation resulted in an 18% yield of pure material: boiling point 215 ~
220℃/0.25mm reduced pressure. Example 8 1-n-dodecylthio-2,3-bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamoyloxy)propane (a) 1-n-octadecyloxy-2 in Example 7, When an equivalent amount of 1-n-dodecylthio-2,3-propanediol was used in place of 3-propanediol, the ester described above was obtained as a colorless syrup (stabilizer No. 8). C ₄₃ H ₆₈ O ₆ S: C H S (%) Theoretical value 72.43 9.61 4.50 Calculated value 72.19 9.39 4.52 (b) 1-n-dodecylthio-2,3-propanediol Add n-dodecyl mercaptan to 300 ml flask
60.7 g (0.30 mol) and 0.63 g (0.015 mol, 5 mol %) of lithium hydroxide-hydrate catalyst were added.
The mixture was stirred and heated to 90-100°C. 33.3 g (0.45 mol) of glycidol was added dropwise to the stirred solution over 4.25 hours. The reaction mixture was incubated for an additional 21 hours at 90~
Stir and heat at 95°C. The product was isolated by vacuum distillation yielding 41.3 g (50
%) obtained: boiling point 158-178℃/0.05-0.15mm
Decompression. C ₁₅ H ₃₂ O ₂ S: C H S (%) Theoretical value 65.15 11.67 11.60 Calculated value 65.05 11.85 11.46 Example 9 1-n-octadecylthio-2,3-bis(3
-Methyl-5-tert-butyl-4-hydroxyhydrocinnamoyloxy)propane Methyl 3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate 15.2 g (0.06 mol) and 1-n-octadecylthio-2 , 10.14 g (0.027 mol) of 3-propanediol were heated to about 80° C. and stirred until the mixture was homogeneous. Add sodium methylate (0.292g, 0.0054mol),
The resulting mixture was then heated for 5 hours at 125-145°C at atmospheric pressure and further heated at 135-145°C under 0.5-5 mm vacuum.
It was heated at 145°C for 3 hours. The reaction mixture was then cooled and the catalyst neutralized with 0.5 g (0.008 mol) of glacial acetic acid. The crude product was purified by first removing the bulk (1.0 g) of the unreacted starting material ester under high pressure in a Hitukuman molecular still, followed by chromatography from silica gel using benzene as the developing solvent. I went there. Remove the solvent from the product compartment and heat to 125°C and
Drying to constant weight under 0.1 mm vacuum yielded 9.4 g of the desired ester product as a viscous syrup (stabilizer No. 9). C ₄₉ H ₈₀ O ₆ S: C H S
(%) Theoretical value 73.82 10.12 4.02 Calculated value 73.82 10.12 4.09 Example 10 1-n-octadecylthio-2,3-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)propane Example Methyl 3-methyl-5-tertiary in 9
equivalent of methyl 3,5-di-tert-butyl-4 in place of butyl-4-hydroxyhydrocinnamate
- With hydroxyhydrocinnamate, the above ester was obtained as a crystalline white solid: mp 51-54°C (stabilizer No. 10). C ₅₅ H ₉₂ O ₆ S: C H S (%) Theoretical value 74.95 10.52 3.64 Calculated value 74.98 10.72 3.85 Example 11 1-n-octadecyloxy-2,3-bis(3,5-di-tert-butyl- 4-Hydroxyhydrocinnamoyloxy)propane Methyl 3-methyl-5-tertiary in Example 7
equivalent of methyl 3,5-di-tert-butyl-4 in place of butyl-4-hydroxyhydrocinnamate
- With hydroxyhydrocinnamate, the abovementioned ester was obtained as a crystalline white solid: mp 55-58°C (stabilizer No. 11). C ₅₅ H ₉₂ O ₇ : C H (%) Theoretical value 76.34 10.72 Calculated value 76.35 10.41 Example 12 Unstabilized polypropylene powder [Profax 6501 from Hercules
was thoroughly mixed with 0.2% by weight of the indicated stabilizer compound. A sample of polypropylene was also prepared containing 0.1% by weight of a similar stabilizer and 0.3% by weight of distearyl β-thiodipropionate (DSTDP). Heat the mixed substance at 182℃ for 10 minutes2.
The stabilized polypropylene was kneaded in the roll mill and then rolled out of the mill into a sheet and cooled. The rolled polypropylene sheet was cut into specimens and heated at 218℃ and 19.25Kg/cm ² in a hydraulic press machine.
(275 psi) for 7 minutes. The resulting 0.635 mm (25 mil) thick disk samples were tested for resistance to accelerated aging at 150° C. in a forced draft oven. Material is considered defective when the disc sample shows the first signs of decomposition (eg, cracks or brown edges). The results are shown in Table 1 below.

【table】

【table】

[Table] Lumu
Although the esters according to the invention are very effective without thioester costabilizers, they exhibit a significant effect in the presence of the costabilizers mentioned above. The ester of the invention with a concentration of 0.2% by weight is
More effective in almost all cases than the control ester listed above and tested at the 0.5% concentration level, and based on the molar concentration of the sterically hindered phenolic moiety as shown in Example 12. More effective than anything else. The 0.2% concentration of ester according to the present invention was tested at 0.5% concentration in polypropylene according to US Pat.
It is more effective than the best 2-(n-octatecylthio)ethyl ester described in No. 3285855. At a concentration of 40% of the stabilizer according to the prior art, the ester according to the invention shows excellent behavior. Compared to liquid mixed ester (Example 5, U.S. Pat. No. 3,779,945), 0.635 mm to 1.02 mm (25
Even thinner layers (from 100 mils to 40 mils) containing esters according to the invention can be used and the material has superior stabilizing effects compared to previous liquid mixed esters, especially in the presence of thioester co-stabilizers. It showed a positive effect. Example 13 Test specimens were treated with various esters according to the invention at 0.2
% by weight and 0.5% by weight of 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chloro-2H-benzotriazole as a co-stabilizer;
Prepared exactly as described in Run 12 except that stabilized polypropylene was included.
The results of the accelerated aging test in a forced drying oven at 150°C are shown in Table 2 below.

[Table] Example 14 Example except that the kneaded polypropylene sheet was cut into small pieces and compressed on a hydraulic machine under a pressure of 19.25 Kg/cm ² (275 psi) at 218°C for 3 minutes.
The specimens were prepared exactly as described in 12. The resulting 0.127 mm (5 mil) thick sheet was exposed to fluorescent sunlight in a dark light environment at a wavelength of 585 mμ, which is a measure of the stabilizing protection conferred by the stabilizers present in the polypropylene. was tested by the discovery of carbonyl absorption in the infrared absorption spectrum of . The time required for failure to occur is expressed as the time required for carbonyl absorption to reach a value of 0.5. Such values are associated with a reduction in the physical properties of polypropylene films to unacceptable standards. The results are shown in the table below.

[Table] Example 15 500 g of unstabilized nylon-6,6 (Zytel 101 from Dupont) pellets was added to a kitchen aid mixer.
Prepare it. With stirring, 1,3-bis(n-octadecylthio) dissolved in 20 ml of methylene chloride.
Slowly add a 0.5% solution (based on the weight of the nylon) of -2propyl 3-(5-tert-butyl-2,3-diethyl-4-hydroxyphenyl)propionate. Sodium hypophosphite (0.5 gm) is dissolved in 20 ml of water and the antioxidant is added and after most of the methylene chloride has evaporated, the solution is slowly added to the nylon pellets with stirring. The stabilized pellets were dried at 80°C for 4 hours under reduced pressure of less than 1 mmHg. Similar operations were performed using a solution of 1-cyclohexylthio-2,3-bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamoyloxy)propane as another sample. Polyamide formulation 0.635cm (1/4″) at 315.6℃
The pellets are extruded through a die to form rods, which are then water-cooled and cut into pellets. Use a 1.905 cm (3/4") Brabender extruder fitted with a nylon screw. Dry the pellets at 80°C for 4 hours at less than 1 mm Hg vacuum. Dry pellets at 57.75 Kg/cm ² (6000 psi). Compressed for 4 minutes at pressure and temperature of 290℃ to a thickness of 0.127
Compression molded into a 5 mil (mm) film. The film is oven aged in a forced draft oven at 150°C and samples are removed periodically. The specific viscosity is determined at 25° C. using a 1% formic acid solution. The sample stabilized with the above stabilizer required a long aging time to reduce its viscosity to half that of the unstabilized sample. Example 16 An unstabilized Hi, Impact, polystyrene resin was treated with 0.01% by weight of 1-n-octadecyloxy-3-n-hexadecylthio- based on the weight of the resin.
Dry blend with 2-propyl 5-tert-butyl-2,3-dimethyl-4-hydroxy-phenylacetate. Another sample is 1-n-octadecyloxy-2,3-bis(3,5-di-tertiary amyl-4-hydroxyhydrocinnamoyloxy)
Repeat the same operation using propane. Next, add resin
Extrusion compounding using a 254 cm (1 inch) 24/1 = L/D extruder at melt temperature (260 °C) and at a temperature of 163 °C and a pressure of 140 Kg/cm ² (2000 psi) for 7 minutes. Compress to form a sheet with a uniform thickness of 2.54 mm (100 mils). Cut the sheet into 5.08cm
A circular test plate measuring 5.08 cm (2 inches x 2 inches). The test plates were then aged in an oven at 80°C and tested using a Hunter Color Difference Meter.
Color was measured periodically using Model) D25. Polystyrene samples stabilized with the stabilizers described above develop an undesired color change (yellow color) substantially later than the time at which undesired color changes occur in unstabilized samples. Example 17 Unstable linear polyethylene (HiFax 4401) was dissolved in methylene chloride with 1-n-hexadecyloxy-3-n-dodecylthio-2-propyl 3- in an amount of 0.2% by weight of the weight of the substrate.
(3-Methyl-5-tertiary octyl-4-hydroxyphenyl)propionate and solvent mixed and then vacuum dried. Next, the above operation is repeated using 1-n-hexadecylthio-2,3-bis(2,3-dimethyl-5-tert-butyl-4-hydroxy-hydrocinnamoyloxy)propane as another sample. Then the L/D ratio is 24:
232.2℃ using 1.905cm (3/4″) extruder
Extrude the resin at a temperature of ASTM after each extrusion
Measure the melt flow rate of the resin sample by Test D-1238. It has been found that polyethylene stabilized with the above compounds suffers from less melt flow rate variation than unstabilized polyethylene. Example 18 An aliquot of SBR emulsion (500 ml of 20% SBR emulsion, commercially available in Texas, USA as Synpol 1500) containing 100 g of rubber previously stored under nitrogen atmosphere is placed in a beaker and vigorously Stirred. Adjust the pH of the emulsion to 10.5 with 0.5N-NaOH solution. Add 50 ml of 25% NaCl solution to the emulsion solution. Add a 6% NaCl solution adjusted to pH 1.5 with hydrochloric acid in small portions while stirring vigorously. When the pH reaches 6.5, the rubber begins to coagulate and the addition is done slowly to ensure uniform stirring. Addition of weakly acidic 6%-NaCl solution
It will end when the pH reaches 3.5. Stir the solidified brittle rubber slurry at a pH of 3.5 for 1/2 hour. Pass the coagulated gum through cheese fibers and wash with distilled water. After three consecutive washes with fresh distilled water, the coagulated rubber was dried to constant weight, first at 25 mm Hg vacuum and then under high pressure (<1 mm Hg) at 40-45°C. Dry rubber (25 g) was heated in a Brabender mixer at 125°C under nitrogen atmosphere and added to it with 1,3-(n-
dodecylthio)-2-propyl-3-methyl-5-
Add 0.1% by weight of tertiary amyl-4-hydroxyphenyl acetate with mixing. The above operation is repeated using 1-n-dodecylthio-2,3-bis(3,5-dioctyl-4-hydroxyhydrocinnamoyloxy)-propane as another sample. A portion of the rubber is aged in a furnace at 100℃. Various gelling times are measured on the rubber. Rubbers stabilized with the above compounds gel less than non-stabilized samples. Example 19 0.1% of the acidic scavenger dicyandiamide
1-n-dodecyloxy-3-n-octadecylthio-2-propyl 5-tert-octyl-2,3-dimethyl-4 to 50 g of polyacetal resin containing
- Add 0.2% by weight of hydroxyphenyl acetate and mix for 7 minutes at 200°C in a Brabender Plastirecorder. 24.5Kg/cm ² of milled molded product for 90 seconds
(350 psi) to 215° C. into a 1.016 mm (40 mil) sheet and quickly cooled by cold pressure at 24.5 Kg/cm ² (350 psi). The same operation was repeated using 1-n-octyloxy-2,3-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-propane as another sample. The stabilized sheet was then remolded at 21 Kg/cm ² (300 psi) for 3 minutes at 215°C with contact pressure for 2 minutes to form a 3.81 cm x 5.715 cm x 3.175 mm (1.5″ x
1.5" x 125 mils). The blacks are aged in an oven at 60°C and the weight loss is measured over time until the weight loss of the specimen reaches 4%. It takes longer for the sample to reach this 4% weight loss than for the unstabilized sample. EXAMPLE 20 1-n-octyloxy-
3-n-octadecylthio-2-propyl 3-
Dry mix 1.0% by weight (5-tert-butyl-2,3-dimethyl-4-hydroxyphenyl) propionate. Multifilaments with a denier of 60/10 are melt spun at a melt temperature of 290°C and cold drawn from 3 to 1. As another sample 1-
The same operation as above is repeated using dodecyloxy-2,3-bis(2,3-dimethyl-4-hydroxyphenylacetoxy)-propane. The drawn fibers are wound into skeins and aged in a furnace at 140°C. Stabilized materials have better tensile strength after 24 hours than non-stabilized materials. Example 21 Stabilized high temperature lubricating oil was mixed with 1,3-bis(-
cyclohexylthio)-2-propyl 3-(5-
0.05% by weight of tertiary-butyl-2,3-dimethyl-4-hydroxyphenyl)-propionate and 1-n-octadecylthio-2,3-bis(3,5-di-tertiary) as another sample. Butyl-4
-Hydroxyphenylacetoxy)propane
They are prepared by incorporating 0.05% by weight of each separately into a lubricant consisting of diisoamyl adipate.
The stabilized composition meets US standard Mil-I-7808°C.
The lubricants are compared with unstabilized lubricants heated in the presence of air and metal catalysts at 175° C. according to the test method described in . After 72 hours, the control containing no stabilizer contains more sludge and is more viscous than the stabilized lubricant.

Claims (1)

[Claims] 1. Organic substances susceptible to thermal, oxidative and ultraviolet decomposition by the following formula: [In the formula, when R ₁ and X represent a sulfur atom,
R ₂ is each independently an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkylthioethyl group having 4 to 27 atoms in the chain, or an alkyl group having 4 to 27 atoms in the chain. represents a polyoxyalkylene group, Z and X are an oxygen atom or a sulfur atom, R ₂ has the same meaning as R 3 when X is an oxygen atom, and R ₃ has _the following formula: (In the formula, R ₄ is an alkyl group having 1 to 4 carbon atoms, R ₃ is an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms, and R ₆ is a hydrogen atom. or a lower alkyl group having 1 to 4 carbon atoms, and A represents a group represented by a covalent carbon bond or a linear or branched lower alkylene or alkylidene group having 1 to 8 carbon atoms] A stabilized organic substance composition comprising a compound represented by the following as a stabilizer.