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United States Patent 0 Patented Apr 3,657,322 United States Patent 0 Patented Apr. 18, 1972 2 group. A second (lower)alkyl group (R) is optionally 3,657,322 present either (a) in the other position ortho to the hy CYCLOALIPHATIC DIALKYLHYDROXYPHENYL droxy group or (b) meta to the hydroxy group and para ALKANOATES to the ?rst (lower)alkyl group. Referred are the di(low Martin Dexter, Briarclilf Manor, and David H. Steinherg, Bronx, N.Y., assignors to Ciba-Geigy Corporation, er)alkyl-p-phenolic groups, e.g., R is (lower)alkyl, and Ardsley, N.Y. although not so limited, the (lower)alkyl groups on the No Drawing. Continuation-impart of application Ser. No. p-phenolic group are preferably branched groups such as 372,083, June 2, 1964. This application June 26, 1967, t-butyl. Other arrangements, however, such as for ex Ser. No. 648,998 ample a 3-t-butyl~6-methyl-p-phenolic group or a 3,5-di Int. Cl. C07c 69/76 10 methyl-p-phenolic group are included. US. Cl. 260-473 S 3 Claims It will be appreciated from the foregoing description associated with Formula I that the mono- and polyhydric alicyclic alcohols from which the esters of the present in ABSTRACT OF THE DISCLOSURE vention are derived will contain a fundamental alicyclic Alkylhydroxyphenylalkanoic acid esters of mono- and ring skeleton of from 4 to 12 carbon atoms, i.e., em polyhydric alicyclic alcohols, prepared by known esteri brasive of the carbon skeletons of from cyclobutane to ?cation or transesteri?cation procedures, are stabilizers cyclododecane. This ring skeleton may be considered as of organic material subject to oxidative deterioration. composed of (a) several divalent units of Formula I or (b) of (i) one or more such units and (ii) one or more 20 divalent aliphatic chains. CROSS REFERENCE In a ?rst embodiment of this invention, the alicyclic alcohol is monohydric and the novel ester derived there This is a continuation-in-part of copending applica form will contain one of the above de?ned divalent alikyl tion Ser. No. 372,083, ?led June 2, 1964, now abandoned. hydroxyphenylalkanoyloxyalkylene units, hereafter “di DETAILED DESCRIPTION 25 valent ester unit” and one divalent aliphatic chain of up This invention pertains to alkylhydroxyphenylalkanoic to 11 carbon atoms, hereafter “divalent aliphatic chain.” acid esters of mono- and polyhydric alicyclic alcohols, The divalent aliphatic chain in the case of esters derived and to compositions otherwise subject to oxidative dete from monohydride alcohols will contain at least three rioration stabilized by the incorporation therein of such carbon atoms, preferably 4- to 5, the two valence bonds 30 esters. being on different, non-adjacent carbon atoms of the In particular, the present invention relates to alicyclic chain. Each of the two valence bonds of this divalent ali compounds having from 4 to 12 carbon atoms in the ali phatic chain is joined to one of the two bonds of the di cyclic ring and consisting of: valent ester unit, thereby constituting an alicyclic ring (a) From 1 to 6 divalent alkylhydroxyphenylalkanoyl having at least 4 carbon atoms in the ring skeleton. Thus, oxyalkylene units of the structure: 35 for example, the novel esters derived from the monohy dric alcohol cyclopentanol will contain (a) a single di valent ester unit of the de?ned structure wherein that por (ower)1 a 1k y 1 0 tion of the structure —-(CxI-I2x_1)< is methylidyne, x thus being 1, and (b) the single divalent aliphatic chain 40 tetramethylene, whereas the ester derived from cyclo (I) hexanol will contain the identical divalent ester unit but the divalent aliphatic chain pentamethylene. The novel esters derived from 1,4-dimethylcyclohexane-l-ol, on the wherein: other hand, will contain (a) a single divalent ester unit 45 x is l or 2, and of the de?ned structure wherein —(C‘xH2x_1)< is ethyl R is hydrogen or lower alkyl; and idyne, x thus being 2, and (b) the single divalent aliphatic chain 3-methylpentamethylene. The compounds thus em (b) From 0 to 3 divalent aliphatic chains of from 1 braced by this ?rst embodiment may be represented by the to 11 carbon atoms; both of the free valences of any such formula: divalent aliphatic chain being bound to the same or to 50 separate divalent alkylhydroxyphenylalkanoyloxyalkylene units of the above structure, and each of the free valences (lower) alkyl 0 of any alkylhydroxyphenylalkanoyloxyalkylene unit, inde HO (lower) alkylene -C-O-(Cxl-l2x_1)[l alkylene (Ia) pendent of the other free valence of the same unit, be ing bound either to a separate divalent alkylhydroxyphen 55 ylalkanoyloxyalkylene unit of the above structure or to a free valence of a divalent aliphatic chain. By the term “alky” and derivations thereof employ ‘In a second embodiment of this invention, the alicyclic ing the root “alk,” such as “alkylene,” or “alkylidene,” alcohol from which these esters are derived is polyhydric, containing from 2. to 6 hydroxy groups in the ring skele “alkanoy ” and the like, is intended a group containing 60 a branched or straight chain hydrocarbon chain of from ton, the number of divalent ester units in the ?nal ester 1 to 20 carbon atoms inclusively. Representative of such corresponding to the number of hydroxy groups in the alkyl groups are thus methyl, ethyl, propyl, butyl,.t-bu alcohol from which it is derived. The polyhydric alicyclic tyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, elcosyl alcohol may be fully hydroxylated, i.e. each of the carbon and the like. When the term “alky ” is herein quali?ed by 65 atoms making up the ring skeleton bears a hydroxy group, the designation “(lower),” there is intended a branched in which case the esters derived from such an alcohol will or straight chain hydrocarbon of from 1 to about 6 car consist of from four to six divalent ester units and no di bon atoms. valent aliphatic chains, each of the divalent ester units It will be observed in Formula I that the alkanoyl por being bound to two other such units. For example, the tion of these alicyclic esters bears a (lower) alkyl-p-phe 70 esters derived from the inositols will contain six divalent nolic group. This phenolic group exhibits at least one units as de?ned above wherein -(CxH2X_1)< is methyl (l0wer)alkyl group, in a position ortho to the hydroxy idyne, x thus being 1. The compounds thus represented by . 3,657,322 3 4 this ?rst aspect of this second embodiment may be repre While the foregoing alcohols can exist in the form of sented by the formula: different stereoisomers, e.g., optical isomers and/or geo metric isomers, this does not affect the properties of the ?nal esters. Thus either a mixture of such isomers or the separated isomers themselves can be subjected to the procedures herein described without substantially 3' (1b) altering the properties of the ?nal esters obtained. These alkylhydroxyphenylalkanoic acid esters of mono wherein y has a value of from 4 to 6. and polyhydric alicyclie alcohols are stabilizers of organic ‘In another aspect of this second embodiment, the poly 10 material normally subject to oxidative deterioration. Ma hydric alicyclic alcohol from which these esters are de terials which are thus stabilized according to the present rived are partially hydroxylated, i.e., some but not invention include synthetic organic polymeric substances all of the ring carbon atoms making up the ring skeleton such as vinyl resins formed from the polymerization of bear a hydroxy group. The hydroxy groups of such par vinyl halides or from the copolymerization of vinyl ha tial hydroxylated alicyclic alcohols may (a) be on ad 15 lides with unsaturated polymerizable compounds, e.g., jacent carbon atoms; (b) on nonadjacent carbon atoms or vinyl esters, a,/3-unsaturated ketones, u,?-unsaturated al (c) a combination of the foregoing. As an example of the dehydes and unsaturated hydrocarbons such as butadienes ?rst of these, (a), the alcohols cyclopentane-1,2-diol; and styrene; poly-ot-ole?ns such as polyethylene, poly cyclohexanol-l,2-diol and cyclooctane-l,2-diol may be propylene, polybutylene, polyisoprene and the like, in mentioned. The esters of the present invention derived 20 cluding copolymers of poly-a-ole?ns; polyurethanes such from these three alcohols will thus each contain two di as are prepared from polyols and organic polyisocyanates; valent ester units as previously defined wherein polyamides such as polyhexamethylene adipamide; poly -—(CxH2x_1)< in each is methylidyne, one valence bond esters such as polymethylene terephthalates; polycarbon of one of these units being joined to one valence bond of ates polyacetals; polystyrene, polyethyleneoxide; and the other with the remaining valence bond of each of the copolymers such as those of high impact polystyrene con units being bound to the divalent alicyclic chains tri taining copolymers of butadiene and styrene and those methylene, tetramethylene and hexamethylene, respective formed by the copolymerization of acrylonitrile, butadiene ly. ‘Such compounds may thus be represented as follows: and/or styrene. Other materials stabilized according to 11 the present invention include lubricating oil of the ali phatic ester type, e.g., di-(2-ethylhexyl)-azelate, penta go@ ( lower) alkylene ~C-0- (0x334?alkylene erythritol tetracaproate and the like; animal and vegetable derived oils, e.g., linseed oil, fat, tallow, lard, peanut oil, R o cod liver oil, castor oil, palm oil, corn oil, cotton seed oil (Is) and the like; hydrocarbon material such as gasoline, both (lower)al.kyl/ 35 natural and synthetic diesel oil, mineral oil, fuel oil, dry ing oil, cutting ?uids, waxes, resins and the like, fatty As examples of the second class, (b), of partially acids such as soaps and the like.
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