DE2064951A1 - Benzoates as stabilisers for organic - materials - Google Patents

Abstract

Benzoates as stabilisers for organic materials. Stabilising agents consists of new cpds. of formula (I) opt. in polymerised form (where A is a group of formula -OCnH2n- or -(OCxH2x)y-; n is >=3; x and y are each 2 or 3; the alkyl groups each contain 1-6C atoms). Cpds. (I) and their polymers are used for stabilising organic materials against degradation by ultraviolet light, esp, polyalkenes such as polypropylene. Lubricating oils, animal and vegetable oils, hydrocarbons, waxes, resins soaps and fatty acids can also be stabilised.

Description

Benzoate Monomers The present invention relates to new benzoate monomers, which contain sterically hindered phenolic groups. The polymers of such monomers can be used alone or in combination with other stabilizers to stabilize organic compounds are used, which normally decompose through are subject to ultraviolet light.

The monomers according to the invention have the following general formula: wherein the di-remainder A where n is a number equal to 3 or greater and x and y are 2 or 5, and in which the sum of the carbon atoms of the (lower) alkyl radicals is at least 4.

In the general formula above, the phenolic group has two Alkyl substituents. An alkyl substituent is in the ortho position to the hydroxy group and a second alkyl group is either (a) in the other ortho position to the Hydroxy group or (b) in the meta position to the hydroxy group and in the para position to the first alkyl group. The di- (lower) -alkyl-p-phenol groups are preferred, in which the alkyl groups are branched and, for example, tert-butyl or isopropyl groups represent. However, other arrangements are also possible, e.g.

the 3-tert. -Butyl-6-methyl-4-hydroxyphenyl group, the 3, 5-diisopropyl-4-hydroxyphenyl group, the 3, 5-di-tert. -butyl-4-hydroxyphenyl group, the 3-isopropyl-5-methyl-4-hydroxyphenyl group or the 3, -di-n-hexyl-4-hydroxyphenyl group.

The term "(lower) alkyl" means a group having a straight chain or branched hydrocarbon having 1 to 6 carbon atoms. Examples such alkyl groups are methyl, ethyl, isopropyl, n-propyl, tert-butyl or n-hexyl groups.

The monomers described above can be prepared by the following two processes: 1) Esterification of hydroxyalkyl-α, β-unsaturated esters with benzoic acids bearing a hindered phenolic group represented by the following equation: Although benzoic acid can be used in this method, as indicated in the equation, it is preferred to use acid halides, and particularly the acid chlorides of benzoic acid.

Non-limiting examples of hydroxy-alkyl-α, ßunsaturated Esters are the following: CH2 = C (CH3) CCO (C3H6) OH hydroxypropyl methacrylate CH2 = C (CH3) CO (OCH2-CH2) 2OH diethylene glycol monomethacrylate.

Benzoic acids containing sterically hindered phenolic groups, and their acid chlorides are extensively described in the patent literature, e.g. in U.S. Patent No.

3,285,855. Examples of useful benzoic acids are: 3,5-diethyl-4-hydroxy-benzoic acid 3,5-diisopropyl-4-hydroxy-benzoic acid, 3,5-di-tert-butyl-4-hydroxy-benzoic acid, 3-methyl-5-tert-butyl-4-hydroxy-benzoic acid 3-ethyl-5-tert-butyl-4-hydroxy-benzoic acid, 3-methyl-6-tert-butyl-4-hydroxy-benzoic acid 3-methyl-6-isopropyl-4-hydroxy-benzoic acid, 3,6-diethyl-4-hydroxy-enzoic acid, 3,6-di-tert-butyl-4-hydroxy-benzoic acid and the acid chlorides of the above benzoic acids.

2) esterification of α, β-unsaturated acids and hydroxy-alkyl benzoates as represented by the following equation; Similar to the first method, as shown in the equation, acids can be used, but acid halides, and particularly acid chlorides, are preferred.

An example of a useful α, B-unsaturated acid chloride is the following: CH2 = C (CH3) COCl nethacryloyl chloride The hydroxyalksrlbenzoates are preferably produced by addition of epoxies, preferably ethers; srlen- and propylene oxide on benzoic acids, as indicated under the above process 1) This procedure is a well-known reaction that is described in Houben-Weyl, "methods of organic chemistry, Vol. 14/2, pages 436 to 446 (Georg-Thieme-Verlag, Stuttgart, 1962).

Examples of monomers according to the invention are: The present invention also relates to the polymers made from the monomers described above and their use as stabilizers for organic materials which are normally subject to decomposition by ultraviolet light. Another embodiment of the present invention is a process for the preparation of such polymers, which consists in that (a) a monomer which is derived from a, β-unsaturated acid and a benzoic acid which contains a sterically hindered phenolic group, and ( b) a free radical initiator converts under polymerization conditions.

The initiator is a compound which turns into an alkyl or aryl radical can dissociate. Accordingly, according to the present invention, for manufacture of polymeric stabilizers used a one-step process, eliminating the hitherto known multi-step processes are avoided.

An essential reactant in the preparation of the polymeric stabilizers is thus an initiator which reacts with a monomer in such a way that the polymeric stabilizers are obtained directly, ie in one step. These initiators include azo-nitriles and azo-derivatives, which dissociate into alkyl or aryl radicals at temperatures which are suitable for the polymerization reactions. The best known example of an azo-nitrile is 2,2'-azobisisobutyronitrile and the dissociation reaction that provides the required alkyl radical goes as follows: Other azo-nitriles and azo-derivatives which can be used in the reaction with the monomers described above to produce the desired products according to the invention are described by J. Brandrup and EH Immergut, Polymer Handbook (John Wiley and Sons) 196, pages II -3 to II-14 and include z. B. a: 2-cyano-2-propyl-azo-formamide 2,21-azo-bis-isobutyronitrile 2,2'-azo-bis-methylpropionitrile 1,1'-azo-bis-1-cyclobutanenitrile 2,21-azo -bis-2-methylbutyronitrile 4,4'-azo-bis-4-cyanopentanoic acid 1,1'-aso-bis-1-cyclopentanenitrile 2,2'-azo-bis-2-methylvaleronitrile 2,2'-azo-bis -2-cyclobutylpropionitrile 1,1-azo-bis-1-cyclohexane-nitrile 2,2'-azo-bis-2,4-dimethylvaleronitrile 2,2'-azo-bis-2,4,4-trimethylvaleronitrile 2.2 '-Azo-bis-2-benzylpropionitrile 1,1'-azo-bis-1-cyclodecanenitrile azo-is- (1-carbomethoxy-3-methylpropane) phenyl-azo-diphenyl methane phenyl-azo-triphenyl methane azo-bis-diphenyl methane 3 -Tolyl-azo-triphenylmethane.

Certain other peroxgdirritiators are in a similar manner with the Preparation of the polymeric stabilizers according to the invention useful, the Usable perozyd initiators are the ones that are capable of immediate action Alkyl or aryl radicals to decompose. The alkyl or aryl radical becomes either by instantaneous decomposition or by a rearrangement reaction of the primary decomposition products the peroxide compound formed.

Of the peroxides, for example, the aliphatic acyl peroxides are most useful and a preferred aliphatic peroxide is acetyl peroxide. The decomposition of this compound to alkyl radicals can be described as follows: Reaction II follows reaction I momentarily. In the presence of iodine, only CH3I is obtained; which is evidence of the instantaneous formation of the methyl radical. In addition to acetyl peroxide, lauryl peroxide and decanoyl peroxide, the preferred peroxides and other aliphatic acyl peroxides containing up to 18 carbon atoms, are also suitable as initiators for the polymerization of the above monomers. Such peroxide compounds include propionyl peroxide, butyryl peroxide, isobutyryl peroxide, oyclobutane acetyl peroxide, heptanoyl peroxide, caprylyl peroxide, cyclohexane acetyl peroxide, nonanoyl peroxide, myristoyl peroxide, stearoyl peroxide and the like.

Other groups of peroxides that can be used are Ketone peroxides and aldehyde peroxides. It has been found that when you can do the above Peroxides used only a partial polymerization of the benzoate monomers themselves revealed, indicating that the alkyl radicals are instantaneous during decomposition were formed. However, the ketone peroxides and the aldehyde peroxides generally gave lower yields of the polymer stabilizers and some yellow-colored ones were obtained Polymers, which indicates that in addition to the polymerization also oxidation of the sterically hindered phenolic group occurred.

The polymers of the present invention include homopolymers of the above described monomers and copolymers thereof with other ethylenically unsaturated Monomers. The polymerization of the monomers can take place in bulk, in solution, in in the suspension or in the emulsion according to well known methods. The preferred method of polymerization is solution polymerization using from solvents such as benzene, toluene, xylene and other aromatic solvents or chlorinated solvents such as chloroform, tetrachlorethylene and the like and initiators, as described above, in amounts between 0.01% and 2%, based on the weight of the monomers. The polymerization temperatures depend on the initiator and are generally between 40 and 100 ° C.

It was also found that when carrying out the polymerization the solvent advantageously through the use of either iistearyltbiodipropionate or dilauryl thiodipropionate could be replaced. These connections are in general known as t'Synergistics' as they include the effects of antioxidants of the polymeric benzoates according to the invention. If you have either distearyl thiodipropionate or dilauryl thiodipropionate as a solvent in the polymerization of the above If the monomers mentioned are used, two important advantages are achieved: (1) the separation the solvent after polymerization is avoided and (2) solidifies the benzoate polymer / synergist mixture at room temperature after polymerization to a white mass that can be easily pulverized. Such powders are preferred over highly viscous or solid polymers as additives. The above Synergists become synergist to one part in proportions of about three parts Used antioxidant.

It should be noted that in the preparation of oligomers, i.

Low molecular weight benzoates that polymerize desirably in the presence of chain transfer agents teln (chain transfer agents), such as mercaptans, is carried out. Examples of such chain transfer agents are alkyl mercaptans, such as n-octyl, n-dodecyl, n-hexadecyl mercaptans et e, comonomers are important in the synthesis of oligomeric and polymeric stabilizers because that they change the physical properties of the polymeric stabilizer can, deho the solubility properties as well as the solid properties of the polymeric stabilizers can be influenced and in addition can be expensive Monomers can be partially replaced by less expensive comonomers.

The copolymerization behavior of the monomers according to the invention is predictable depending on its class of monomer, i.e. a monomer of Acrylatart behaves similarly to an alkyl acrylate. A monomer behaves in a similar way of the fumarate type in the copolymerization is similar to an alkyl fumarate. Comonomers, which are used in the copolymerization with acrylates, boumarates and itaconates are well known to those skilled in the art and are e.g. B. more specifically described by C.E. Schildknecht, Vinyl and Felated Polymers11, John Wiley and Sogs, New York, 1952.

When methacrylate monomers according to the invention are used, are the preferred comonomers alkyl (1 to 24 carbon atoms) acrylates and methacrylates, Styrenes, vinyl esters, butadiene and isoprenes including chlorinated or fluorinated Derivatives of these compounds. If the monomers according to the invention are used, the preferred comonomers are vinyl ethers, vinyl esters, olefins, preferably Propylene, butylene and isobutylene, styrenes and vinyl monomers, especially those containing nitrogen Vinyl pyridine and vinyl pyrrolidone.

The polymers of the present invention are useful as exceptional good ultraviolet light stabilizers for organic materials susceptible to decomposition subjected to ultraviolet light, materials made in accordance with the present Invention stabilized include synthetic, organic, polymeric Substances such as resins formed by the Polymerization of vinyl monomers or through polycondensation reactions, e.g. polyvinyl halides, Polyvinyl esters, polymeric aldehydes and unsaturated hydrocarbons such as polybutadienes, Poly - olefins, such as polyethylene, polypropylene, polybutylene, polyisoprene and the like, including copolymers of poly-aolefins, polyurethanes, such as those made from polyols and organic polyisocyanates; Polyamides, such as polyhexamethylene adipic acid amide and polycaprolactam, polyester, such as polymethylene or polyethylene terephthalate; Polycarbonates; Polyacetals; Polystyrene; Polyethylene oxide; and copolymers, such as high-impact styrene-containing copolymers of butadiene and styrene and those formed by interpolymerization of acrylonitrile, butadiene and / or styrene. Others stabilized according to the invention Materials include a lubricating oil of aliphatic ester types, e.g. di- (2-ethylhexyl) azelate, pentaerythritol tetracaproate and the like; animal and vegetable oils, e.g. flaxseed oil, fat, talc, Siiinal, peanut oil, cod liver oil, castor oil, palm oil, corn oil, Cottonseed oil and the like; Hydrocarbon materials such as gasoline, mineral oil, fuel oil, Drying oil, cutting fluids, waxes, resins and the like; Fatty acids, soaps and the like

In general, the inventive stabilizers are in one Amount of from about 0.05 to about 10 percent by weight of the stabilized composition is used. A particularly preferred range for polyolefins such as polypropylene is about 0.1 to about 1%.

Although the polymers are useful as stabilizers per se its greatest value in the ability to test the effectiveness of a variety of other compounds, especially phenolic compounds, greatly improve those used as stabilizers used for organic materials that are normally subject to decomposition will.

Thus, the compounds according to the invention can be classified as synergistic agents because, when combined with stabilizers, they show the ability to increase the overall stabilization to a degree which by far exceeds that which can be achieved on the basis of the additive properties of the individual components The stabilizers with which the compounds according to the invention can be combined are generally phenolic triazines, phenolic phosphonates, phenolic esters and phenolic hydrocarbons. The various classes of antioxidants are described below: 1) Phenolic compounds of the general formula Q- (CH2) WA where Q means, A means - cR (OooR '') 2 R denotes hydrogen or lower alkyl, R 'denotes lower alkyl, R ″ denotes an alkyl group having 6 to 24 carbon atoms and w is an integer from 1 to 4.

Examples of the compounds shown above are i Di-n-octadecyl- (3-tert-butyl-4-hydroxy-5-methylbenzyl) -malonate Di-n-octadecyl-α- (3-tert-butyl-4-hydroxy-5-methylbenzyl) -malonate, the in the Dutch patent association Er. 6711199, di-n-octadecyl-a, a'-bis (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, which is described in Dutch Patent No. 6803498.

2) Phenolic compounds represented by the following general formula Q-R examples for the compounds shown above are: 2,6-di-tert. butylphenol 2,4,6-tri-tert-butylphenol 2,6-dimethylphenol, 2-methyl-4,6-di-tert-butylphenol, and the like.

3) Phenolic compounds of the following formula: Q-CwH2w-Q 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol) 2,2n-Zethylene-bis- (6-tert-butyl-4-ethylphenol) 4,4'-butylidene-bis (2,6-di-tert-butylphenol) 4,4 '- (2-butylidene) -bis- (2-tert-butyl-5-methylphenol) 2,2'-methylene-bis-t6- (1-methylcyclohexyl) -4-methylphenol 3 and the same.

4) Phenolic compounds of the formula: R-O-Q Examples of such Compounds are: 2,5-di-tert-butylhydroquinone 2,6-di-tert-butylhydroquinone 2,6-di-tert-butyl-4-hydroxyanisole.

5) Phenolic compounds of the formula: QBQ Examples of such compounds are: 4,4'-thio-bis- (2-tert-butyl-5-methylphenol) 4,4'-thio-bis- (2-tert-butyl -6-methylphenol) 2,2'-thio-bis- (6-tert-butyl-4-methylphenol) 6) Phenolic compounds of the formula Examples of such compounds are: Octadecyl (3,5-dimethyl-4-hydroxybenzylthio) acetate Dodecyl (3,5-di-tert-butyl-4-hydroxybenzylthio) propionate 7) Phenolic compounds of the formula wherein T is hydrogen and R or Q have the meanings given above.

Examples of such compounds are: 1,1,3-tris- (3,5-dimethyl-4-hydroxyphenyl) -propane 1,1,3-tris- (5-tert-butyl-4-hydroxy-2-methylphenyl) ) -butane n, 1, 5, 5-tetrakis- (3'-tert -butyl-4 ydroxy-6 -methylplienyl) -np ent an 8) Phenolic compounds of the formula wherein B1, B2 and B3 are hydrogen, methyl or Q, provided that when B1 and B3 are Q, B2 is hydrogen or a methyl group, and when B3 is Q, B1 and B2 are hydrogen or methyl.

Examples of such compounds are: 1,4-di- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tertramethylbenzene 1,3,5-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene.

9) Phenolic compounds of the formula where Z denotes NHQ, -SD or -OQ, D denotes an alkyl group having 6 to 12 carbon atoms or - (CwH2w) -S-R ″.

Examples of such compounds are: 2,4-bis- (n-octylthio) -6- (3,5-di-tert-butyl-4-hydroxyaniline) -1,3,5-triazine 6- (4-Hydroxy-3-methyl-5-tert-butylanilino) -2,4-bis- (n-octylthio) -1,3,5-triazine 6- (Hydroxy-3,5-dimethylanilino) -2,4-bis- (n-octylthio) -1,3,5-triazine 6- (4-Hydroxy-3,5-di-tert-butylanilino) - 2,4-bis- (n-octylthioethylthio) -1,3,5-triazine 6- (4-Hydroxy-3,5-di-tert-butylanilino) -4- (4-hydroxy-3,5-di-tert-butylphenoxy) -2- (n-octylthio) -1,3,5- triazine 2,4-bis- (4-hydroxy-3,5-di-tert-butylanilino) -6- (n-octylthio) -1,3,5-triazine.

The above phenolic triazine stabilizers are described in more detail in U.S. Patent 3,255,191.

10) Phenolic compounds of the formula wherein Z 'is -OQ, -SD or -S- (CwH2w) -SD.

Examples of such compounds are: 2,3-bis- (3,5-di-tert-butyl-4-hydroxyphenoxy) -6- (n-octylthio) -1,3,5-triazine 2,4,6-tris- (r-hydroxy-3,5-di-tert-butylphenoxy) -1,3,5-triazine.

6- (4-Hydroxy-3,5-di-tert-butylphenoxy) -2,4-bis- (n-octylthioethylthio) -1,3,5-triazine 6- (4-Hydroxy-3-methylphenoxy) -2,4-bis- (n-octylthio) -1,3,5-triazine 6- (4-Hydroxy-3-tert-butylphenoxy) -2,4- bis- (n-octylthioethylthio) -1,3,5-triazine 6- (4-Hydroxy-3-methyl-5-tert-butylphenoxy) -2,4-bis- (n-octylthio) -1,3,5-triazine 2,4-bis (4-hydroxy-3-methyl-5-tert-butylphenoxy) -6- (n-octylthio) -1,3,5-triazine 2,4,6-tris- (4-hydroxy-3-methyl-5-tert-butylphenoxy) -1,3,5-triazine 6- (4-hydroxy-3,5-d-tert-butylphenoxy) -2-bis- (n-octylthiopropylthio) -1,3,5-triazine 6- (4-Hydroxy-3,5-di-tert-butylphenoxy) -2,4-bis- (n-dodecylthioethylthio) -1,35-triazine 2,4-bis- (4-hydroxy-3,5-di-tert-butylphenoxy) -6-butylthio-1,3,5-triazine 2,4-bis- (4-hydroxy-3,5-di -tert-butylphenoxy) -6- (n-octadecylthio) -1,35-triazine 2,4-bis- (4-hydroxy-3,5-di-tert-butylphenoxy) -6- (n-dodecylthio) -1,3,5-triazine 2,4-bis (4-hydroxy-3 , 5-di-tert-butylphenoxy) -6- (n-octylthiopropylthio) -1,3,5-triazine 2,5-bis- (4-hydroxy-3,5-di-tert-butylphenoxy) -6- (n-octylthioethylthio) -1,3,5-triazine 2,4-bis- (4-hydroxy-3,5-d-tert-butylphenoxy) -6- (n-dodecylthioethylthio) -1,3,5-triazine.

The phenolic triazine stabilizers described above are more specific described in U.S. Patent No. 3,255,191.

11) Phenolic compounds of the following general formula [Q-CzH2z-COO-C2H2z] p-R "" - (R) 4-p where p is an integer from 1 to 4, z is an integer from 0 to 6 and R '' 'a tetravalent radical, such as an aliphatic hydrocarbon with 1 to 30 carbon atoms, an aliphatic mono- or dithioether with 1 to 30 carbon atoms, or an aliphatic mono- or diether of 1 to 30 carbon atoms.

Examples of such compounds are: Subclass I n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate n-Octadecyl-3,5-di-tert-butyl-4-hydroxyphenyl acetate n-Octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate n-Hexyl 3,5-di-tert-butyl-4-hydroxyphenylbenzoate, n-Dodecyl-3,5-di-tert-butyl-4-hydroxyphenylbenzoate Neo-dodecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate Dodecyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate Ethyl-a- (4-llydroxy-D, 5-di-tert-butylphenyl) -isobutyrate, octadecyl-α- (4-hydroxy-3,5-di-tert-butylphenyl) -isobutyrate Octadecyl α- (4-hydroxy-3,5-di-tert-butylphenyl) propionate subclass IT 2- (n-Octylthio ~ ethyl-3,5-di-tert-butyl-4-hydroxybenzoate 2- (n-octylthio) -ethyl-3,5-di-tert-butyl-4-hydroxyphenyl acetate 2- (n-Octadecylthio) ethyl-3,5-di-tert-butyl-4-hydroxyphenyl acetate 2- (n-octadecylthio) -ethyl-3,5-di-tert-butyl-4-hydroxybenzoate 2- (2-Hydroxyethylthio) ethyl 3,5-d-tert-butyl-4-hydroxybenzoate 2,2'-thiodiethanol-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -acetate diethyl-glycol-bis - [(3,5-di-tert-butyl-4-hydroxyphenyl) -propionatj 2- (n-Octadecylthio) ethyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 2,2'-thiodiethanol-bis-3- (3,5-di-tert. -butyl-4-hydroxyphenyl) propionate Stearamido-N, N-bis- [ethylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] n-Butylimino-N, N-bis- [ethylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 2- (2-StearoylOxyäthylthio) -äthyl-3,5-di-tert-butyl-4-hydroxybenzoate 2- (2-Hydroxyäthylthio) -äthyl-7- (3-methyl-5-tert-butyl-4- hydroxyphenyl) heptanoate 2- (2-stearoyloxyethylthio) ethyl 7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate Subclass III 1,2-propylene glycol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] Ethylene glycol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] neopentyl glycol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) - propionate] Ethylene glycol bis (3,5-di-tert-butyl-4-hydroxyphenyl acetate) Glycerol-1-n-octadecanoate-2,3-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -acetate Pentaerythritol tetrakis-3,3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 1,1, -1-trimethylol-tris-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate sorbitol hexa- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate] 1,2,3-butanetriol-tris- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 2-hydroxyethyl-7- (3-methyl-5-tert-butyl- 4-hydroxyphenyl) heptanoate 2-stearoyloxyethyl 7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate 1,6-n-hexanediol bis - [(3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate].

The above phenolic ester stabilizers of subclasses I, II and III are described in more detail in U.S. - Patents 3,330,859, 3,441,575 and the German patent ....... (patent application P 14 93 779.2).

12) Phenolic compounds represented by the following formula wherein x is 1 or 2.

Examples of such compounds are: dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate Di-n-octadecyl-3-tert-butyl-4-hydroxy-5-methylbenzyl phosphonate Di-n-octadecyl-1- (3,5-di-tert-butyl-4-hydroxyphenyl) ethane phosphonate Di-n-tetradecyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, di-n-hexadecyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate Didocosyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, di-n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate.

It has been found that if the polymer is against oxidative and ultraviolet light decomposition is to be protected, is a solid material, such as polypropylene, polyethylene, nylon, polyacetal, polyurethane, styrene /; ßu t; adiene rubber, Acrylonitrile / butadiene / styrene rubber and the like, the polymeric antioxidant is a relative should be of low molecular weight, i.e. it should be an oligomeric substance that is, a polymer having a molecular weight between about 400 and about 6000. The most useful and the highest stabilizer activities were achieved by the use of oligomers having a molecular weight between about 500 and about 1500.

Polymeric benzoates with a higher degree of polymerization are not Compatible with high molecular weight polymers and therefore with substrates this type is less effective.

It has also been found that when this is against ultraviolet light and polymeric material to be protected against oxidative decomposition not a solid material, but a liquid or a semi-liquid, such as an oil or a Wax, which polymeric stabilizers can have a higher molecular weight, i.e., a molecular weight above about 6000. At a higher degree of polymerization sometimes there are other advantages. Polymeric stabilizers act on oils with a high molecular weight, e.g. additionally as a thickener and as a viscosity index improver.

As already indicated above, the polymers according to the invention are ren Benzoates useful as additives for various polymeric systems. However it is also possible to combine small amounts of a monomer according to the invention with other monomers, form the polymers that must be protected against oxidative decomposition, to mix-polymerize. In such a case, the monomer residue according to the invention forms an integrated part of the polymer system. Small amounts of the present Monomers can therefore with butadiene / styrene, acrylonitrile / butadiene / styrene, ethylene and other monomers are copolymerized to form polymers that counteract the oxidative decomposition must be protected. Thus, depending on the end use monomer residues according to the invention part of an oligomer or one Be polymer system with high molecular weight. The amounts of inventive Monomers that can be copolymerized can be from about 0.05 to about 5 % By weight, and preferably from about 0.1 to about 2 *, vary.

The polymeric stabilizers can be prepared using conventional methods be incorporated into polymers. E.g. the stabilizers can be replaced by a suitable device in the substrates be incorporated how by grinding the stabilizer on hot or cold roller mills in a Banbury mixer or in other well known devices of this type or by incorporation of the stabilizer in a mold powder. The antioxidant can also be in a solution of the Polyolefin material are incorporated, after which this solution is then used for production of films, for wet or dry spinning of fibers, monofilaments and the like. can be used.

General Procedure 1 for Making the Monomers: To a solution 0.1 mol of 2-hydroxyalkyl methacrylate in 30 g of dry pyridine was added slowly a solution of 0.1 mol of 3,5-di- (lower) -alkyl-4-hydroxy-benzoyl chloride in 50 g dry benzene. During the addition, the temperature of the reaction mixture became kept at 50C and then allowed to warm to room temperature. After a The precipitated pyridine hydrochloride was filtered off by filtration for an hour at room temperature separated and the solvent in the filtrate evaporated on a rotary evaporator. The residue was redissolved in ether with 1N hydrochloric acid and Water washed. The ether layer was then dried over sodium sulfate, filtered and the ether evaporates. The residue obtained can be distilled or made from heptane be recrystallized.

General Procedure II for Preparing the Monomers A solution of 0.133 moles of 2-hydroxyalkyl methacrylate in 30 g of methylene chloride became one vigorously stirred solution of 0.133 mol of 3,5-di- (lower) -alkyl-4-hydroxybenzoyl chloride added in 50 g of methylene chloride at room temperature. After the addition is complete the reaction mixture was refluxed for 6 hours, cooled to room temperature and filtered through 100 g of neutral aluminum oxide to remove traces of unreacted Remove acid chloride. After evaporation of the solvent, the obtained Residue unicrystallized twice from a hean / benzene mixture (4/1).

Examples 1 and 2 Benzoate monomers 1 and 2 are prepared by Esterification of the specified acid chlorides and the specified alcohols using the synthetic procedures as described under Methods I and II above.

Examples of Starting Materials Benzoate Monomers means an isopropyl group and means a tert-butyl group.

Example 3 Homopolymers of Monomers of Examples 1 and 2 Homopolymers of monomers of Examples 1 and 2 having an average molecular weight from 1,200 to 40,000 were made. 100 parts of a mixture of 2- (3, -di-tert-butyl-4-hydroxybenzoyloxy) -ethyl methacrylate, prepared according to Example 1, and n-dodecyl mercaptan in a molar ratio, 300 Parts of benzene and part of azobisisobutyronitrile were placed in a vessel under nitrogen completed and polymerized for 17 hours at 700C.

The resulting polymers and oligomers were isolated and characterized. All high molecular weight homopolymers are white brittle powders, whereas the oligomers with molecular weights below 1800 are sticky, highly viscous oils.

Example 4 Alternating interpolymers of monomers of the examples 1 and 2 100 parts of a mixture of equimolar amounts of benzoate monomers Examples 1 and 2 and one of the comonomers given below, 300 parts of chloroform and 1 part of azobisisobutyronitrile were sealed in an ampoule under nitrogen and polymerized at 7000 for 16 hours. The resulting polymer solutions were diluted to 10% solutions in chloroform and in 20 times the amount of methanol failed. The comonomers used were: vinyl ethers, such as methyl, ethyl, Butyl, hexyl, 2-methoxyeth and 2-chloroethyl vinyl ether, vinyl esters such as vinyl acetate, Vinyl propionate, vinyl benzoate and isopropenyl acetate, olefins, such as isobutene, styrene and substituted styrenes such as p-chlorostyrene.

Example 5 Evaluation of the polymeric stabilizers under the action of light (actinic light) In this example, those prepared in Examples 3 and 4 are used Polymers evaluated in terms of stabilization against light. Of the The test is carried out using a device for irradiating with fluorescent sunlight and Ultraviolet Light (FS / BL unit), which is essentially an American design Cyanamid is made up of 40 fluorescent tubes with alternating fluorescent Contains sunlight and ultraviolet light (20 each).

The 0.635 mm (25 mil) samples prepared as described above and applied to white cardboard will be 5.08 cm (2 inches) from the lamps attached remotely on a rotating drum. The panels are exposed in the exposure device (FS / BL unit) until they are sufficiently brittle, so that if you bend them around 1800 they break smoothly.

The stabilized polymers show good resistance as opposed to decomposition by actinic light.

Claims (2)

P a t e n t a n s p r ü c h e 1. Monomer compounds of the general formula wherein the di-radical A is the group denotes in which n is a number equal to 3 or greater and x and y are 2 or 3, and in which the sum of the carbon atoms of the (lower) alkyl radicals is at least 4. 2. Monomers according to claim 1, characterized in that both (lower) alkyl groups are tertiary groups and are in the ortho position to the hydroxy group.