DE1937384A1 - Stabilizers - Google Patents

Description

E. M ο r c k July 16, 1969

Corporation

Darmstadt

Stabilizers

It is known to add organic products such as plastics, fats or oils against thermal or oxidative degradation phono intermetallic compounds as stabilizers .. Particularly so-'suitable phenol derivatives have been solche.verwendet where, two standing ortho to the phenolic hydroxyl positions by groups that are very rough-filling - are substituted, for example, by tertiary butyl groups. The bulky groups in these stabilizer molecules serve to stabilize the pienoxyl radical that is formed during the abstraction of the hydrogen atom of the phenolic hydroxyl group, which acts as an italcal chain breakdown reaction, in such a way that no new chain is added The prerequisite for a good stabilizing effect of phenol derivatives was therefore the presence of a sterically shielded phenolic hydroxyl group.

It has now been found that, surprisingly, the phenol ethers and phenol esters of the formula I

009 8 87/1181

where IL alkyl or alkanoyl ait up to 18 C-Atcucii or Ar,

It ₀ II or optionally substituted by Ar alkyl, alkoxy or alkali oxyloxy with up to 9 carbon atoms,

Ho and Ii ₅ H or alkyl aite up to G carbon atoms,

R ^ II, Ar, Ar-oxy, Ar-thio or optionally through-Ar mono- or polysubstituted alkyl, alkoxy, Alkanoyloxy. Or carbalkoxy with up to 18 carbon atoms,

Rg II, alkyl or alkanoyloxy with up to 6 carbon atoms or optionally by alkyl of up to 3 carbon atoms substituted cyclopentyl or cyclohexyl, and

Ar phenyl or by alkyl, alkoxy, alkanoyloxy odex-carbalkoxy with up to 18 carbon atoms or by cyclopentyl or cyclohexyl, which also by alkyl with up to 3 carbon atoms can be substituted, substituted. Phenyl

means, ■ "■" ■ · - · '. "

with the proviso that R. does not mean Pormyl and that no aromatic nucleus carries more than one tertiary butyl group,

highly effective stabilizers against the thermal and / or are oxidative degradation of organic products.

The invention accordingly relates to the use of compounds of formula I for stabilizing organic products such as plastics, oils or fats.

The subject of the invention is fox-ner a method for stabilizing organic products such as plastics, oils or Fats, which is characterized in that an effective amount of at least one compound of the formula I is added to these products clogs.

1911

1937304

In the compounds of the formula I, Tl., Straight-chain or branched alkyl or alksnoyl ax up to IS Q- ^ atoms or Ar. Examples of alkyl groups that may be mentioned are; Methyl, Ethy 1, η- or iso-propyl, n-, sole-, iso- or tert. Butyl, n-Ainyl, Isoarayl, 2- or 3-n-Pentyl, 2-Methylbutyl- (2), 1-, 2- or 3-n-IIexyl ,, 2-i, ictiiylpontyl- (2), 2- : iethylpentyl- (3), 3-methylpentyl- (3), 2,3-dimothylbutyl- (2), 1-, 2-, 3- or 4-n-ileptyl, 2-methylhexyl- (2), 2-ethylhexyl- (3), 1-, 2-, 3- or 4-h-octyl, 2-methyl-heptyl- (2), 3 -}. Iethylheptyl- (3), 2,4-üi- · methylhexyl- (3), 2-ethylhexyl- (1), 2,3-dimethylhexyl- (3), 2,3,4-trinethylpentyl- (2), 2,3, ^ - trimethylpentyl- iS), 2 , 2,3-trimethyl pentyl - (- i), 2,2 _} 4 ~ triethyl pentyl - (<i =) > i-, 2-, 3-, 4- or 5-nonyl, S-methyloctyl-Cl), 2-methyloctyl- (2), 2-methyloctyl- (3), 2,4-dimethyllieptyl- (l), 2,4-diuethylheptyl- (2), 2-ethyllieptyl- (l), 2-methylhexyl- (l ), 3- "Propylhexyl- (1), decyl, undecyl, iodecyl, 2,2,4-tri-ethyl-3-tert-butylpentyl- {3), 2,2,4,6,6-pentamethyl-heptyl - (4), Tridecyl, Tctradecyl, P; enta- * · decy 1, Ilexadecy 1, 2,2,4,4, 6, G, S-IIeptamethyInony 1- (S- ', 2,2, 6, 6 - »- 'Tetraraetliyl-4-ncopentylheptyl- (3), heptadecyl, octadocyl and the isomers of these groups .

Allcanoyl groups, which are shown as the last R. inirage lcoEiiaen, are for example: Acetyl, Propionyl, Butyryl, Isobutyryl, Valeroyl, Isovaleroyl, Methyläthylacetyl, Frimethylacetyl, Capronoyl, Qnanthoyl, Cäpryloyl, Pelargonooyl, Teutadecanooylecanoyl, Trinoadecanooylecanoyl., Trinoadecanoylecanoyl., Trinoadecanoylecanoyl , Palnitoyl, margarinoyl and stearoyl. Finally, the radical R _{1 can} also be an aryl group Ar. In the stabilizing active ingredients of the formula I, the aryl group Ar denotes the phenyl radical or preferably a phenyl group which is mono- to di-oimally substituted by alkyl, alkoxy, alkanoyl oxy and / or carbalkoxy with up to 18 carbon atoms. Furthermore, phenyl groups can infi- age that. alone or in addition to the groups mentioned by cyclopentyl · - _f or Cyclohcxylreste which in turn v / ieder nit by alkyl 1-3 OB Atoiaen may be substituted, are substituted. Usually, however, no phenyl group bears more than one

00S887 / 1981

1B373B4

Cycloalkyl radical. Examples of such aryl groups Ar are: Metliylphenyl, text. Butylphenyl, Peiityl phenyl, hexylphenyl .., (2-Aethylliexyl) -jplienyl, Ociylphony !, Nonylplienyl, Doaexfylplienyl, .. ", - HeXadecylplietiyl, methoxy or Ae: _{tliQxyphenyl;,} butoxyphenyl, octyloxyphenyl, Nonyloxypheiiyl, dodecyloxyphenyl, Aceii oxy phenyl, PropionyJ.oxypliBiiyl, Butyryloxyphenyl, Valerpyloxypiienyl, Trlmetliylaaetoxy-phenyl, ilethylätiiylaoetoxy-pheayl, CaproiToyloxyphenyl, Capryloyioxypiienyl, Caprinoyloxyphenyl, Lauroyloxyplienyl, palmitoyl oxy phenyl, Stearoyloxyphenyl, Cycloliexylphenyl, (2- or 3-Motliylcyclohexyl -) - phenyl, cyclopentyl · - phenyl, (2- or 3-ethylcyclopentyl) -phenyl, 2-methoxy-4-methylphenyl, 2-Aeei; ox5 ' ^: -4-methylphenyl, 2-methoxy-4-tert. butyl phenyl, 2-isopropyl-4- Ethoxypheny 1,2-tert-butyl-S-aetoxyphonyl, B-metlioxy-S-iS-räetliylcyclohexyl) -5-ethylphenyl, 2-methoxy-4-ethyl-G-tert. "Butylphenyl., 2-acetoxy-3 -tcrt.l »utyl · -5-πetl ^ ylpllenyl ,. ^ 2 ■ -ΛoetQxy-3-ts ~ n ^ αtίllylöycIol ^ exyl) - ^ ff- · xlethyll3hen, yl _ί ■ 2-Apetoxy- -4-ätIiiyl-'6 ~ tert * "Iiirtyi: plienyi _f -2-Me- tl ^ 1-4-net..hoxy- 5-to.rt, _# butyl-. phenyl, 2-i-ethyl-4-a-acetoxy-o-tert-butyl phenyl, 4- * Met, h6xy-2, ΰ -dipentyl phenyl, 4-acetoxy-2,5-di pen ty! phenyl, 2-isop.ropy.l-4-trimethylacetoxy-5-ethoxypiienyl and 2,6-dinethyl-4-ethox3 "phenyl.

It reads the called ₀ lcann Vfasserstoff or optionally selenium by Aisubstituiertes AlUyI, alkoxy or alkanoyloxy with up to 9-G Atöincn mean "As unsubstitüierte alkyl, alkoxy and alkanoyloxy groups, for example: methyl, ethyl, n-propyl, isopropyl, n-, sec.-, iso- and tert * butyl, n-aryl, isoeynyl, tert-pentyl, neopentyl, ii-IIexyl, isohexyl, 2- or 3-methylpeutyl, methoxy, ethoxy, n- or iso-propoxy, ^ n- , Iso, sec. or tert-butoxy, acetoxy, propionyloxy, butyryloxy, isobutyryloxy, valeroyloxy, isovaleroyloxy, methylethyiacetoxy and trimethylacetoxy. Of the groups of this type substituted by Ar, the Ar-substituted lower alkyl groups are of particular importance, for example benzyl, 1- or 2-phonylethyl, methoxybenzyl, tert-butylphenyl-ethyl- (i), 2- (p-butoxyphenyl) -propyl - (2), 2- (p-Acetoxyphenyl) -propyl- (2), 2- (p-Triiaethyl-acotoxyphonyl) -propyl- (2), 2-Mothoxy-

009807/1901 " _BA D ORIGINAL

3- (2-r.ictliylcyclohexyl) -5-methylbeni2yl, 2-ethoxy-3- (2-ucthylcyclohexyl) -5-methylbenzyl ,. 2-Mß-tliqxy-d-Uthyl-6-tert-butylbenzyl, 2-acotoxy-4-ethyl-G-tert-butyl-benzyl, 2-acetoxy-3-tert-butyl-5-ethylbenzyl, 1 , l-bis- (2-methyl-4-acetoxy-5-tert-butylphenyl) -butyl- (3), 1,1-bis- (2-methyl-4-methoxy-5-.; tert -butylphenyl) -butyl- (3), l- (2-Mo-thyl-4. ⁱ -u, e: thOxy-5-tert. butylphenyl) -butyl- (i-)., l- (2-methyl-4- acett) xy-5-tert-butylphenyl) -butyl- (l), 2,5-dipentyl-4-methoxybenzyl and 2,5-dipentyl-4-acetoxybenzyl. .

The radicals IU and R- in the formula I can be identical or different and hydrogen or alkyl with up to 6 carbon atoms mean, in particular methyl, ethyl, n- or iso-propyl, n-, sec.-, tert.- or iso-butyl, amyl, isoamyl, tert-pentyl, Neopentyl, ilexyl, isohexyl or 2- or 3-methyi ^ pentyl.

In addition to hydrogen and the above-described alkyl group, the I residues R. are up to 18 C atoms and Ar groups are not linked to Ar groups via oxygen or sulfur atoms, and also alkoxy, alkanoyloxy and carbalkoxy groups with up to 18 C atoms / ie by Ar mono- or disubstituted, in particular lower alkyl groups of importance. Examples include: phenoxy, methylphenoxy, ethylphenoxy, 2,5-dimethylphenoxy, 4-acetoxyphenoxy, 4-butoxyphenoxy, 4-trimethylacetoxyphenoxy, 4-methoxyphenoxy, 2-methyl-4-mothoxy-5-tert-butylphenoxy, 2-methyi -4-acetoxy-5-tert.butylphenoxy, 2-acetoxy-3-tert.butyl-5-methylphenoxy, 2-methoxy-3-tert.butyl-ΰ-methylphenoxy, 2-metlioxy-3- (2-methylcyclohexyl) -5-methylphenoxy, methoxyphenylthio, acetoxyphenylthio, 4-butoxyfhenylthio, 2-methyl-4-methoxy-5-tert.butylphenylthio, 2-methyl- 4-acetoxy-u-tert-butylphenylthio, 2, δ-dipentyl-4 -methoxy-phenylthio, 2,5-di-pentyl-4-acetoxyphenylthio, methoxy, ethoxy, n- or iso-propoxy, n-, sec-, iso- or tert-butoxy, amyloxy ₈ isoamyloxy _s tQrt.Pentyloxy, · neopentyloxy , 'lloxyloxy, heptyloxy, octyloxy, nonyloxyg decyloxy ;, undeoyloxyV ^Aco ^ ^Q ^ ¥ $ Propioiiyi-' oxy, butyrylo: ^, laobutyryloxyp valeroyloxy, isovaloroylöxy, """'

Motlaylatliyla.eetoxy,; "- Ti-inothyla" cetoxy, - Gapronoyloxy, oxy, Gapryloyloxy, Pelargonoyloxy, Caprinoyioxy, Undocanoyloxy, Lauroyloxy, Tridecanoyloxy, Tetradecaiioyloxy, Styradecaiioyloxy, Carboo-propyloxy, Carboo-propyloxy, Carboo-iso-oxoxy, Carboo-iso-oxoxy, Carboo-iso-oxoxy, Carboo-propyloxy, Carboo-iso-oxoxy, Carboo-propylooxy, Carboo-iso-oxoxy, Carboo-iso-oxoxy, Carboo-iso-oxoxy, , Garbppentyloxy, Carbohexyloxy, Carbqoetyloxy> Benzyl, 1- or 2- ■ Phenylethyl, MethoxybenzyT, tert-Butylphenyläthyl- (1), 2- ■ (p-Butoxyphenyl) -propyl- (2), 2- (p-Acetoxyphenyl) ~ propyl- (2), 2- (p-triiaethyl-a.cetoxyphenyl) -propyl- (2), 2-methoxy-3- (2-: methylcyclohexyl) -5-nietlayl-benzyl, 2-acotoxy-3- (2-EiethylcyelO'-hexyl) -5-methylbenzyl, 2-methoxy-4-ethyl-6-tert-butylbenzyl, 2-acetoxy-4-ethyl-6-tert-butyl-benzyl, 2-acetoxy-3-tert .butylö-metiiylbenzyl, l, l-bis (2 ~ uethyl-4-acetoxy-S-tort.butylplienyl) butyl- (3), I ₁ 1-Bishr (2-iae "thyl-4-iaetßosy-5 - ^ ert.bxitylphenyl) -butyl- (3), I- (2-methyl-4-ethoxy-5-tort .butylphonyl) -butyl- (I) ", l- (2-methyl-4-acetoxy-5 -tert.butylphenyl) -butyl- (1), 2, ö-D I-. pentyl-4-ethoxybenzyl and ^, S-dipentyl-cL-acetoxybenzyl.

As nests It _ß koiainen- in the formula I in addition to V / hydrogen infrago: methyl, ethyl, n-propyl, isopropyl, n- _} selc-, iso- and tert. Butyl, n-Arayl, isoainyl, tert-pentyl, neopentyl, n-IIexyl, isohexyl, 2- odei- 3-; methylpentyl, methoxy, ethoxy, n- or iso-propoxy, ή-, iso-, selc, or tert .Butoxy, Acetoxy, Propionyloxy, Butyryloxy, Isobutyryloxy, Valeroyloxy, Isovaleroyloxy, Metliyläthylaeetoxy, Trinethylacetoxy, Cyclopentyl, 2- or 3-Methyl- or Aethyloyclopentyl, Cyclohexyl, 2-Methylcyclohexyl-A-methyl-2-Methylclohexyl, 4-Methylcyclohexyl-3-Methloyyl, 2-isopropyl cyclohexyl, 3-propyl cyclohexyl, S-propylcyclohexyl, 3- or 4-ethylcyclohexyl, 3- or 4-isopropylcyclohexyl or ^ -propylcyclohoxyl.

The compounds of Poriael I are used as stabilizers. Stabilizers of the formula I which are particularly economical to produce and are therefore preferred are those in which two to four of the n _2! I * ₃ , It ^, U _ß and R _{Q are} hydrogen .

BATH

Among other things, compounds containing more aromatic lines For formula I, those in .doriao Ιϊχαιι are preferred which these grains are similarly substituted. Especially too are to be named as those who differ from Bipheuyl ..,, Diphenylätlier, Diphonyl sulfide, diphenyl methane, 2,2-diphenylpropane and 1,1-, diphenylbutane dissipating symmetrical connections »

With the stabilizers according to the invention organic "products from the most varied of areas can be stabilized." A "are" ¹ in particular high molecular weight plastics such as polyolefins, eg polyethylene, polypropylene, polystyrenes, polyamides, polyesters, polyacetals, polyvinyl chloride, polyethers, copolymers of styrene / ilutacfien ·, outadiene / isobutylene; butadione / acrylonitrile; naturicauts Synthetic rubbers such as polyisoprene, polybutadiene, mineral oils, fats, viaxes, long-chain metal coholes and fatty acids, lubricating and liming greases, and cooling and insulating oils.

According to the method according to the invention, such materials are produced stabilized by giving them Q, Oi up to 10 percent by weight, preferably 0.01 to 3 percent by weight of one or more Compound (s) üei · Poriael I added. This clogging can in principle at all processing stages of the product to be stabilized. In the case of high molecular weight, solid products, üie can be obtained by ionic polymerization * Her Stabilizer can also be added during the production process as a result of which "particularly uniform distribution is achieved dos stabilizer in the solid product. In the case of plastics . processed by casting '(e.g. casting resins), tia η mixes the stabilizing active ingredient advantageously to the liquid casting compound; solid products can e.g. also by kneading with a compound of the formula I ^ .n a mixing roller stabilized iiei liquid and semi-liquid organic products such as oils, sliding and lubricating greases, jnan achieves one good stabilization by simple mixing or vigorous stirring optionally at a slightly elevated temperature, with ethene preferably liquid active ingredient at room temperature

009887/1991

Formula I. Using Jfette and Y / axis, .a. Also other solid products, which are soluble in easily removable solvents can also be appropriately stabilized in that one adds the Sta.bilisa.tor in pure or also dissolved form to a solution of this product and then the Solvent removed again. -

The compounds of formula I can also be used together with other known stabilizers have been used. As such In particular, there are also known light and ultraviolet stabilizers in question. Such combinations are the materials to be stabilized in amounts of 0.01 to 10 Percent by weight, preferably from 0.1 to 5 percent by weight added.

The stabilizing effect of the compounds of the formula I was determined, for example, as follows:

Unstabilized polyethylene powder was 0.5% light percent of the active ingredient to be investigated is kneaded in a mixing roller mill for one hour at 140 - 150 C with access to air and then at this temperature and a pressure of 100 kp / cm '"' pressed into 2 mm thick plates. These plates became 10 χ 50 mm large test specimens cut and on these the elongation at break (in percent);,; determined with a tensile force tester. The results are shown in Table I. The commercially available stabilizer was used as the comparison substance 2,6-Di-tert-butyl-4-ethylphenol (experiment no. 2).

0098 87/1981

Tu / belle I: Elongation at break of test specimens made of polyethylene with various stabilizing additives.

Pre-trial
No. stabilizer Elongation at break
in 5ö 1 without 60 2 2,6-l) i-t ert. B.utyl-4-ethyl-phenol • 290 3 4-nonylanisole 330 4-tert-butylphenyl-n-butyl ether 330 5 2- (or 3-) tert-butyl ~ 4-n-butoxyanisole - 360 6th 2- (or 3-) tert-butyl-4-trimethylaoetoxy-
anis.ol 330 7th 4.4 ^L -DiBiethoxybiphonyl. 330 8th 4,4 ^I -diacetoxybiphenyl 330 9 Bis- (2-methoxy-4-ethyi-6-tert.l) ü ^: tyl-
phenyl) methane. 330 _; 10 Bis- (2-acetoxy-4-ethyl-6-tert-butyr-.
phenyl) methane 330 11 " Bls- ^ J-methoxy-3- (2-methylcyclohexyl) - «·
5-methylphenyl7-.niethah 360 12th 2,2-bis (4-n-butoxyphenyl) propane 330 13th 1,1-bis- (2-methyl-4-acetoxy-5-tert, buty1-
phenyl) -but.an 330 14th 1,1-bis- (2-methy l-4-methoxy-5-ter.t. Butyl-
phonyl) butane 330 15th 1,1,3-Tris- (2-methyl-4-methoxy-5-tert.
butyl-phenyl) -butane 330 16 Bis- (2-iaethyl-4-methoxy-5-tert-butyl-
phenyi) sulfide 330

The table shows that the from with the .Y / active substances according to the invention stabilized polyethylene according to existing test specimens the thermal load (during incorporation and pressing) can be significantly more mechanically stressed than those that from the one stabilized with 2,6-di-tert-butyl- * 4-methylphGnol Made of polyethylene.

BATH ORIGINAL

Another advantage of the inventive stabilizers is their compared to the corresponding phenolic pn Stabilizers significantly better solubility in the materials to be stabilized. This property is there in particular Essential where the materials to be stabilized thermally are sensitive so that they are not heated with the stabilizer which is often necessary in order to set a sufficient stabilizer concentration in a reasonable time. The solubility values for some of the invention Active ingredients (experiments 1,2,3,5,6 and 8) and for some phenols (Experiments 4, 7 and 9) are shown in Table II.

Table $ 1: Solubility of stabilizing agents in Peanut oil,

Vers.-No. Stabilizing agent or
Comparison substance solubility
/ g / i00 g peanut
oil/ 1
2
3
4th 4-tert-butylphenyl butyl ether
4-tert-butylphenyl laurate
Lauric acid — 2,4-dimethyl-6-tert.
butylphenyl ester ■ ·.
4 ~ tert-butylphenol • CD
CD
CD
18th 5
6th
7th 2,2-bis (4-trimethylacetoxyphenyl) -
propane
2j2-bis (4-butoxyphenyl) -prQpan.
2,2-bis (4-hydroxyphonyl) propane • 40
CD
0 8th
9 4,4'-bis-trimethylacetoxy-biphenyl
4,4'-dihydroxybiphenyl 2.5
0

Leave the results compiled in this table clearly recognize that the inventive stabilizers better solubility iii non-polar media have ice underlying phenols. *

1181

The stabilizing agents'der general. Formula I. have been produced by methods known per se. In the preferred method is a phenol of formula II

no-if ^v > ~ Ii _{4 I] C}

ILi

wherein R ₂ , Ii ₃ > ^ a> Rr and U _{6 have} the meaning given in formula I,

in an alkaline medium with an alkyl or acyl derivative containing the desired radical R. The corresponding alkyl halides, alkyl or. Dialkyl sulfates, ayl halides, acid anhydrides or acid esters. The reactions themselves take place according to standard processes known from the literature. Solvents for die.se reactions can all be used which are inert to the starting materials under the reaction conditions, in particular hydrocarbons such as benzene, toluene, xylene, tetrahydronaphthalene and deca.hydronaphtha.lin, and ethers such as diethyl ether, tetrahydrofuran, dioxane and, preferably, diether of -Polyglycols such as diethylene glycol dimethyl ether; Furthermore, dimethylformamide, methyl sulfoxide, ketones such as acetone, methyl ethyl ketone or diethyl ketone and carboxylic acid esters such as Es, ethyl acetate or butyl acetate are also suitable. For the alkylations, water, methanol, ethanol, isopropanol, n-butanol and tert-butanol are also suitable as solvents. The reaction temperatures are between -5O ⁰ C and + 150 ⁰ C, preferably between -10 C and + GO ⁰ C. The The reaction mixture is worked up in a conventional manner, for example by pouring it into water and suctioning off the reaction product or extracting it with a suitable solvent such as petroleum ether, benzene or ether.

0 09887/1981

. ■. - BAD ORIGINAL

According to another method, the .Y> ^r irkstpffG the orfindungsgemäßen agents are obtained by reacting, in phenol ethers or esters in a known per se Y. ^r else, ZOB ,, by Friedel-Crafts reactions, alkyl or aralkyl groups as substituents It ₂ until Il introduces _ß.

The alkyl halides, aralkyl halides, alkenes, aralkenes, alkanols or aralkyl alcohols corresponding to the desired radicals are used as starting materials for the introduction of these groups. The catalysts used are those known from the literature for this reaction; aluminum chloride, zinc chloride, iron (III) chloride, boron trifluoride, hydrogen fluoride and sulfuric acid are preferred. If the reaction is carried out in solution, possible solvents are, for example, petroleum ether, carbon dioxide, chlorobenzene and nitrobenzene. The reaction temperatures are between -30 ⁰ C and + 150 ⁰ C, preferably between O ⁰ C and 90 ⁰ C. The reaction mixtures are worked up in a conventional Vie is e, z.Bο by pouring into EisAvasser and extracting the reaction products using a suitable th solvents such as benzene, ether or petroleum ether. In an analogous V / else is done, for example, _o the preparation of the diphenyl sulfide from the active compounds derived by reacting corresponding phenol ethers or esters with Schwefeldichloride This reaction can also be carried out in the absence of a catalyst; In addition to those mentioned above, carbon tetrachloride or 1,2-dichloroethane can also be used as solvents. .

009887/1981

BATH

example 1

220 g of technical nonylphenol (commercially available Isonerengoniisch, prepared by reacting phenol with nonene obtained by triaging propylene; main component 4-nonylphenol) are suspended in 500 ml of 10% sodium hydroxide solution g of dimethyl sulfate are added and the mixture is then heated for 30 minutes to 100 ° C. The cooled reaction mixture is extracted with ether, the extracts are washed with 2 strength sodium hydroxide solution and water and dried over CaCl. After the ether has been distilled off, the remaining 4-nonylanisole is distilled under reduced pressure ; Kp _Q 155 - iö7 ° U.

The following are obtained analogously:

4-octylanisole,

2,4-Dinonylanisο1,

4.4 "-Dimethoxybiphenyl, F. 177-179 ⁰ C ■

4-dodecylanisole

3,4,5-Trimethoxybenzoesäurepropylester, IiPg 175-178 ⁰ C

Bis- (2-methoxy ~ 4-ethyl-6-tert, butylphenyl) methane, mp 122-124 ° C Bis- / 2 "-methoxy-3- (2-methylcyclohexyl) -5-methylphenyl7-methane,

- F.121-122 ⁰ C

Bis (2-methoxy-o-nonylphenyl) methane,

1, l-bis (2-methyl-4-methoxy-u-tert-butylphenyl) -butane,

Kp ₆ 222-226 ^{above sea level}

1,1,3-tris (2-methyl-4-methoxy-5-tert-butylphenyl) butane,

Bp ₈ 295-300 C.

2,2-bis (4-methoxyphenyl) propane.

Example 2

105 g of p-tert-butylphenol and 30 g of sodium hydroxide are used in 500 ml of ethanol dissolved. 70 g of n-butyl bromide are added to this solution, stirs for one hour at room temperature, then heated to boiling for 30 minutes and then distilled the largest Part of the ethanol. The residue is poured into ice water

-..., _r . 00988771981

BATH

and the oil which separates out is absorbed in ether. This solution is _{dried over CaGl 2} , the ether is evaporated and the remaining 4-tert-butylphenyl-butyl ether is distilled under reduced pressure; Kp _Q 118-i2Q ° C.

Analogously the following are obtained: -. ■

2,6-diisopropylphenyl-butyl ether, b.p. 120-125 ⁰ C _Q

2,2-bis (4-butoxyphenyl) propane, Kp_ 173-178 ° C 2,4-dimethyl-6-tert-butylphenyl-dodeoylather, Kp _ß 210-22O ⁰ C

Example 3

32 g of 4,4-dihydroxydiphenyl ^I v / ground boiled in 500 oil acetic anhydride with 0.5 ml of concentrated sulfuric acid for one hour under Jtüokiluß. After stables üüor Naolit aas is crystallized 4,4 sucked -Diacetoxydiphenyl ^I / ater washed with V and dried; F. 162-163 C.

Analog are received!

4-dodecylphenyl acetate, b.p. 174-17o ° C. '2,2-bis (4-acetoxyphenyl) propane, P. 71-73 ⁰ C acetic acid-4-nonylphenylester, Kp _c i65-167 ° C acetic acid-2,4-dinonylphenylester _i acetic acid-4-octylphenylester

Bis- (2-aoetoxy-4-ethyl-6-tert, 1) utylphonyl) methane _A

Kp _K 228-232 ⁰ C.

1,1,3-Tris- (2-iaethyl-4-acet oxy-5-tert-butyl phenyl) -butane,

Kp _r 315-320 ⁶ C ο

- ^ "- aco toxy-3- (2-methylcyclohexyl) -5-Kie thy Iphenyl7-me than,

305-315 ⁰ C.

₄ 1, l-bis (2-methyl-4-acetoxy-5-tert-butylphonyl) butane, "

245-248 ° G

₆ bis- (2-acetoxy-3-tert-butyl-S-methy! Phenyl) methane,

222-224 ⁰ C.

00988 ^ / 1981

Example 4

43 g of potassium salt of 2,4-dinethyl-6-tert.butylphenol (prepared by dissolving 2,4-dimethyl-6-tert.butylphonol ax a small excess of KOH in ethanol, evaporating, taking up the residue in toluene and distilling off the toluene in a vacuum) are dissolved in 120 ml of diethylene glycol dimethyl ether and a solution of 45 g of lauroyl chloride in 50 ml of diethylene glycol dimethyl ether is added dropwise at room temperature while stirring and cooling. The mixture is stirred for a further 2½ hours at room temperature and then poured into an ice cream barrel. The oil which separates out is taken up in petroleum ether, the solution is dried over sodium sulfate and evaporated. The residual lauric acid-2,4-dimethyl-6-tertfbutylphonylester is distilled under reduced pressure \ _5253-258 ⁰ C.

The following are obtained analogously:

Lauric acid-2,6-d.imethylphenylestei ', Kp ₁₂ 217-22O ⁰ C Caprinsäurephenylester, F. 155-160 ⁰ C lauric acid ^ jG-diisopropyl-phenyl ester, bp _fi 222 ⁰ C stearic acid 4-nonylphenylester, Kp, 293-297 ⁰ C lauric acid 4-tert-butylphenyl ester, KPo 227-229 ° C

Kp _D 240-245 ⁰ C

4 _j 4 ^t -Bis- (trimethylacetoxy) -biphenyl, F. 154-156 C 2,2-bis (4-trimethylaceto ^ qrphenyl) propane, F. 116-11S ⁰ C trimethylacetic acid-2,4-dimethyl- 6-tert-butylphenyl ester,

Kp-. 128-132 ° C

Example 5

108 g of anisole are'mit.4.9 g of concentrated sulfuric acid and 3.5 g boron trifluoride heated to 70 ° C. 252 g of technical grade dodecene (commercially available Mixture of isomers, obtained by catalytic tetra-

009887/1981

merization of propylene) and stirred for 3 hours at this temperature. After cooling, it is washed with dilute sodium hydroxide solution and Vifa's cream, _{dried over CaCl 0} and the 4-dodecylanisole thus obtained is distilled under reduced pressure; Kp _r 169-173 ⁰ C.

The following are obtained analogously:

2- or 3-tert-butyl-4-trimethylacetoxy-anise oil, b.p. 137-140 2- or 3-tert-butyl-4-butoxy-aη
2-tert-butyl-4-methoxy-anisole,

⁰ C

2 and 3, respectively-tert-butyl-4-butoxy-anise oil, bp _{4130 to 134} ^0C

4,4'-di-tert-butyl-diphenyl ether, _n Kp, 131 ⁰ C.

Example 6

744 g of 2,5-diisoaniyl anisole are heated to boiling in 2 liters of petroleum ether (boiling range 80-100 ° C). 103 g of sulfur dichloride are added dropwise to the boiling solution and the mixture is refluxed for a further 2 hours. The Ileaktionsmischung with \ vässriger is then 'Natriunhydrogenkai-carbonate solution and dried over CaCl ₀ dried. After the solvent has been stripped off, the bis (2, δ-diisoamyl-4-ynethoxyphenyl) sulfide that remains is distilled under reduced pressure; Bp - 268-270 ° C.

The following are obtained analogously:

Bis (2,5-diisoamyl-4-acetoxyphenyl) sulfide, bp _ß 266-268 ° bis (2-methyl-4- ^ acetoxy-ot ert. Butylphenyl) sulfide,

₀ .. 2o0-2öö ^O C

Bis- (2-iaethyl-4-raethoxy-ö-tert.butylphenyl) sulfide,

F. 129-132 ⁰ C.

0 0 98 8 77 1981

Claims (1)

Pa te ηt aηs check 1 J use of compounds of the formula I. R ₂ wherein R. is alkyl or alkanoyl with up to 18 carbon atoms or ^H Ar, · Rp II or optionally substituted by Ar Alkyl, alkoxy or alkanoyloxy with up to 9'C atoms, R ₀ and R _r II or alkyl with up to 6 carbon atoms, R. H, Ar, Ar-oxy, Ar-thio or optionally by Ar mono- or polysubstituted alkyl, alkoxy, alkanoyloxy or carbalkoxy with up to 18 carbon atoms, R ₆ .II, alkyl, alkoxy or alkanoyloxy with up to 6 carbon atoms or optionally cyclopentyl or cyclohexyl substituted by alkyl with up to 3 carbon atoms, and ¹ Ar phenyl or by alkyl, alkoxy, alkanoyloxy or carbalkoxy with up to 18 carbon atoms or by, Cyclopentyl or cyclohexyl, which can also be substituted by alkyl with up to 3 carbon atoms, substituted phenyl means " with the proviso that R ^ does not mean Pormyl and that no more aromatic nucleus than a tertiary dutyl group wearing, to stabilize plastics, fats and oils. 00888 »/ 19Π 2. Use of compounds of the formula I according to claim 1, characterized in that a total of 0.01 to 10 percent by weight of one or more of these compounds is added. .. "." ..- 3. Use of compounds of the formula I according to the claims 1 and 2, characterized in that at least one of the following compounds is used! 4-nonylanisole
4-dodecylanisole 4-0cty! Anisol. - 2- or 3-tert-butyl-4-butoxy-anisole
2- or 3-tert-butyl-4-trimethylacetoxy-anisole 4-tert-butylphenyl-butyl ether 4-octylphenyl acetate. - 4-nonylphenyl acetate
4-dodecylphenyl acetate. 4-nonylphenyl stearate.
4-tert-butylphenyl laurate 2,6-dimethylphenyl laurate
2,6-diisopropylphenyl laurate 2,4-dimethyl-6-tert-butylphenyl laurate 2,4-dimethyl-6-tert-butylphenyl trimethyl ester 4j4 ¹ -Dimethoxybiphenyl
4,4 ^t -Bis- (trimethylacetoxy) -biphenyl bis- (2-Mothoxy-4-ethyl-6-tert-butylphenyl) -iaethane bis- (2-acetoxy-4-ethyl-6-tert-butylphenyl) -methane . Bis- (2-aoetoxy-3-tert-butyl-5-methylphenyl) methaYi 008817 / τι ·! 2,2-dis (4-methoxyphenyl) propane 2,2 ~ bis (4-butoxyphenyl) propane 2,2-bis (4-acetoxyphenyl) propane 2,2-bis (4-trimethyla.cetoxyphenyl) propane 1,1- * bis (2-iaethyl-4-methoxy-5-tert-butylphenyl) butane 1,1,3-tris- (2-methyl-4-methoxy-5-tert * butylphenyl) butane 1,1-bis- (2-methyl-4-a.ce t oxy-5-tert. Butylphenyl) butane 1,1,3-Tris- (2-iaethyl-4-acetoxy-o-tert-butylpllenyl) -butane Bis (2-iaetliyl-4-iaethoxy-5-tert-butylphenyl) sulfide Bis (2,5-diisoaciyl-4-acetoxyphenyl) sulfide Bis (2,5-diisoamyl-4-ynethoxyphenyl) sulfiü Bis- (2-Iaethyl-4-acetoxy-ΰ-tert. Butylphenyl) sulfide 009887/1981 '5. The method according to claim 4, characterized in that one a total of 0.01 to 10 percent by weight of one or more Compound of the formula I is added. 6. Vei'fahreii according to claims 4 and 5, characterized in that a total of 0.01 to 10 percent by weight adds to one or more of the following compounds: 4-nonylanisole 4-dodecylanisole 4-octylane sol 2 or. 3-part-butyl-4-butoxy-anisole ■ 2-or / .3-tert-butyl-4-trimethyla.cetoxy-anisole 4-tert-butylphenyi-butyl ether, 4-octylphonyl acetate, 4-nonylphenyl acetate, acetic acid -4-dodecylphenyl ester stearic acid - ^ - nonylphenyl ester lauric acid 4-tert-butylphenyl ester lauric acid -2, G-dimethylphenyl ester 2,6-rdiisopropylphenyl lauric acid 2,4-dimethyl-6-tert-butylphenyl laurate 2,4- ^ trimethyl acetic acid dXmBthyl-6-tert-butylphenyl ester 4,4 ¹ -Dirnethoxybiphenyl 4,4. »- Bis- (triinethylacotoxy) -biphenyl Bis- (2-methoxy-4-ethyl-G-tert-butylphenyl) -methane HIs- (2- acetoxy ~ 4-ethyl-G-tort.butylphenyl) -raothane bis- (2-aceto2 £ y-3-tert. buty 1-ö-we t hy 1 phenyl) -me f hau 0 QBB i 7 / \ S 8 1 ^BÄD original 4. Process for stabilizing plastics, oils or Fats, characterized in that at least one compound of the formula I 11, -0 ^ VS R, R _r R- wherein IL is alkyl or alkaiioyl with up to 18 carbon atoms or χ-Ar, R ₂ II or optionally substituted by Ar alkyl, alkoxy or alkanoyloxy with up to 9 C-. Atoms, Ro and R _r H or alkyl with up to 6 carbon atoms, R ^, H, Ar, Ar-oxy, Ar-thio or optionally by Ar.substituted or polysubstituted to alkyl, alkoxy, Alkanoyloxy or "carbalkoxy with up to 18 carbon atoms, R "II, alkyl, alkoxy or alkanoyloxy with up to 6 C atoms or optionally by alkyl with up to Cyclopcntyl or cyclohexyl substituted to 3 carbon atoms, and Ar is phenyl or by alkyl, alkoxy, alkanoyloxy or carbalkoxy with up to 18 carbon atoms or by cyelopentyl or cyclohexyl, also by alkyl can be substituted with up to 3 carbon atoms, substituted pheny!. "means, with the proviso that IL does not mean formyl and that no aromatic nucleus "as a tertiary eutyl group wearing, clogs. 009887/1981 SAD ORIGINAL ; " ²² ~ 193738Λ xy-S- (2-niethylcyclohexyl) ~ 5 ~ Eiethylphenyl7'-nethane Bis - / jZ-ace t oxy-3 - ^: (2-ne-t hy Icy c 1 ohexy 1) -o-me t hy 1 phe nylf -me than 2, 2-Bls- (4-Eiethoxyphenyl) -propane 2,2-bis- (4-buto:; yphenyl) -propane 2 ^ -Bis-id-acetoxyphenyl) -propane 2 _J 2-Eis- ( 4-triinetliylacetoxyphenyl) -i) ropan i, 1 -B is - (2-iaethy 1-4-me thoxy-5-t er t, huty lphe ny 1) -butane 1,1,3-Tris- (2 -iacthyl-4-methoxy-5-tert-butyl phenyl) -butane 1, i-bis- (2-methyl-4-aeetoxy-5-tert-butylphenyl) -butane 1,1,3-tris- (2- methyl-4-acetoxy-5-tert.; butylphenyl) -butane bis- (2-nethyl-4-iuethoxy-5-tert.butylphcnyl) -sulficl bis- (2, S-diisoanyl ^ -acetoxyphenyl) -sulfide bis- (2,5-diisoa.uyl-4-niethoxyphenyl) sulfide bis - ^ - methyl - ^ - acetoxy-S-tert.butylphenyl) sulfide. BAD OBK31NAL