DE2304270A1 - PROCESS FOR STABILIZING ORGANIC MATERIALS AGAINST THE DESTROYING EFFECT OF ULTRA-VIOLET RAYS - Google Patents

Description

Dl ·: ¹ .-! <-. -. Wirth

Dr. V. C · ^: -'- ^ -. Wsr

You ¹ . "- ■"".: ■ '■ - ^ Ϊ - birg Dr. P. V-. ', .- ■■'. , Ο /. D. Gudel

Frarik; urtiM, Qt. Eschenheimer sir. 39-

feiL c ζ Aa

Case 150-3367

Process for stabilizing organic materials against the decomposing effect of ultra-violet rays ,

The invention relates to a method for stabilizing organic materials against the decomposing effect of ultra-violet rays, which is characterized by being used as stabilizers compounds of the general formula

(D

309832/1201

- 2 · · Cace 15 ^ -3367

wherein FL, Rp and R, independently of one another, hydrogen, halogen or an alkyl, cycloalkyl or cyclo-.alkylalkyl radical, an alkoxy, cycloalkoxy or cycloalkylalkoxy radical, the cyano group or a radical of the formula -COO R ₁ . wherein

Ru is hydrogen or an alkyl, cycloalkyl or cycloalkylalkyl radical or a phenyl radical which is optionally substituted by at most ji> alkyl radicals or an equivalent of a divalent or trivalent cation,. .. JC ₁ and X ₀ independently of one another hydrogen, halogen, hydroxyl ^ ~ nitrile, an alkyl, cycloalkyl or cycloalkylalkyl radical or an.Alkoxy, cycloalkoxy or cycloalkylalkoxy radical is used. If R ₁ , R ₂ or P is an alkyl radical, this can be primary, secondary or tertiary, straight-chain or branched as desired. Examples of primary radicals R 1, R _p or R are: methyl

Ethyl, propyl / butyl, pentyl, rexyl and the unbranched alkyl radicals with 7 to 12 carbon atoms. Examples of secondary alkyl radicals are: isopropyl, 2-butyl, 3-methyl-2-butyl, 2-pentyl, 2 _r 2-dimethyl-3-butyl _f 2-hexyl, 3-hexyl, 2-methyl-3-pentyl, 3-methyl-2-pentyl _/ 4-methyl-2-pentyl,

2,2-dimethyl-3-pentyl _r 2,4-dimethyl-3-pentyl, 2-heptyl / 3-heptyl, 4-heptyl, 2-methyl-3-hexyl, 4-methyl-3-hexyl,

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5-methyl-3-hexyl, 3-ethyl-hexyl-4, 2,2-dimethyl-3-hexyl, 2, 4-dimethyl-3-hexyl, 2,5-dimethyl-3-hexyl, 3,4- Dimethyl-2-hexyl, 2-methyl-3-heptyl, 3-methyl-2-heptyl, 3-methyl-4-heptyl, 4-methyl ~ 3-heptyl, 5-methyl-3-hoptyl _# 6-methyl- 2-heptyl, 2-octyl, 3-octyl, 4-octyl, 2,2,4-tri-ethyl-3-pentyl, 5-ethyl-2-heptyl, 2,2-di-ethyl-3-heptyl, 2,6-dimethyl-4-heptyl, 2-methyl-3-octyl, 3-methyl-4-octyl, 6-ethyl-3-octyl, 2-decyl, 5-decyl, 2 _# 2-diiriethyl-3 -octyl, 2-methyl-4-nonyl, 3-methyl-4-nonyl _f 6-ethyl-3-decyl / 7-ethyl-2-methyl--4-nonyl /. 2-dodecyl, 2, 6,8-tri-ethyl-4-nonyl _t Examples of tertiary alkyl radicals for R ₁ , R ₂ or R ₅ are tert-butyl »2-methyl-2-butyl, 2,3-di-methyl-2- butyl, 2-methyl-2-pentyl , S-methyl-S-pentyl, 3-ethyl-3-pentyl, 2 _r 4 ~ dimethyl-2-pentyl _f 2-methyl-2-hexyl, 3-methyl-3 -hexyl , 3,4-dimethyl-3-he.xyl, 3 _f 5-dimethyl-3-hexyl, 2-methyl-2-heptyl, 3-methyl-3-heptyl, 4-methyl-4-heptyl _/ 2 , 3,4-trimethyl-3-pentyl, 2,4,4-trimethyl-2-pentyl _r 3-ethyl-3-heptyl, 2-methyl-2-octyl _/ 4-methyl-4-octyl.

As the primary alkyl radical, R _{1, R 0} or R each have 1 to 12, preferably 1 to 8 carbon atoms. As a secondary alkyl radical 3-12, preferably 3-8 carbon atoms and as a tertiary alkyl radical 4-12, preferably 4-8 carbon atoms.

309832/1201

If R ,, Rp or R are a cyeloalkyl radical, they have 5-12, preferably 5-8 and especially 6 carbon atoms. Examples are. Cyclopentyl, cyclohexyl, cycloheptyl, 2-, 3- or 4-methyl-cyclohexyl, cyclooctyl, 2,5 - * 2,6-, 3,4- or 3,5-diniethyl-cyclohexyl, 1-cyolohexylpropyl, 2- Propyl-cyclohexyl, 3,3,5-trin: ethyl-cyclohexyl, 2-butyl-cyclohexyl, 4-tert. Butyl-cyclohexyl, 3-Kethyl-6-isopropylcyclohexyl and cyclododecyl .. Further examples are 1-methylcyclopentyl, 1-methyl-cyclohexyl, 1-methyl-cycloheptyl, 1-propyl-cyclopentyl and 1-butyl-cyclopentyl. If R ,, Rp or R is a cycloalkylalkyl radical, this has 6-12, preferably 6-8, carbon atoms. Examples are

Cyclohexyl-ethyl, 2-cyclohexyl-ethyl, cycloheptyl-ethyl, 3-cyclohexyl-propyl, cyelooctyl-ethyl, cycloundecyl-r-ethyl and cyclododecyl-methyl. In addition, R-, Rp or R-. also a branched radical such as, for example, 2- methyl -1-propyl. 2,2-dimethyl-1-propyl, 2-ethyl-1-butyl, 2-ethyl-1-butyl, 2,2-dimethyl-1-butyl, 2-1-ethyl-1-pentyl, 3-methyl- l-pentyl, ^ -Methyl-1-pentyl, 2,4-dimethyl-1-pentyl, 2-ethyl-1-hexyl, 2,2-dimethyl-1-hexyl, 2,2,4-trimethyl-1- pentyl, 4-methyl-2-propyl-1-pentyl, 3,7-dimethyl-1-octyl, 2,2-dimethyl-1-decyl, the above limits apply. The halogens here are fluorine, chlorine and bromine, preferably chlorine.

3 09832/1201

± 'ju -

2304278

If R ,, R ₂ or R- is an alkoxy, cycloalkoxy or cycloalkylalkoxy radical, then the above examples for R- ,, R ₂ and R- apply, with the difference that instead of methyl, methoxy, ethyl, ethoxy, cyclohexyl , Cyclohexyl- oxy etc. is to be set. Further examples are tetradecyloxy, hexadecyloxy, octadeeyloxy, doeosanyloxy.

PiIr R ₂ , the stated primary and secondary alkyl, cycloalkyl and cycloalkylalkyl radicals with up to 12, preferably at most 8, carbon atoms apply. If R. is phenyl, this phenyl can be substituted by a maximum of 5 alkyl, cycloalkyl or cycloalkylalkyl radicals having 1-12, preferably 4-9, carbon atoms. These substituents are preferably branched, such as isobutyl, isoamyl or tertiary butyl, and together have a maximum of 22 carbon atoms. If R ₂ ^ is a cation, this can be nickel, copper, manganese, or another, preferably divalent, metal ion.

X. or X ₂ denote calogen, an alkyl, cycloalkyl or cyeloalkylalkyl radical or an alkoxy, cyolpalkoxy or cyeloalkyialkoxy radical with 1 to 22 carbon atoms, the _{statements made for R 1} , R ₀ and R in principle apply to these radicals, but, for example, the radicals tetradecanyl, ilexadecanyl, octadecanyl, nonadecanyl, doeosanyl, or the corresponding Cxy compounds are to be added.

309832/1201

230427

If X _{1 is} hydrogen, then Xp preferably denotes an alkoxy group in the para position to the aryl bond. Some of the compounds of the formula: (I) are new and of particular importance. For example the compounds of the formula

(Ia)

viorin

R ₁ and IV, have the above meaning, R'_ is hydrogen or the radical -COOR ^ where R ^ has the above meaning, X 'and X' independently of one another are hydrogen, an alkyl, cycloalkyl or cycloalkylalkyl radical or an alkoxy, Cycloalkoxy or cycloalkylalkoxy radical with up to 22 carbon atoms mean v / obei either X ^f , or X ' _{p has} a meaning other than hydrogen. A further embodiment are the compounds of the formula

30983 2/1201

- 7 - Case 150-3367

2304276

where R-, and R _? independently of one another hydrogen or

Methyl,

R ¹ -y hydrogen or the -COOR '"- group, in which R ¹ J, hydrogen or an equivalent of a 2- or

Trivalent cations and

X "is an alkoxy, cycloalkoxy or cycloalkyalkoxy group with preferably 1-18 and especially 8-12 carbon atoms. Another embodiment are compounds of the formula

(Ie)

where X ' ^M ρ denotes an alkoxy, cycloalkoxy or cycloalkylalkoxy group with up to 18 carbon atoms and the remaining abovementioned substituents are hydrogen.

Another embodiment to be mentioned are connections the formula

(M)

309832/1201

X 'is an alkyl, cycloalkyl or cycloalkylalkyl radical with 4 to 12, preferential travel with 6-9 especially with 8 carbon atoms and the remaining ones, abovementioned substituents are hydrogen.

The synthesis of the compound of formula (I) - takes place according to well-known methods, the quinoline synthesis, as these are compiled in textbooks and handbooks. Siohe e.g. R.C. EiderfJelÜ, Heterocyclic Compounds, Wiley, New York I950-1952 or Organic Reactions VII, 59. In particular the quinoline synthesis according to Pfitzinger should be mentioned a compound of the formula

(II)

with a ketone of the formula

CH-

(III)

condensed in an alkaline medium, and then optionally decarboxylated. Well-known methods are used

309832/1201

- 9 - Case 150-3367

such as in J. Org. Cheni. 18, 12o9-1224 (1953).

A compound of the formula is preferably used

. CH ^

Q ^ "JOT ^λ (HIa)

HO '^^ X'g

wherein the S ¹ Ub substituents X 'and X' have the above meaning.

For use as stabilizers, the compounds of the formula (I) are sensitive to light, oxygen and heat Substances incorporated or applied as a protective layer to the substances to be protected. Because of their stabilizing The new compounds used in this way protect the sensitive substances from destruction. Particularly The possible applications in the plastics sector are numerous. It can be used, for example, with the following plastics: cellulose acetate • cellulose acetobutyrate, Polyethylene, polypropylene, polyvinyl chloride, polyvinyl chloride acetate, Polyamides, polyurethanes, polystyrene, ethyl cellulose, cellulose nitrate, polyvinyl alcohol, polycarbonates, Silicone rubber, cellulose propionate, melamine-formaldehyde resins, Urea-formaldehyde resins, allyl casting resins, Polymethyl methacrylate, polyester and polyacrylic

309832/1201

-Io - Case 15o-J >> 57

nitrile and corresponding copolymers, such as acrylonitrile-butadiene-styrene copolymers. Natural substances can also be stabilized, such as rubber. The substances to be protected can be in the form of plates, rods, coatings, foils, films, tapes, fibers, granules, Powders and in other forms of processing or as solutions, emulsions or dispersions. Incorporation or the materials to be protected are coated according to methods known per se. A particularly important one Application method consists in the intimate mixing of a plastic, for example polypropylene in granulate form, with the new compounds, e.g. in a kneader, and in the subsequent extrusion. ' One obtains in this way a very homogeneous mixture, which is important for good protection. When extruding, for example, films are obtained Tubes or threads. The latter can be woven into textiles. In this mode of operation, the stabilizer is in front of the Processing into a textile material with the. Mixed polypropylene.

Plastics do not necessarily have to be fully polymerized

or be condensed before mixing with the new connections are made. You can also use monomers or prepolymers or precondensates with the new stabilizers

309832/1201

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Mixers and only afterwards convert the plastic into its final form by condensing or polymerizing.

The stabilizers of the formula (I) can not only be used v / ground to stabilize clear films / plastics and the like, they can also be used in opaque, semi-opaque or translucent materials are used whose surface is subject to ultraviolet degradation Sensitive to light, air and heat. Examples of such materials are: foamed plastics, opaque films and coatings, opaque Papers, clear and opaque colored plastics, fluorescent pigments, polishes for automobiles and furniture, creams and lotions and the like, regardless of whether they are opaque, clear or are translucent.

309832/1201

Case 15O-3367

The present invention also relates to the materials which contain compounds of the formula (I) for stabilization. As shown above with a few examples, the incorporation of the compounds into the materials to be protected can be carried out in any processing stage according to methods known per se, wherein the amount of incorporated protective agents can vary within wide limits, for example between 0.01 and 5 * ρ> preferably between $ 0.05 and $ 1, based on the materials to be protected. The stabilized organic materials can only contain compounds of the formula (i) or additionally contain bovine auxiliaries to improve the properties. Such aids are, for example: UV absorbers and stabilizers against destruction by heat and oxygen. Of the latter, especially those that belong to other classes of substances than the compounds of the formula (I), such as, for example, 2-hydroxy-benzophenones, 1,2,3-triazoles, organic compounds of sulfur, tin and the three- valuable phosphorus or nickel salts of organic carboxylic acids. With such mixtures of stabilizers, the stabilizing effect is often particularly high because there is a synergistic effect.

In the following examples, parts mean parts by weight and the percent weight percent «. The temperatures are in degrees Celsius specified.

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Case 15o ~ 33o7

Example!:

HO

A mixture of 125.0 parts of isatin, 115.6 parts of 2-hydroxyacetophenone, II9 parts of KOH and 680 parts of methanol is refluxed for 30 minutes in a stirred flask. The reaction mixture is then poured onto 1.5 liters of ice water and acidified with hydrochloric acid. The precipitated yellow acid (2- (2 * -hydroxy) phenyl-3-carboxyquinoline) is filtered off, washed with water and dried at 00 ⁰ C. The dried acid is heated to 180 ° C. in 2oo ml of quinoline with 5 g of Cu powder until the decarboxylation has ended. The solvent is distilled off, and the brown residue dissolved in alcohol and repeatedly crystallized under ¹ addition of animal charcoal. M.p. 117-118 ° C.

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Case 150-3367

Example 2

6.5 parts of 2 "hydroxy"" ⁱ (" octyloxy-acetophenone and 3.0 parts of 2-aminobenzaldehyde are placed in Ιοο, ο parts of methanol and, while stirring, lo.0 parts of 2N NaOH are added at room temperature. The mixture is then Stirred 6/2 hours at 80 ° The dark solution is cooled and poured onto 200 parts of water, a precipitate precipitating out, and the mixture is adjusted to pH 7 with 2N sulfuric acid crystallized from alcohol-dioxane (10: 1), pale yellow needles.
E l em ent aranal? _r ^r s e:

Calc .: C 79 »0 # H 1.1% N 4.0 #, 0 9.15 g

Π ρ Γ · Γ "7Q" 1 ^ TT Ύ Pi ^ t M h * C \ ^c ii Π Q

With regard to constitutional form, see below in Table 1, Example 2. Further new compounds were prepared by analogy processes and are listed in Table 1:

3098 3 27 1 20 1

Case 150-5367

Tabel

• 6 _r 5 4th 4 ' HO ^ t ^7th Position and Art Qi 6 ' 8th JO example
No-.

2 4 * -oetyloxy

3 5 '- (fcert.) Butyl

4 4-carboxy-4'-hydroxy

5 4-carboxy-4'-oetyloxy

6 Nickel salt from Example 4

Example 7 (Use of the compounds of the formula (T))

Unstabilized polyethylene is used on a roller mill. 180 ° mixed homogeneously with 0.5% of the compound described in Example 2 of Table 1 and processed into foils 0.3 mm thick. These are tested for resistance in a climate test using the De La Rue method. The test was carried out at 40 °, at 75 % relative humidity, with strong air renewed, with 16 sunlamps and 16 backlamps

309832/1201

Case 150-3367

Philips company.

Example δ

A wood varnish is produced with the following composition: 18.00 % cellulose acetobutyrate

2.00 % dibutyl phthalate 2o, 7o % butyl acetate 33.4o % xylene 8.35 % methyl isobutyl ketone 8.35 % cyclohexanone 9.2o % n-butanol

This I, ack is used to varnish bleached maple pournier. Yellowing occurs quickly on exposure. If you add 0.2% 2- (2'-hydroxyphenyl) quinoline to the paint of the above composition, the; Yellowing of the lacquered wood was very much delayed.

309832 / 12Q1

Claims (1)

Claims 1. Process for stabilizing organic materials against the corrosive effects of ultra-violet Rays, characterized in that the stabilizers used are pre-compounds of the general formula (I) viorin R,., R _? and R independent of other V / a «iif: rstoff, Kalogen or an alkyl, cycloalkyl or cycloalkylalkyl radical, an alkoxy, Cycl'oallcoxy- or cycloalkylalkoxy radical, the cyano group or a radical of the _{formula -COO R 2} , viorin Yl ₁ . Hydrogen or an alkyl, cycloalkyl or cycloalkylalkyl radical or a phenyl radical optionally substituted by a maximum of 3 alkyl radicals or an equivalent of a divalent or trivalent cation, X. and Xp independently of one another hydrogen, halogen, hydroxyl, nitrile, an alkyl, cycloalkyl or cycloalkylalkyl radical or an alkoxy, cycloalkoxy or cycloalkylalkoxy rust. means used. 309832/12 ü 1 - 18 - 'Case 150-2367 ■ 2. Method according to claim 1, characterized in that man o, ol - 5 percent by weight of the compound of a formula I used. j5. Process according to Claims 1 and 2 _}, characterized in that 0.05-1 percent by weight of the compound of the formula (I) is used. H. Process according to claims 1 to ;) _s characterized in that wan a compound of the formula (la) JlWJl. HO where R, and R _{0 have} the above meaning, R '., hydrogen or the radical -COORh where Rn has the above meaning, X' and Χ 'independently of one another are an alkyl, Cycloalkyl or cycloalkylalkyl radical or one Alkoxy, cycloalkoxy or cycloalkylalkoxy rust with up to 22 carbon atoms mean, where either X ', or X'p has a meaning other than hydrogen has 'used'. 3 0 9 8 3 2/1201 Case 150-3367 23Q4270 5- method according to claims 1-3? characterized, that one has a Yorbindiing of the formula (ro) vjorin R *, and ni independently of each other hydrogen c .- '3.ei Methyl, R '. Hydrogen or the -COOn '^ - group, in which R ¹ ^. Hydrogen or an equivalent of a 2- od er 3-v; like cation and X _"o an alkoxy or cycloalkoxy Cycloalkyialkoxygi'uppe NIIT vorzugswei. ^C> e and I-I8 verwandet mean especially 8-12 C-atoms. 6. The method according to claims 1-3 *, characterized in that that one can connect the Forrr.el (Io) vjorin X ^ cd non alkoxy, Cy -3 Ic alkoxy or cycloalkyl means alkoxy with up to 18 carbon atoms, 309832 / 12Ü1 BAOORfGlNAL - 2ο - Case used . ' ?. Method according to claim 6, wherein X ¹¹ ' _{2 is} an alkoxy, Cycloalkoxy or cycloalkylalkoxy radicals with 8-12. C atoms means used. 8. The method according to claims 1-3 »characterized in that that you can get a compound of the formula (Id) wherein X ^f , an alkyl, cycloalkyl or cycloalkyl radical having 4 to 12 carbon atoms is used. 9 'Organic materials according to claims 1 to are stabilized. Io. Polypropylene stabilized according to claim 9 /. Process for the preparation of compounds of the formula (Ia) according to claim 4, characterized in that .man a compound of the formula ^R 2 309832/1201 - 21 - Case 150-3567 with a ketone of the formula CH, ι -> O = C condensed in an alkaline medium, where R ,, Rp, R ¹ ^, X ¹ - and X * have the meaning according to claim 4. 12. The method according to claim 11, characterized in that R 'means the carboxyl group, whereby after the Condensation decarboxylates the connection established. 13. Compounds of the formula (Ia) 14. Compounds of the formula (Ib) 15 Compounds of the formula (Ic) 16. Compounds of the formula (Id) S A N ü 0 Z AG. V -.- U 309832/12 0