DE1670951A1 - Alkylene bis (benzotriazolyl phenols) - Google Patents

Description

FARBENFABRIKEN BAYER AG LEVERKUSZN-Bayeiwerk

r * ttnt-Abttüut My / BS

20. Uo λ 1367

Alkyl βη-bia- (benztriazolyl-phenols)

The present application relates to new alkylenebi (benztriazolyl-phenols) of the general formula I

1 2
where the radicals R and R can be identical or different and are hydrogen, an alkyl, cycloalkyl or aralkyl radical with a maximum of 10 carbon atoms or an aryl radical, which can optionally be further substituted, a hydroxy, alkoxy, carboxy, carbalkoxy, Mean carbonamide, sulfonamide, alkylsulfone, arylsulfone or acylamino group or a halogen radical, R ^ and

4th
R represent identical or different radicals and represent hydrogen, an alkyl radical with 1-4 carbon atoms, a cycloalkyl radical with 5-6 carbon atoms, or a benzyl or aryl radical optionally substituted in the aromatic ring, η is an integer from 1- 4 and m are an integer from 1-3,

109808/2174 Ie A 11 098

as well as their production and their use as UV absorbers.

Preferred compounds of general formula 1 are included

3 4 1

those in which Fr and R are hydrogen and R and

R as well as η and m have the meaning mentioned. Such connections show a particularly favorable specific extinction coefficient.

Oils according to the invention compounds of the general formula I are particularly suitable as UV absorbers for polymers such as polystyrenes, polyacrylonitrile, polyacrylates and their copolymers, polydienes, e.g. B. polybutadiene, polyvinylidene chloride, polyvinyl chloride, polypropylene, polyethylene, polyester, e.g. B. polyethylene terephthalate, polycarbonates, polyamides, e.g. B. polycaproleate, and polyurethanes, those polymers having the Torrang, which at higher temperatures, z. B. above half of 150 ° are processed. The substances according to the invention are added to the polymers in amounts of up to about 5 #, preferably in amounts of 0.1-2 #.

The invented compounds offer an unexpected combination of excellent properties: they not only have well-stored absorption spectra and excellent lightfastness, but are also characterized by extraordinary resistance to sublimation, high specific absorption coefficients and good compatibility with plastics.

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109808/2174

The 2- (2'-hydroxy-5'-niethylphenyl) -benztriazole described in DAS I.lö5.bic, which is frequently used in industry as a UV absorber for polymers , shows a favorable absorption spectrum, a high specific extinction coefficient and a good one Resistance to light and heat, due to its easy Subli mierbarkeit arise for the incorporation into plastics, whose processing takes place at relatively riohen temperatures, difficulties, whereby special equipment precautions and to compensate for Sublimationsveriusten an increased effort are required. Corresponding substitution products with longer alkyl chains do not give satisfactory results either. Although they show slightly improved sublimation behavior, their specific absorption coefficient is reduced compared to the corresponding products with short-chain alkyl residues. A compensation for the lower specific. Absorption through the use of larger amounts of absorber are also limited by the undesired property changes caused by the polymers.

The compounds according to the invention can be incorporated in a wide variety of ways , for example by mixing them with the polymers prior to their further processing at a higher temperature by adding them to the melt of the poly mers, or by adding suspended polymers during their processing. If appropriate, they can also be added to the starting materials for the preparation of the polymers, and Terlleren cannot absorb its absorption capacity even in the presence of other customary light or heat stabilizers, oxidation and friction agents and the like.

Le A 11 09c - 3 - _B

BATH

10 9 8 0 8/217 /,

The new compounds can be prepared analogously to the information in DAS IJ85.6IO column j $, paragraph 2, whereby alkylenebisphenols or alkylenebis-aminophenols are to be used for the compounds according to the invention, but the preparation by reaction of 2- ( 2 ^f -hydroxyphenyl) benzotriazoles of the general formula II

II

1 2 wherein R, R , η and m have the meanings given above and the phenol-flat ring in o- and / or p-position to the OH group must be substituted by hydrogen, with compounds which the introduction of the grouping

B? R ⁴

cause, in the presence of acids or under conditions of the Priedel-Crafts synthesis in inert solvents such as glacial acetic acid, Nitrobenzene or carbon disulfide.

For the preparation of compounds of the formula I suitable Auegaignrerbindungen of the formula II are, for example following:

2- (2 · -Hydroxy-5'-methoxyphenyl) -benztriazole 2- (2 ^f -hydroxy-5'-methoxyphenyl) -5-methyl-benzotriazole 2- (2 · -hydroxy-5 * -phenoxy -pheny1) -benz triazole

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i; .- ;, vv ■ * SAD ORIGINAL

10 9808/2176

2- (2 · -Hydroxy-5'-methyl-phenyl) -5,6-diehlor-benzotriazole 2- (2 · -Hydroxy-5'-phenyl-ph.enyl) -5-chlorobenztrlasol 2- (2-hydroxy-5'-cyclohexyl-plienyl) -5-chloro-beiiztriazole 2- (2'-Hydroxy-5 ■ -cyelohexyl-phenyl) -benztriazole 2- (2'-Hydroxy-5'-phenyl-phenyl) -benztriazole 2- (2'-Hydroxy-5'-methyl-phenyl) -benztriazole 2- (2'-Hydroxy-5'-amyl-phenyl) -benztriazole 2- (2 * -Hydroxy ~ 5'-1ert.butyl-phenyl) -benztriazole 2- (2 · hydroxy-phenyi) -benztriazole

2- (2'-Hydroxy-5'-carbethoxyphenyl) -benztriazole * k

2- (2 »-hydroxy-4 ', 5-dimethyl-phenyl) -benztriazole-5-eartoone acid butyl ester

2- (2'-Hydroxy-5'-methyl-phenyl) -benztriazole-5-carboxylic acid butyl

Cyclohexyl 2- (2-hydroxy-5'-methyl-phenyl) -benztriazole-5-carbonic acid

2- (2-hydroxy-5'-methyl-phenyl) -benztriazole-5-carbonic acid diethylamide

2- (2 · -Hydroxy-5'-methyl-phenyl) -benztriazole-S-carboxylic acid

2- (2 »-hydroxy-4 ', 5'-dichloro-phenyl) -benztriazole %

2- (2-hydroxy-5'-methyl-phenyl) -benztriazole-5-ethylsulfone H- (2-hydroxy-4'-propionyloxyphenyl) -benztriazole 2- (2-hydroxy-phenyl) -5-methoxy -6-methyl-benzotriazole 2- (2 »-hydroxy-5 ^! -Methyl-phenyl) -benztriazole-5-sulfonic acid diethylamide

2- (2 · "hydroxy-5 '~ methyl-phenyl) benzotriazole-5-methyleulfon, 2- (2-hydroxy-5 ^{f f} -cyclohexyl) benzotriazole, 2- (2'-hydroxy-5 ¹ -o -tolyl-phenyl) -benztriazole.

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ORIGINAL 109808/2174

For the introduction of grouping

R 'R

suitable compounds are, for example, carbonyl compounds and α-chloroalkyl ethers. As carbonyl compounds for example called paraformaldehyde, as a-chloroalkyl ether Chlorine ethyl methyl ether.

The parts given in the following examples are parts by weight, the degrees are to be understood as degrees Celsius, K is the specific extinction coefficient given in / and A. max denotes the absorption maximum.

Example 1;

450 parts of 2- (2'-hydroxy-5'-methyl-phenyl) -benztriazole are dissolved in 3900 parts of ice-cream vinegar by heating to 100 °, 33 parts of paraformaldehyde are added with stirring and 196 parts of conc. Sulfuric acid are added dropwise at 100 °. Into the reaction mixture in 30 minutes. The mixture is subsequently stirred at 115 ° for four hours, allowed to cool and the precipitate formed is filtered off with suction. The precipitate is washed neutral and dried at 120 °. 448 parts of 2,2'-methylenebis- / 4-methyl-6-benztrlazolyl- (2) -phenol_7 »which, after recrystallization from chlorobenzene, melts at up to 284 °, λ _, _Q _ 346 am; K = 75.8 (CHCl _x )

Max

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109808/2174

Example 2:

Mau gives 56.25 parts of 2- (2'-hydroxy-5-methyl-phenyl) -benztria »ol in 300 parts of nitrobenzene and adds 33.3 parts of aluminum chloride at 5-10 °. At this temperature, 10 g of chloroethyl methyl ether are added dropwise and the reaction mixture is then heated up to 90 ° as a lease. At 60 ° the evolution of hydrogen chloride begins. After the development of hydrogen chloride has ended, the mixture is cooled, and the reaction mixture is poured into a mixture of 1000 parts of ice and 100 parts of conc. Hydrochloric acid entered. The nitrobenzene is evaporated off with steam, the residue is isolated and washed neutral. 48 parts of 2 ₁ 2'-methylenebla- / ~ 4-methyl-6-benzotriazolyl- (2) -phenol_7 are obtained.

Example Jt

67.2 parts of 2- (2 ^l -hydroxy-5 ^l -nonyl-phenyl) -bed «triazole are dissolved in 368 parts of Elseaslg, 8.8 parts of chloromethyl methyl ether and 10 parts of conc. Sulfuric acid added. Hydrogen chloride escapes during heating to 100 °. The mixture is stirred for two hours, cooled and decanted from the separated OsI. The oil is dissolved in methylene chloride, washed neutral and, after evaporation, reprecipitated from 130 parts of butanol. After working up the mother liquors, 38 parts of a resin of 2.2 ^l -methyleubls- / ~ 4-nonyl-6-benzotriazolyl- (2) -phenol ^ / · 71 _max 344 m; K = 50.0

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TO 9808/2 17th

Example 4:

To compare the different sublimability, 6 parts of each substance A - D were placed in an externally heated, calculable sublimation apparatus provided with a fingertip, and the amount of the substances sublimed under certain conditions was determined and compared in a table.

Substance A
Substance B

2- (2-hydroxy-5-methyl-phenyl) -benztrlazole

2- (2-hydroxy-3 ', 5'-di-tert-butyl-phenyl> benztrlazole

Substance C = 2- (2'-Hydroiy-3 ¹ -methyl-5'-tert.-butyl-phenyl) -

5-chlorobenztrlazole

Substance D = 2,2'-Methylenble- / ~ "4-methyl-6-benztriazolyl-1 [2) -

phenol_7

temperature
of the heating bath

Torr substance tent sublimate sublimate / ßmjKg / äln_7 Z * elle_7 C * J

150 ° 0.2 A. 22nd 6th 100 150 ° 0.2 B. 30th 2.9 47.7 150 ° 0.2 C. 30th 3.2 52.8 150 ° 0.2 D. 30th O O 250 ° 0.1 D. 60 0.04 0.66 250 ° 40 C. 60 4.0 66.7 250 ° 40 B. 60 2.7 45.2 250 ° 40 A. 60 4.2 69.5 Le A 11 098 - 6 -

109808/2174

Example 5:

To determine the effectiveness of the compounds according to the invention as UV absorbers in polypropylene, the following tests were carried out: a) 100 parts of polypropylene

0.2 parts of 2.2 ^f -Methylene-bis- / ~ 4-methyl-6-.benztriazolyl- (2) -phenol_7

0.25 parts of a hardening agent for wetting the surface of the granulate

such as B. sulphurized hoof oil are intimately mixed in a mixing drum and then in a kneading screw Melted with a slot die at a temperature of 210 - 220 ° and injected into strips 0.3 - 0.4 mm thick. A slight stretching of the plastic can be achieved by slightly accelerating the trigger.

Experiment as described under a), however

b) using 0.2 parts of 2- (2'-hydroxy-5 ^l -methylphenyl) -benztriazole instead of the 2,2'-methylene-bis - / "~ 4-« ethyl 6-benztriazolyl- (2) - phenol__7.

Experiment as described under a), however

c) without using a UV absorber.

The tapes produced according to a), b) and c) do not differ visually from one another, but they are visually different Cured white paper stapled and with a UV lamp

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109808/2174

(Pa. Ho truer UVAHALTS 365, ö mu) irradiated, so it glows Paper under foil c due to the one that was passed through Particularly intense blue UV light, clearly blue under foil b and under slide a does not appear at all.

With the same amount of UV absorbers used in & and b and almost the same specific Sxtinktlonnkoeffisienten of the » den.UV-Ab «rber eats Foil« b # in © c? eil de © UV light. The 2- (2-hydroxyl-5'-methyl pbenTl) «beiistriasol evaporated partially during the manufacture of the tapes.

6ϊ

a) For 100 parts of molten polycarbonate made from 2,2- (4,4'-dioxydlphenyl) propane with a K value of 50, 0.2 parts of 2,2'-methylene-bis- / ~ 4-methyl-6-benzotriasolyl are added - (2) -phenol__7 as UV absorber entered and homogeneously distributed with stirring. The material is taken as a strand or tape from the stirred tank discharged and granulated. In the extruder, the granulate is drawn out in the form of threads, bristles, foils or plates or pressed into molded parts in the injection molding machine. They have very good light and heat resistance. Tor allen does not take place during hot deformation or in the manufacture of threads, tapes and foils Volatilization of the UV absorber takes place. The optical and mechanical properties of the polycarbonate are not adversely affected.

Le A 11 098 - 10 -

! AD 109808/2174

b) If 0.2 parts of 2- (2'-hydroxy-? ^f - "ethyl-phenyi) -benzotriazole are used in the UV absorber, there is a clear need for production of threads, foils, bristles or tapes a, which can be easily demonstrated by the test described in Example 5.

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Claims (10)

Patent claims: where the radicals R and R can be identical or different and are hydrogen, an alkyl, cycloalkyl or Aralkyl radical with a maximum of 10 carbon atoms or an aryl radical which is optionally further substituted can be a hydroxy, alkoxy, carboxy, carbalkoxy, carbonamide, sulfonamide, alkylsulfone, arylsulfone or Acylamino group or a halogen radical, R ^ and R represent identical or different radicals and for hydrogen, an alkyl radical with 1-4 C atoms, one Cycloalkyl radical with 5 C C atoms, or optionally one benzyl or aryl radical substituted in the aromatic ring, η is an integer from 1-4 and m is an integer Mean number from 1-3. 2. Z | 2'-methylenebia- / ~ 4-methyl-6-benztriazolyl- (2) -phenol J. 3. ² f2'-methylene-bis- / "4-nonyl-6-benztriazolyl- (2) -phenol J. Ie A 11 098 - 12 109808/2174 BATH ORIGINAL 4. Use of Allcylen-bis-Cbenztriazolyl-phenols) the formula HO 1 2
where the radicals R and R can be identical or different and are hydrogen, an alkyl, cycloalkyl or aralkyl radical with a maximum of 10 carbon atoms or an aryl radical, which can optionally be further substituted, a hydroxy, alkoxy, carboxy, carbalkoxy, Mean carbonamide, sulfonamide, alkylsulfone, arylsulfone or acylamino group or a halogen radical, Br and 4th
R represent identical or different radicals and represent hydrogen, an alkyl radical with 1-4 carbon atoms, a cycloalkyl radical with 5-6 carbon atoms, or a benzyl or aryl radical optionally substituted in the aromatic ring, η is an integer from 1- 4 and m are an integer from 1-3, as UV absorbers in polymers. 5. Use of 2,2-methylene-bis- ^I / ~ 4-iaethyl-6-benztriazolyl- (2) -phenol_7 as UV absorbers in polymers. 6. Use of 2,2'-methylene-bls- / ~ 4-nonyl-6-benBtriaaolyl * (2) -paenol_7 as UV absorber in polymers. Le A 11 098 - 13 - 109808/2174 7. Use of alkylene-bis (benztriazolyl-phenols) according to Claim 4 as a UV absorber in polyolefins, polyesters, polyvinyl chloride and polyvinylidene chloride. 8. Use of 2.2 ^l -Methylene-bia- / ~ 4-methyl-6-benztriazolyl- (2) -phenol_7 all UV absorbers in polypropylene, polyethylene, polycarbonate and polyvinyl chloride. 9. Use of 2,2'-methylene-bia - / "~ 4-nonyl-6-benztriazolyl- (2) -phenol_7 as DV Abaorber in polyethylene, polypropylene Polycarbonate and polyvinyl chloride. 10. With the compounds of claim 1 protected against UV-Stählung polymers. Le A 11 098 '- 14 - COPY 109808/2174