CH651832A5 - PYRAZOLE COMPLEXES. - Google Patents

Description

The present invention relates to new complexes of pyrazole compounds with polyalkylpiperidines, their preparation and their use as light stabilizers. The invention relates to compounds of the formula

II

c - r

0 ©

Ni

(I) /

+2

XA

yH2 °

wherein the formula in the square brackets is an anionic residue of a pyrazole compound,

R is a saturated, optionally substituted aliphatic radical, an aromatic or heterocyclic radical or a cycloalkyl (C6-s) radical,

A is a 2,2,6,6-tetraalkylpiperidine compound which has at least one hydroxyl, an ether or amino group as a substituent or as part of a substituent in the 4-position,

x 1 or 2

y is zero or 1 and the sum of 25 x + y is 1 or 2.

Compounds of the formula c-r1 are preferred

*1

Ni

(la) /

+2

xA.1

yh0O

wherein

R 'alkyl (Ci-22), cycloalkyl (C6-8), aralkyl (C? -Io), the aryl nucleus of which may additionally be substituted by hydroxyl and / or 1 or 2 alkyl radicals having 1-6 C atoms, one Phenyl radical, which can be substituted by a hydroxyl group in the meta or para position, 1 or 2 alkyl and / or alkoxy radicals having 1 -8 carbon atoms and / or phenyl, this phenyl radical carrying at most 3 substituents, a furan, Thiophene or benzothiophene radical, where these radicals can be substituted by 1 or 2 alkyl radicals with 1-4 C atoms, Ri alkyl (Ci-4), a phenyl radical which is substituted by 1 or 2 alkyl radicals with 1 -12 C atoms or 1 or 2 alkoxy radicals with 1-12 carbon atoms or phenyl or the radical phenyl-O- can be substituted, or 3,5-di-tert-butyl-4-hydroxybenzyl, R2 alkyl (Ci-4), phenyl or such phenyl or benzyl substituted by Ri,

A 'a compound of the formula

/ Œ3

(a),

R3H2C OL

R4 is hydrogen, and 40 R5 -OH, -NH2 or one of the radicals (b) or (c) -X-RÖ

H3C

-X-F ^ -X-X NH

^ "^ 2 * 3

h3c

(b),

(c),

wherein

R3 independently of one another hydrogen or alkyl (Ci-4),

50

X -O-, -NH-, -N [alkyl (Ci-4)] -,

ré alkyl (Ci-i8) which is optionally interrupted by oxygen or ss -NH- or -N [AIkyI (Ci-4)] - or is substituted by -COOalkyl (Ci-i8),

R7 alkylene (C2-i2) which is optionally interrupted by oxygen, -NH- or -N [alkyl (Ci-4)] - or R4 and R5 together with the ring carbon atom to which they are attached, a known per se, -O- or -N <T having heterocyclic 5-, 6- or 7-membered, preferably 5- or 6-membered ring, and x and y have the meaning given above.

The alkyl radicals mentioned (^ C3) can each be straight-chain or branched.

In the above formulas, R preferably denotes R 'and preferably R ", i.e. alkyl (Ct-i2), phenyl, which may be replaced by 1 or 2 alkyl (Ci-8) and / or hydroxyl or

651832

Alkoxy (Ci-4) is substituted, preferably R '", i.e. alkyl (Ci-4) may be substituted, or

Alkyl (C4-i2) or phenyl, preferably phenyl.

Ri preferably means R'i, i.e. Alkyl (Ci-4) or phenyl> ^ CH-

or alkyl (Ci-4) phenyl, preferably R "i, i.e. alkyl (Ci-4)

or phenyl, preferably phenyl. Ri as alkyl preferably means methyl.

R2 is preferably R'2, i.e. Alkyl (Ci-4) or phenyl,

preferably alkyl (Ci-4), preferably methyl.

R3 is preferably hydrogen.

R4 is preferably hydrogen and Rs is a radical of 10 Rio hydrogen or optionally substituted alkyl (Ci-4) (ba) or (ca)

-NH-R'6

[preferably by -COOalkyl (Ci-is)], n 1 or 2,

H, C 3 \ CH,

3rd

- NH - alkylene (C2_12) -NH- / NH

/ CH,

(ba), Ri i for n - 1: is -ch2

- (CH2) r and

"Rl3 Rbv

"CH2-O- cm

(ca),

CH2-oh

(CH2-) rOH

20th

for n = 2:

h3c where all R3 and R4 are hydrogen, R '6 is alkyl (C4-i2) or - (CH2-) mCOOalkyl (Ci-i8), m 1-4, preferably 1 or 2, or R4 and Rs together with the common C -Atom a heterocyclic ring.

Preferred ring systems are those (d) to (g):

-CH2. 25 - (CH2-) r.

_ ^ / Rl3 Rl3 ^^

"^ CHz-O-CH2 ^

xm-

~ (CH2-) r

*

c;

Rs

I.

.O-C-R9

I.

-C-N-R10

II

O

(d),

*

-C

-O

-O/

✓ R11

(e)

^ CH2) p -NH

rNull or 1,

R13 is hydrogen, methyl, ethyl or hydroxyethyl,

P 1-4,

30 q 1 or 2,

R.12 for q = 1: alkyl (Ci-is), cycloalkyl (Cs-8), phenyl, and for q = 2: alkylene (C2-8) or phenylene.

Y1 and Y2 independently of one another -O- or -NH-, Xi oxygen or sulfur.

3S In formulas (e) and (g) the residues in the brackets are preferably identical, insofar as n = 2 and q \ .l

R4 is preferably hydrogen and Rs is NH2 or -NH- (CH2-) nCOOalkyl (Ci-i8) or R4 and Rs together form a ring (d) in which Rs and R9 together with the common 40 C atom form a cyclododecylidene ring and Rio is hydrogen.

The compounds corresponding to the non-complexed pyrazoles and the 2,2,6,6-tetraalkylpiperidines are known per se or can be prepared in an analogous manner known per se.

The process for the preparation of the compounds of the formula I is characterized in that 1 mol of an optionally hydrated compound of the formula

Yi

*

c;

-C-N

I.

-Y2-C

--R12

50

(g)>

55

where the carbon atom marked with * means the "common ring carbon atom".

The substituents R8-R12 and q preferably have the following meanings: Rs and R9 independently of one another hydrogen, alkyl (Ci-3o), benzyl; or Rs = hydrogen and R <> phenyl, alkyl (Ci-4) phenyl, chlorophenyl, 4-hydroxy-3,5-tert-butylphenyl, naphthyl; or Rs and R9 together with the common carbon atom to which they are attached form a cycloalkylidene (Cs-is) ring which is formed by

60

(II),

, T. +2 Y "? 0 Ni •

heated with x mol of compound A in an inert solvent, optionally with removal of the water released, 65 and the complex formed isolated in a manner known per se.

The compound of formula II can also be prepared in situ, e.g. by inserting the appropriate pyrazolone

Compound and nickel acetate or pyrazole sodium salt with nickel chloride.

Compounds of formula II and their preparation are e.g. described in DE-OS 2,410,370.

Analogously, the complex of formula I can be prepared in situ by heating a pyrazolone compound or an alkali salt thereof with a nickel salt, preferably nickel acetate, and a 2,2,6,6-polyalkylpiperidine compound in a suitable solvent (for example an alcohol), if appropriate with Removal of water released.

Suitable solvents for the preparation of the compounds of formula I are e.g. Benzene, toluene, xylene and related compounds, which can be refluxed and the water removed using a water separator.

The present invention also relates to a process for stabilizing plastics against degradation by light, characterized in that the plastics to be stabilized are given a compound of the formula I in a concentration of 0.01 to 5% by weight, preferably 0.02 to 1 % By weight before, during or after polymer formation.

The invention also relates to plastics stabilized by this process, which contain 0.01-5% by weight, preferably 0.02-1% by weight, of a compound of the formula I as light stabilizers, and also active ingredient concentrates, so-called masterbatches, which contain a compound of formula I in a concentration of 20-80% by weight, preferably 40-60% by weight.

The applications in the plastics sector are particularly numerous. For example, for polyolefins, especially polyethylene and polypropylene, ethylene / propylene copolymers, polybutylene, as well as polystyrene, chlorinated polyethylene, and polyvinyl chloride., Polyester, polycarbonate, polymethyl methacrylates, polyphenylene oxides, polyamides such as nylon, polyurethanes, polypropylene oxide, polyacetals, phenol-formaldehyde resins, Epoxy resins, polyacrylonitrile and corresponding copolymers as well as ABS terpolymers. The compounds according to the invention are preferably used to stabilize polypropylene, polyethylene, including high molecular weight polyethylene, ethylene / propylene copolymers, polyvinyl chloride, polyester, polyamide, polyurethanes, polyacrylonitrile, ABS terpolymers, terpolymers of acrylic esters, styrene and acrylonitrile, copolymers of styrene and Acrylonitrile or styrene and butadiene, preferably for polypropylene, polyethylene, ethylene / propylene copolymer or ABS.

Natural substances can also be stabilized, such as rubber and also lubricating oils. The incorporation takes place according to methods known per se. A particularly important application method is the intimate mixing of a plastic with the new compounds in the melt e.g. in a kneader or by extrusion, injection molding, blow molding, spinning to corresponding articles. Polypropylene or polyethylene in granular, semolina or powder form is preferably used.

When processing e.g. extrusion, injection molding, rotary molding or blow molding gives, for example, foils, films, hoses, tubes, containers, bottles, profile parts, threads or tapes or even foams. You can also coat metal wires with the polymer melt using a suitable extruder.

The plastics do not necessarily have to be completely polymerized or condensed before they are mixed with the compounds according to the invention. You can also mix monomers or prepolymers or precondensates with the stabilizers according to the invention and only

651832

afterwards during or after condensing or polymerizing the plastic into its final form.

In addition to the compounds of the formula I, further stabilizers can be added to the plastics. Such further connections are e.g. Antioxidants based on sterically hindered phenols, or costabilizers containing sulfur or phosphorus, or a mixture of suitable sterically hindered phenols and compounds containing sulfur and / or phosphorus. Such connections are e.g. Benzofuranone (2) and / or indo-linone (2) compounds, sterically hindered phenols such as ß- (4-hydroxy-3,5-di-tert.-butylphenyl) propionic acid stearyl ester, tetrakis [methylene-3 (3 ', 5 '-ditert.-butyl-4-hydroxyphenyl) propionate] methane, 1,3,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3 , 5 tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -l, 3,5-triazine-2,4,6 (IH, 3H, 5H) -trione, bis (4-tert. butyl-3-hydroxy-2,6-dimethylbenzyl) dithiolter ephthalate, tris (3.5 ditert. butyl-4-hydroxybenzyl) isocyanate, triester (cler ß- (4-hydroxy-3,5-ditertbutyl-phenyl) Propionic acid with l, 3,4-tris- (2-hydroxyethyl) -5-triazine 2,4,6 (IH, 3H, 5H) -trione, bis [3,3-bis- (4'-hydroxy-3- tert-butyl-phenyl) -butanoic acid] -glycol ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-butyl-4-hydroxybenzyl-) benzene, 2,2'-methylene- bis- (4-methyl-6-tert-butylphenyl) terephthalate, 4,4-methylene-bis- (2,6 ditert. butylphenol, 4,4'-butylidene-bis - (- tert. butyl-meta- cresol), 4,4-thio-bis- (2-tert-butyl-5-methylphenol), 2,2 '-methylene -bis- (4-methyl-6-tert-butylphenol). Antioxidant co-stabilizers can also be added, e.g. sulfur-containing compounds, e.g. Distearylthiodipropionate, dilaurylthiodipropionate, tetrakis (methylene-3-hexyl-thiopropionate) methane, tetrakis (methylene-3-dodecyl-thiopropionate) methane and dioctadecyldi-sulfide or phosphorus-containing compounds such as e.g. Trinonyl phenyl phosphite; 4,9-distearyl-3,5,8,10-tetraoxadiphospha-spiroundecane, tris (2,4-ditert.-butylphenyl) phosphite or tetrakis (2,4 ditert.-butylphenyl) -4,4 'biphenylylene- diphos-phonit.

The compounds according to the invention and their mixtures mentioned above can also be used in the presence of further additives. Such are known per se and e.g. described in DOS 2'606'358. These include e.g. to the group of aminoaryl compounds, the UV absorbers and light stabilizers such as the 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, 1,3-bis (2'-hydroxybenzolylbenzenes, salicylates, cinnamic acid esters, esters of optionally substituted benzoic acids, sterically hindered amines, oxalic acid diamides.

Other additives are e.g. Flame retardants, antistatic agents and other additives known per se.

The compounds of the formula I are eminently suitable for use in stove enamels, in particular vehicle finishes, especially two-coat finishes such as e.g. Metallisé paintwork for automobiles. Such coatings, in particular car paints, which contain a compound of the formula I or a mixture of such compounds are the subject of the invention. Such vehicle paints are known.

All types used in industrial painting, preferably stoving paints, are suitable as paints. The latter are vzw. "baked" at over 100 ° C to obtain optimal properties. In particular, in combination with the light stabilizers mentioned, lacquers (so-called wet lacquers) which contain as binders are preferred: combinations of oil-modified polyester resins (oil alkyd resins) and melamine-formaldehyde resins or combinations of externally crosslinking polyacrylate resins and melamine-formaldehyde resins or combinations of saturated polyesters and melamine-formaldehyde resins or themselves5

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

651832

6

crosslinking polyacrylate resins or also polyacrylate resins with copolymerized styrene. In addition, two-component acrylate resin lacquers consisting of acrylate resin containing hydroxyl groups and aliphatic or aromatic isocyanates are also suitable, as are thermoplastic polyacrylate resin lacquers. Also worth mentioning are two-component polyurethane resin paints consisting of hydroxyl group-containing polyester resins and / or polyether resins, cured with aliphatic or aromatic isocyanates. For Métallisé paints, the thermoplastic polyacrylate resins or externally crosslinking polyacrylate resins in combination with butanol-etherified melamine resins and also hydroxy group-containing polyacrylate resins, hardened with aliphatic isocyanates, are of particular importance. The powder coatings known per se, which e.g. were treated with a solution of a compound of formula I. Cross-linking polyacrylate resins, e.g. described in H. Kittel, textbook of paints and coatings, Berlin, vol. I, part 2, "page 712 or also in US-P 3,062,763.

The compound of the formula I can be added to the lacquer in any stage of the lacquer production, in solid or dissolved form. The compound of the formula I is advantageously used in dissolved form in a suitable solvent in a highly concentrated form.

By adding amounts of 0.02-5% UV stabilizer, mainly 0.2-2% according to formula I to the varnishes, the light and weather fastness of organic pigments in those in stove enamels can be significantly increased, and the tendency to form two layers of cracks -Paintings during weathering are significantly reduced and gloss retention can be significantly improved.

Surprisingly, this is also evident, in particular, in the case of metallisé coatings, and an excellent long-term stabilization of the clear coat film of two-layer metallisé coatings with regard to hairline cracking and gloss retention.

The stabilization of two-layer metallic coatings, as is usually used in the automotive industry, can be done either by adding to the base coat and / or by adding to the clear coat. Adding it to the clear coat alone shows a significant improvement in weathering stability.

Metallisé paints according to the invention can be produced in 15 many shades and also in light pastel shades.

The following examples illustrate the invention.

20 Example 1

5.5 g of l-phenyl-3-methyl-4-benzoyl-pyrazolone and 6.2 g of 2,2,6,6-tetramethyl-4-aminopiperidine are placed in 20 ml of ethanol and heated to 50 ° C. creating a clear solution. 2.5 g of nickel acetate tetra-25 hydrate are added to the solution and the resulting green solution is stirred at 70 ° C. for 1 hour, cooled and poured onto ice water,

whereby the product fails. The precipitate is filtered off, washed with water and dried. A green product of mp: 111 ° -l 15 ° C. of the formula vi * "*" 2 is obtained

nl h3c ch3

nh h20

h3c ch3

Example 2 7.6 g of nickel salt of the formula ch.

Ì

A.e

N X0C

«= 3) 3

Ni

2 ^ 0

with 3.6 g of the compound of formula

7

651832

Solvent is distilled off and the residue is pulverized. A green powder with a melting range of (130 ° C. sintering) at 140-147 ° C. clear green melt is obtained, which represents the (2a) anhydrous 1: 1 complex of the two compounds.

Replacing the p-tert-butylbenzoyl compounds (Ni complex) in the above experiment with the corresponding benzoyl compound gives compound No. 11 in Table 1, mp. 152-156 ° C.

Analogously as in Examples 1, the Verbin-in 100 ml xylene fertilize for 3 hours on a water separator of Table 1. X means 1 and 2 y cooked, resulting in a dark green solution. The zero or 1st

Table 1 O

TT

Ni 2+ * x A * yH20

2nd

No.

Ra

CHs

ra2- <ss

2 <□> -

CHa och3

nh2- (

/ -

3 <□> -

C3H7

/

'—R ~

4 CHs

CHj

KH2- <

/

'—R-

5 Œ-

CHs

nh2- <

/

'—R-

CH3

Verb. (2a) from Example 2

651 832 8

Table I (continued) No. Ri Rz R

7 CH3 CHî —verb. (2a) from Example 2

• Q-

cm

-CsHis

Verb. (2a) from Example 2

CHb rcr-py-Œ 2-Œ2-

Verb. (2a) from Example 2

10 CH3

CHs

<□> -

Verb. (2a) from Example 2

11 <□> -

CHs

<ö> -

Verb. (2a) from Example 2

Example 4

The complex compounds from Example 3 are examined for their speed in organic solvents, compared with the solubility. It exhibits a greatly increased solubility of individual components.

connection

Solubility in xylene

Gì

3>

N>

Ni

+2

2H20

<30%

Compound (2a) from Example 2 Complex compound from Example 2

<10%> 60%

Example 5

0.5 pph of the compound of Example 2 are worked into a non-UV-stabilized polypropylene in a mixer kneader at 180 ° C. A 3 mm thick plate is pressed from the kneading mill. A 0.3 mm thick film is also produced. The film is in the Atlas Weatherometer WRC 600

(Xenon lamp) exposed and the damage by the UV light at the increase in the carbonyl band at 5.8 u. determined in the compensation procedure. You get very good results compared to the sample without UV stabilizer.

According to the German DIN standard 53453, stampings on the 3 mm plate are made after exposure in the Atlas Weathero

9

651832

WRC 600 measured the change in impact strength. In comparison to the sample without UV stabilizer, very good results are also obtained.

The other specified compounds are used in an analogous manner.

Example 6 Use in car topcoat.

Paint build-up

Structure of the two-layer Metallisé paint from a base coat and a clear coat according to the following composition.

I. Base coat, consisting of (GT = parts by weight):

12.60 GT commercially available polyacrylic resin, cross-linking

(Viacryl SC 344, Vianova, Vienna) (delivery form 50% in

Xylene / butanol 4: 1) according to definition DIN 53 '186

2.19 GT commercial butanol-etherified melamine resin,

medium reactive, delivery form 72% in isobutanol (Maprenal

MF 800, Casella) produced by polycondensation from 1

Mol of melamine with 3-6 mol of formaldehyde, etherified with 3-6

Mol of butanol as defined in DIN 53 '187

0.96 pbw of butanol

0.26 pbw of colloidal silica

7.05 pbw xylene

52.00 GT cellulose acetobutyrate solution, 20% (composition see below)

6.80 pbw aluminum paste, non-floating (non-leafing), commercial form 65% in alkyl glycol acetate according to definition DIN 55'923 18.14 pbw butyl acetate

Cellulose Acetobutyrate Solution '

20.00 pbw of cellulose acetobutyrate

Acetyl content approx. 13.6%

Butyryl content 38.7%

Hydroxyl content 1.25%

Viscosity in poise (d.Pa.s), 20 ° C in acetone: 2.0 s 10.00 GT butanol 35.50 GT xylene 35.00 GT butyl acetate 100.00 GT

io II. clear coat (top coat)

consisting of

80.00 GT polyacrylate resin (analogous to base coat)

13.75 GT melamine resin (analogous to base coat)

15 4.50 pbw of butyl glycolate 7.50 pbw of solvent, aromatic mixture boiling range approx. 186-212 ° C

6.00 GT solvent, aromatic mixture boiling range approx. 155-178 ° C

20th

Execution:

Paint build-up Base coat I additionally colored with 0.3 GT copper phthalocyanine blue C.I. Pigment Blue 15: 1, applied by spraying, layer thickness approx. 20 | i (without UV stabilizer). 25 Overpainted (spray application, after the base coat has dried)

a) with clear varnish according to II

b) with clear lacquer according to II additionally containing 1 part by weight of the compound from Example 2

a) and b) baked at 140 ° C for 30 minutes.

Weathered 1 year Florida, 5 ° inclination to the south. 35 sheets according to example b) achieve a significantly better rating than those according to example a).

The other specified compounds are used in an analogous manner.

B

Claims (7)

651832 +2 wherein R 'alkyl (Ci-22), cycloalkyl (C6-8), aralkyl (C7-io), whose aryl nucleus can additionally be substituted by hydroxyl and / or 1 or 2 alkyl radicals having 1-6 C atoms, a phenyl radical , which may be substituted by a hydroxyl group in the meta or para position, 1 or 2 alkyl and / or alkoxy radicals with 1 -8 carbon atoms and / or phenyl, this phenyl radical carrying at most 3 substituents, a furan, thiophene or benzothiophene radical, where these radicals can be substituted by 1 or 2 alkyl radicals with 1-4 C atoms, R i alkyl (Ci-4), a phenyl radical which is substituted by 1 or 2 alkyl radicals with 1-12 C atoms or 1 or 2 alkoxy radicals with 1-12 C atoms or phenyl or the radical phenyl-O- can be substituted, or 3,5-di-tert-butyl-4-hydroxybenzyl, Rî alkyl (Ci-4), phenyl or as in Ri substituted phenyl or benzyl, A 'a compound of the formula (a), h3c 2R3 1V-CK H3c (la), XA ' ïh2 ° X -O-, -NH-, -N [alkyl (Ci-4)] -, ró alkyl (Ci-i8) which is optionally interrupted by oxygen, or -NH- or -N [alkyl (Ci-4)] - or is substituted by -COOalkyl (Ci-i8), 35 R7 alkylene (C2-i2) which is optionally interrupted by oxygen, -NH- or -N [alkyl (Ci-4) j- or R4 and R5 together with the ring carbon atom to which they are attached, an -O- and / or -NC-containing heterocyclic 5-, 6- or 7-membered, preferably 5- or 40 6-membered ring, and x and y have the meaning given in claim 1. 2. Compounds according to claim 1 of the formula 20th Ni 2nd PATENT CLAIMS 1. Complexes of pyrazole compounds with polyakylpiperidines of the formula (I) / M- +2 Ni where the formula in the square brackets represents an anionic residue of a pyrazole compound, R is a saturated, optionally substituted aliphatic radical, an aromatic or heterocyclic radical or a cycloalkyl (Gj-s) radical, A is a 2,2,6,6-tetraalkylpiperidine compound which has at least one hydroxyl, an ether or amino group C - R * xA * yHo0 as a substituent or as part of a substituent in the 4-position solution, x 1 or 2 Y is zero or 1 and the sum of x + y 1 or 2 mean. 3rd 651832 Paintings, in particular vehicle paints, with 0.01 to 5% by weight, preferably 0.02 to 1% by weight, of a compound of formula I. 3. A process for the preparation of the compounds of formula I according to claim 1, characterized in that 1 mole of a compound of formula 45 50 C - R (n). Ni + 2 • y H £ 0 55 wherein Rj are independently hydrogen or alkyl (C1-4), R4 is hydrogen, and Rs -OH, -NH2 or one of the radicals (b) or (c) -X-Rô (b), (C), with x mole of compound A, where A, x and y have the meaning given in claim 1, heated in an inert solvent. so 4. A method for stabilizing plastics against degradation by light, characterized in that the mass of the plastics to be stabilized before, during or after the polymer formation 0.01 to 5%, based on the weight of the plastics mass, a compound of the formula 65 I, according to claim 1, adds. 5. A method for stabilizing plastics, according to claim 4, characterized in that coating compositions for industrial coatings, preferably stoving 6. Stabilized plastics which contain from 0.01 to 5% by weight of a compound of the formula I as a light stabilizer, prepared by the process according to claim 4. 7. active ingredient concentrates which are intended to stabilize plastics against degradation by light and which contain 20 to 80% by weight of a compound of the formula I according to claim 1.