DE2410370C2 - New pyrazole compounds, processes for their preparation and the use of pyrazole compounds to stabilize organic materials - Google Patents

Description

2. Process for the preparation of the compounds of the general formula (I) according to claim 1, characterized in that one mole of the compound of in a known manner general formula (III)

20th

30th

35

40

45

3. Use of pyrazole compounds of the general formula (II)

OMe

for stabilizing organic materials, in which

R2 'is an alkyl radical with 1-22 carbon atoms, a cycloalkyl radical with 6-8 carbon atoms, a Aralkyl radical with 7-10 carbon atoms, whose aryl nucleus is additionally represented by hydroxyl and / or 1 or 2 alkyl radicals with 1-6 carbon atoms can be substituted, a phenyl radical by a Hydroxyl group, 1 or 2 alkyl and / or alkoxy groups with 1-8 carbon atoms and / or Phenyl can be substituted, this phenyl radical having a maximum of 3 substituents, a furan, thiophene or benzothiophene radical, these radicals being represented by 1 or 2 Alkyl radicals can be substituted with 1-4 carbon atoms,

means and Ri, R3 and Me have the meaning according to claim 1.

4. Use of the compounds of formula (I) and (II) according to claims 1 and 3 for Stabilizing polyolefins, polyesters, polymethyl methacrylates, polyphenylene oxides ^ polyurethanes, polystyrene, polypropylene oxide, polyamides, polyacrylonitrile, ABS terpolymers, terpolymers of Acrylic esters, styrene and acrylonitrile, copolymers of styrene and acrylonitrile or styrene and butadiene.

5. Use according to claim 4 for stabilizing polypropylene and polyethylene.

N \

-CH ₂ C

The invention relates to nine pyrazole compounds and their preparation as well as to the use (Π1) dur.p of pyrazole compounds for stabilizing

organic materials as described in the claims

A preferred embodiment is the use of compounds of the formula (II a)

with one mole of the general formula (IV)

R ₂ COCI (IV)

converts, and if Me is an equivalent of nickel or cobalt, converts the product obtained into the corresponding Me salt, where Ri to R _{3 have} the meaning given in claim 1.

(Ua)

OMe

wherein

Ri 'and R3' independently of one another are an alkyl radical with 1-4 carbon atoms or a phenyl radical substituted by 1 or 2 alkyl radicals with 1-4 C atoms can be substituted, mean, and

Me and R2 'have the meaning according to claim 3 to have.

Mention should also be made of the preferred use of compounds of the formula (II b)

15th

(Cb)

20th

OMe; _{/ 2}

40

25th

wherein

Ri "the phenyl radical, which is replaced by an alkyl radical with 1,2,3 or 4 carbon atoms can be substituted, or methyl,

R ₃ "is an alkyl radical with 1, 2, 3 or 4 carbon atoms or the phenyl radical,

R2 "is an alkyl radical with 8-11 carbon atoms, a Cyclohexyl radical, a phenylethyl radical, its aryl nucleus additionally by a hydroxyl group and / or 1 or 2 alkyl radicals with 1, 2, 3 or 4 carbon atoms may be substituted, a phenyl radical by a hydroxyl group, 1 or 2 Aiityl- or a Alkoxy group with 1, 2, 3 or 4 carbon atoms and / or phenyl can be substituted, however carries at most 3 substituents, or a radical of furan, thiophene, benzothiophene, which may be substituted by a methyl or ethyl group, and

Me 'mean nickel or cobalt.

45

Unless otherwise specified, the alkyl radicals are naturally occurring or synthesizable primary, secondary or tertiary, straight-chain or branched in question.

The nickel salts can also contain 1-2 mol of water of crystallization. The reaction is advantageously carried out in an inert organic solvent, it being possible for the starting materials to be dissolved or also suspended therein. The mixture is preferably heated to from 20 ^° C. to 110 ^° C., whereupon hydrogen chloride is split off. This can be allowed to escape from the reaction vessel at an elevated temperature. In general, however, it is more expedient to carry out the reaction in the presence of acid-binding agents, such as, for example, CaO, alkali metal carbonate or bicarbonate, pyridine, trialkylamine or m> dialkylaniline. The reaction takes place in the absence of moisture. Suitable solvents are e.g. B. benzene, xylene, cymene, diphenyl ether, tetrahydrofuran. Dioxane. If Me is an equivalent of nickel or cobalt, the compound of the formula (I) in which Me is hydrogen can first be converted into the alkali metal salt, e.g. B. by dissolving the compound of formula (I) in alcohol and adding an alkali hydroxide such as NaOH or KOH. A salt is then added to the reaction mixture, e.g. B. the chloride, whereupon the desired product is obtained.

A preferred embodiment is the direct production of the metal salt from the compound of Formula (I) in which Me is hydrogen by adding the latter reacts directly with the acetate of nickel or cobalt. This reaction is carried out preferably in an alcohol such as methanol, ethanol, propanol, and the like. at room temperature to the reflux temperature of the solvent. When it cools down, the product mostly fills up.

If this is not the case to a sufficient extent, the precipitation can be accelerated by adding water will.

For use as stabilizers, the compounds are converted into substances sensitive to light incorporated or applied as a protective layer to the substances to be protected. Through her The new compounds used in this way preserve the sensitive substances with a stabilizing effect Destruction. Organic materials suitable for this treatment are, for example: polyolefins, in particular Polyethylene and polypropylene, polyester, polymethyl methacrylate, polyphenylene oxide, polyurethane, polystyrene, ABS terpolymers, polyamides such as nylon, polypropylene oxide, polyacrylonitrile and the like Copolymers. The compounds according to the invention are preferably used for stabilization of polypropylene, polyethylene, polyester, polyamide, polyurethanes, polyacrylonitrile, ABS terpolymers, terpolymers of acrylic ester, styrene and acrylonitrile, copolymers of styrene and acrylonitrile or styrene and Butadiene.

Natural substances can also be stabilized, such as rubber, cellulose, wool and silk. The substances to be protected can be in the form of plates, rods, coatings, foils, films, tapes, fibers, Granules, powders and in other processing forms, or as solutions, emulsions or dispersions are present. The incorporation or coating of the materials to be protected takes place according to per se known methods. A particularly important application method is intimate mixing a plastic, for example of polypropylene in granular form, with the new compounds, for. Am a kneader and in the subsequent extrusion. A very homogeneous one is obtained in this way Mixing what is important for good protection. When extruding, for example, films are obtained Tubes or threads. The latter can be woven into textiles. In this way of working, the Stabilizer mixed with the polypropylene before processing into a textile material, however, can also treat textile thread and textile fabric with the new stabilizers, for example in an aqueous one Liquor which contains a dispersed compound of the formula (II). Suitable for this procedure Textiles made from polyethylene terephthalate and cellulose acetate. Plastics do not necessarily have to be fully polymerized or condensed before mixing with them the new connections. You can also use monomers or prepolymers or precondensates mix with the new stabilizers and only afterwards the plastic into its final shape transfer by condensing or polymerizing.

The stabilizers can not only be used to clear films, plastics and the like

stabilize, they can also be used in opaque, semi-opaque or translucent materials whose surface is sensitive to degradation by ultraviolet light, air and heat. Examples of such "materials are: foamed plastics, opaque films and covers, opaque papers, clear and opaque colored plastics, fluorescent pigments, Automotive and furniture polishes, creams and lotions and the like.

The amount of incorporated protective agents varies between 0.01 and 5%, preferably between 0.05 and 1%, based on the weight of the materials to be protected.

In the following examples, parts are parts by weight and percentages are percentages by weight. the Temperatures are given in degrees Celsius.

The specified structures are secured by microanalysis and spectral analysis

crystallized. The compound with a melting point of 187-188 ° C. of the formula is obtained

example 1

A mixture of 17.4 parts of 1-phenyks-methyl-pyrazolone (5), 11.2 parts of CaO and 19.6 parts of 4-tert-butylbenzoyl chloride is refluxed for 30 minutes in 100 parts of dioxane. The resulting thick mush is poured into 200 parts of water at room temperature with stirring. The resulting brown solution will acidified with dil. HCl, the precipitate which has separated out is filtered off with suction, washed neutral, dried and removed Methanol crystallizes). The compound of melting point 107-109 ° C. of the formula is obtained

H ₃ C

C (CHj) ₃

C (CHj) ₃

Example 3

3.75 parts of 1,3-diphenyl-4 [3 ', 5'-di-tert-butyl-4'-hydroxy] bea7oyl-5-hydroxypyrazole are placed in 60 parts of ethanol and heated to 45.degree 4 parts of 2N KOH solution are added to the mixture, followed by a solution of 0.94 parts of NiCl ₂ -6 H ₂ O in 20 parts of ethanol for 10 minutes. The solution immediately turns green and KCl precipitates. After a reaction time of 30 minutes, the KCl is filtered off and the green solution is evaporated. The solid residue is washed with water, filtered off with suction and dried at 120 °. The compound with a melting point of 250 ° C. of the formula is obtained

C (CHj) ₃

C (CHj) ₃

10 parts of the compound obtained are dissolved in 20 parts of methanol to prepare the nickel salt and treated with the stoichiometric amount Nickelacetal The mixture is then heated for 30 minutes at 70 ⁰ C and allowed to cool. The resulting green precipitate is filtered off with suction, washed with methanol / water 1: 1 and dried at 110.degree. Mp. 205 ° C. A practically quantitative yield is obtained. The cobaite salt is obtained in an analogous manner.

B e i s ρ i e 1 2

A mixture of 8.26 parts of 1,3-diphenylpyrazolone (5), 332 parts of CaO and 93 parts of 3,5-di-tert-butyl-4-hydroxy-benzoyl chloride are refluxed in 100 parts of dioxane for 2 hours . The mixture is then cooled to room temperature and the solution consisting of 50 parts of 2N HCI and 100 parts of ice water, gego ^c sen. The deposited precipitate is filtered off with suction, washed neutral and the nickel salt can also be prepared analogously to Example 1 from methanol.

B e i s ρ i e 1 4

34.8 parts of 1-phenyl-3-methyl-pyrazolone (5) and 13.2 parts of CaO are placed in 40.0 parts of dioxane at room temperature. The mixture is then heated in a (V'jßd (80 ⁰ C). With stirring, 43.7 parts of lauric acid chloride starting zuzutropfei at 75 ° C reaction temperature ". The acid chloride is added over 45 minutes. The temperature rises bic to 95 ⁰ C., and at the end a thick, brown, easily stirrable part is formed After the addition of the acid chloride, the mixture is left to react for 1 hour at 80 ° C. It is then cooled to 50 ° C., 100 ml of methanol and 100 ml of methanol are added in succession 23.0 parts of hydrochloric acid, after the latter has been added, more is left

stir for 30 minutes; then added to the mixture all at once with 24.8 parts of nickel acetate and stirred for 30 minutes at reflux (internal temperature: 7O ⁰ C). The precipitated nickel complex is at 50 ° C

Sucked off, washed with 1.5 parts of water and crystallized free of halogens. M.p .: \ ^Λ 2 - 128 C. is obtained and then connects the 2 times with 30 parts of methanol and dried at dung of formula 1 0 ⁰ C dried!. Mp. 144- 148 ⁰ C. It is the nickel salt of the compound obtained of the formula

! I - ι nll-C, Cv

o ^N s

H ₁ C CC ₁₁ H ,,

ONi ,,,

To prepare the corresponding cobalt complex, the procedure is analogous to that in Example I or 3 described.

Example 5

A mixture of 53.3 g of 1-phenyl-3-methyl-pyrazolone (5), 8.5 g of CaO and 44.0 g of thiophene-2-carboxylic acid chloride is stirred in 120 ml of dioxane at 95 ° C. for 2 hours. After cooling to 50 ° C., 100 ml of methanol and 30 ml of conc. HCI. It is then allowed to stir for a further 30 minutes. The whole is then poured into 500 ml of ice water, a voluminous precipitate separating out. The precipitate is filtered off with suction, washed with water and crystallized from methanol. M.p .: 133- 136 ^C C. to yield the compound of formula

CH ₃

OH

Example 6

A mixture consisting of 20.2 g of 1-phenyl-3-npropylpyrazolone (5) and 62 g of CaO is heated to 75 ° C. in 80 ml of dioxane. At the same temperature, the mixture is stirred at 14.7 g over the course of 15 minutes thiophene-2-carboxylic acid chloride are added, keeping the reaction temperature to 95 ⁰ C. the mixture is allowed to rise the whole for 1 hour at 95 ° C to react further and then distilled off the dioxane. 100 ml of methanol and 10 ml of concentrated HCl are added to the thick, brown paste that remains and the mixture is refluxed for 30 minutes. The resulting clear brown solution is poured onto 200 ml of ice water. The reaction product precipitates in the process. The precipitate is filtered off with suction, washed with water and extracted from ethanol N η
N

OH

I) e i s ρ ι e I 7

12.5 G of compound of Heispiel b are placed in 100 ml methanol at 45 <5.0 g Nickclacetat 6 H ₂ O. The mixture becomes without further heating. Stirred for 1 hour. The resulting green precipitate is filtered off with suction, washed with water and dried at 90.degree. Smf ..: 145-1 55 "C. The compound of the formula is obtained

n - C Ml-

O -Ni.

Example 8

18.8 g of 1-p-tolyl-3-methylpyrazolone (5) and 6.18 g of CaO in 100 ml of dioxane are mixed with 14.7 g of thiophene-2-carboxylic acid chloride at 90 ° C. over a period of 30 minutes. The dioxane is then distilled off in a water jet vacuum. The thick paste that ^{remains is concentrated at 60 °} C. with 80 ml of methanol and 10 ml. HCl added and refluxed for 30 minutes. 11.8 g of nickel acetate 6 H ₂ O are then added to the whole, the mixture is stirred for a further 30 minutes and then cooled to room temperature. The resulting green precipitate is filtered off with suction, washed with water and dried. M.p .: 180-184 ⁵ C The compound of the formula is obtained

CH,

O
C-

O - Ni -, -

CH

Example 9

11.4 g of the compound from Example 5 are in 100 ml A solution of 1.6 g of NaOH in 10 ml of water was added to methanol at 45 ° C. and the mixture was stirred for 30 minutes. then the yellow solution is dissolved in 4.6 g NiClj · 6 H2O in 20 ml of water are added. After the addition of the nickel chloride, a green precipitate separates out Sucked off at room temperature, washed with water and get-Dcknet. M.p .: 175-180 "C. The Compound of formula

Example 10

11.4 g of the compound from Example 5 are mixed with 5.0 g of cobalt (II) acetate in 150 ml of methanol at 45 ° C. while stirring. After the addition of the salt, a precipitate separates out. The yellowish precipitate is filtered off with suction at room temperature, washed with water and dried. M.p .: 165-170 ⁰ C. to yield the compound of formula

CH,

The compounds listed in Tables 1 and 2 is produced in an analogous way.

Table 1

R, CO-R,

OH

M.p.

CH,

CH,

CH ₃

157-159

147-149

151-152

C (CH,),

CH,

109-110

OCH, C (CH ₃ ),

CH,

> 260

ΓΓΓΗΑ

rortset / unt!

No. R,

1!

12th

Snip. ⁰ C

14 CH ₃

CH,

CH ₁

CH,

-CH ₃

O VCH ₃ -CH ₃

O V-CH ₁

O / -C (CH ₁ ),

C (CH ₁ ),

CH ₂ CH ₂ - ^ O V-OH
C (CH ₃ ),

η - C _n H ₂₃

C (CH ₃ ),

OV-OH

C (CH ₃ ),
H

Ιίΐιν

45-47

90-92

193-194

133-135

59-61

106-109

69-70

132-135

O VC (CH ₃ J ₃

77 -78

100-101

127-130

165-166

-CH ₃ - C ₉ H ₁₉ (n)

label le 2

Il

C - K.

14th

OMc,

No. H ₁

22 the same.

23 the same

25 the same.

26 the same

27 the same.

28 the same.

29 desg'i.

K.

CH.

CH,

CH,

CH.,

CH,

CHj

CIIj

CH ₃

CH ₃

C (CH,).,
o \ -OH

C (CH ₁ ),

C (CHj) ₃

o \ -OH

C (CHj),

- C _s H, T <n)

Mon Snip / C

Ni> 200

O V-C (CH,)., Ni

O VC (CH ₃ ), Ni

Ni

C (CHj) ₃

oHo

Ni

227-240

Ni> 260

Ni> 200

227-240

Ni> 260

145-170

C (CHj) ₃

OH Ni 180-190

230-238

30 desg !.

CH,

O> —OCH,

Ni

195

15th ? unu R ₁ 24 10 370 nCH. C ₁₃ H ₂₇ 16 Me M.p. ^o C Furl , el R. C ₈ H ₁₇ (Ii) CH ₁ , Ni. CH ₃ R, C ₁₁ Hb (II) C ₁₇ H ₃₅ Ni 115-120 OCH ₃ C (CH ₁ Ij C (CHj) ₂ - <ζθ \ - C (CH ₃ ), 31 nCjH ₇ ^ OVOH Ni 164-169 the same <°> C (CH ₃ J ₃ C (CH ₃ ) J. the same Ni 170 32 the same the same C (CH ₃ ), Ni - 110 33 the same HO ^ O ^ CH.-Cl > ^ C ₁₁ H ₂ , 34 the same C (CHj) ₃ Ni 148-150 the same 35 the same H ₂ - Ni ~ 150 the same 36 CH ₃ Ni - 175 the same CH ₃ Ni 150 37 the same CH ₃ Ni 150 38 the same CH ₃ Ni 150 39 the same -CH ₃ Ni > 250 40 -CH ₃ -CH ₃ Ni - 170 41 -CH ₃ Co ~ 185 42 the same -CH, Co > 200 43 Co - 125 44 the same 230 240/8 45

continuation R. 24 1 R ₃ 0 370
18th 17th No. -CH ₃ Rj Me m.p. ° C 46 C (CHj) ₃ the same - <^ o \ - OH Co > 240 47 the same - CHj C (CHj) ₃ 48 the same -CjH ₇ - / ΟΥ- C (CHj) ₃ Co ~ 225 49 -CH ₃ / oN-OCH ₃ Co-205 50 -CH ₃ - / θ) Co 160-175 51 the same -CH ₃ -C ₁₁ Hu Co 110-115 52 the same -CH ₃ - <^ hN Co ~ 190 53 the same -CH ₃ - \ Oy- C (CH ₃ ) J Co> 200 J 54 the same -CH ₃ - CnHu (n) Co 114-120 1 55 ^ 2 ^ CH ₃ -CH ₃ -CH ₃ Co 175-185 1 56 - C ₁₅ H "Ni 150 I. -C ₃ H ₇ -C ₁₁ Hu Ni 140-145 I. 57 the same - CHj 58 the same ^ ~ θ \ Ni 155-160 59 Comparative experiments
Polypropylene
a) Press plates, thickness: 0.3 mm
100 g unstabilized polypropylene powder (Propathen
Hl · '20), which contains 0.1 g calcium stearate, was used with
0.1 g of an antioxidant (Irganox 1010) and that in the -C ₇ H ₁₅ Ni ~ 140 / o \ - C (CHj) ₃ Ni> 250 amount of
UV stabilizer added. The antioxidant and the
UV stabilizers were added to this in ; ■
Dissolved acetone. Then the polypropylene was in ■ '■ {
h ". a laboratory mixer for 5 minutes at 1800 rpm.!
mixed until all the acetone had evaporated. The powdery ^:
Mixture was then on a roller mill during -:
Treated for 5 minutes at 170-18O ⁰ C and 34/28 rpm, '

ground after cooling and at 230 ⁰ C under a result

Pressure of 30 tons processed into pressing plates 0.3 mm thick (pressing time approx. 5 minutes). b.

As a measure of the stabilizing effect with respect to photo- oxidation, the period of time is used up to which the carbonyl band formed by oxidation at 1715 cm- 'in the infrared spectrum has reached an intensity increase Δε of 0.06.

The compound of the formula

(CH) ₃ C

used.

Results:

UV stabilizer

Example 3
Example 4
Table 2, No. 37
Table 2, No. 43

CR ₂

ONi

1/2

Rj - C ₁₇ H ₃₅

comparison

without stabilizer

with comparison substance

Ni

Conc hours tration,% 0.25 2016 0.25 980 0.25 1584 0.2: " 1440

0.25

0.25 0.25

0.25

1025

985 1005

380 684

15th

20th

UV stabilizer Conc hours I. 570 tration, Vl 670 Table 2, No. 23 0.25 540 Table 2, No. 25 0.25 Table 2, No. 29 0.25 150 Comparison: 400 without stabilizer - hours with reference substance 0.25 UV stabilizer Conc tration,%

Example 3 0.50 852

Table 2, No. 28 0.50 800

Table 2. No. 37 0.50 697

Table 2, No. 38 0.50 790

Table 2, No. 44 0.50 697 Comparison:

without stabilizer - 150

with comparison substance 0.50 620

30 100 parts of unstabilized polypropylene powder (Profax 6501) are mixed with 0.1 part of calcium stearate, 0.1 part of Irganox 1010 and 0.25 part of the light stabilizer of the formula

H ₃ C

c— <o

ONi ₁

C (CH ₃ ),

(D

CH ₃

treated as above under experiment a) (processing to press plates 03 mm thick) and tested. That the following result was obtained.

UV stabilizer

Concentration,%

hours

Compound (1) 0.25 660

With comparison substance 0.25 560

b) Ribbon, 25μ thick

After the treatment of the polypropylene on the roller mill, as described above under a), the material obtained granulated (2 - 4 mm size) and extruded on an extruder at about 220 ° C and im Ratio 1: 8 stretched, so that ribbons with a thickness of 25 μ were obtained.

c) ABS, 0.1 mm foils

40 g of ABS granules (Cycolac DM from Marbon, an ABS with medium impact strength) were ^{mixed with 32 mg of stabilizer in a kneader (Brabenderplastograph) at 180 °} C. under nitrogen for 10 minutes.

The still hot kneading mass was pressed into a plate of 1 mm at 200 ° C, and from this plate were with the same press produced 0.1 mm thick foils.

Representative samples of the films were exposed to a weathering device (climatest, De la Rue) for 30 hours exposed.

Results

The aging of the film was based on the increase in the C = O band measured in infrared at 5.8 μ.

UV slabilisalor C = O bands increase after 30 hours of CT (A c) Example 10 0.04 Table 1, No. 1 0.11 Table 1, No. 2 0.16 Table 1, No. 3 0.10 Table 1, No. 17 0.06 Table 2, No. 36 0.08 Comparison: without stabilizer 0.62 with reference substance 0.19

Claims (1)

Patent claims: 1. Compounds of the general formula (I) OMe 10 wherein Ri is an alkyl radical with 1-4 carbon atoms, a Phenyl radical, which is replaced by 1 or 2 alkyl radicals with! - 12 carbon atoms or 1 or 2 alkoxy radicals with 1 - 12 carbon atoms or phenyl or the radical phenyl — O - can be substituted, R _{2 is} an alkyl radical with 8-18 carbon atoms, a cycloalkyl radical with 6-8 carbon atoms, an aralkyl radical with 7-10 carbon atoms, whose aryl nucleus is additionally represented by hydroxyl and / or 1 or 2 alkyl radicals with 1-6 carbon atoms can be substituted, a phenyl radical, which by a Hydroxyl group, 1 or 2 alkyl and / or alkoxy groups with 1-8 carbon atoms and / or Phenyl is substituted, this phenyl radical having a maximum of 3 substituents, a furan, Thiophene or benzothiophene radical, these radicals being replaced by 1 or 2 alkyl radicals with 1-4 C atoms can be substituted, R3 alkyl with 1-4 carbon atoms, phenyl or as with Ri substituted phenyl or benzyl, and Me means hydrogen or an equivalent of nickel or cobalt.