DE4414795C1 - New 1,3-di:ketone(s) with functional gps. for use as thermal stabilisers for e.g. PVC - Google Patents

Abstract

1,3-Diketones of formula (I) are new, where m = 3-5; either (a) X and Y = -COZ, or (b) X = -COOR1, -COO(CH2)mCOCH2COPh or -CONHR1 and Y = -COOH or -COO(1/n(M)n+), or (c) X = -CO-O-R2-O-CO-Ar-COO-(CH2)m -CO-CH2-CO-Ph or -CO-NH-R3-NH-CO-Ar-COO-(CH2)m-CO-CH2-CO-Ph and Y = -COOH or -COO(1/n(M)n+), or (d) X + Y = gp. of formula (ii) -(iv); Z = OH or -O(1/n(M)n+); M = a metal ion with a charge of n = 1-4; R1 = 1-20C alkyl; R2 = 2-12C alkylene; R3 = 2-12C alkylene, m- or p-phenylene or -Phe-A-Phe-; Phe = p-phenylene; A = O, S or SO2; and Ar = gp. of formula (i). Also claimed is prepn. of (I) comprising esterifying OH-contg. 1,3-diketones (II) with trimellitic acid derivs. (III) in a mole ratio of 1:1 or 1:2 and opt. converting the prods. into carboxylic acids or salts, esters, amides or imides thereof by transesterification with water, metal hydroxides or salts, mono- or poly-hydric alcohols, amines or diamines.

Description

The invention relates to 1,3-diketone derivatives with functional groups and their Use as stabilizers against the thermal degradation of chlorine-containing Polymers. Also a process for their production.

It is known that chlorine-containing polymers, such as. B. polyvinyl chloride (PVC) under the decomposition of heat and light and that these polymers therefore Stabilizers must be added to the thermal degradation and thus to prevent discolouration of the molded parts even with long-term use. Polymers containing chlorine are particularly common during processing Temperatures of over 200 ° C heated, which makes it already in the manufacture of the Moldings to severe discoloration and deterioration of the mechanical Properties is coming.

To protect chlorine-containing polymers against the harmful effects of light and heat are added to stabilizers prior to processing into molded parts. As Stabilizers are primarily metal carboxylates based on cadmium, lead, zinc, Barium and calcium as well as organic tin compounds are known, mostly in Can be used in combination with organic costablizers (Lit. R. Gächter and H. Müller (ed.) Taschenbuch der "Kunststoff-Additive", 2nd edition 1983, pp. 199-260).  

In addition to the actual effectiveness of these stabilizer mixtures are for the practical application also other properties, especially their Volatility, tendency to migrate and toxicity are crucial.

1,3-Diketones are also organic stabilizers for chlorine-containing polymers known that are effective in combination with Ba, Zn and Ca carboxylates and their Use for example in US 3,493,536, US 4 123 499, US 4 244 848, US 4 252 698, US 4,282,141, US 4,381,360, GB 788,428, DE 27 16,389, EP 35,268 and EP 346,279 is disclosed. These diketones known from the prior art have various disadvantages such as high volatility, required addition of others, possibly volatile organic costabilizers and relatively low long-term effects. The Stabilization of the chlorine-containing polymers with commercially available 1,3-diketones, e.g. B. Stearoylbenzoylmethane, brings a bright initial color, but in the course of Processing is not maintained over a long period of time.

The results of the tests of the basic approach, the basic approach with addition a commercial diketone and the basic approach with the addition of Stabilizers according to the invention with regard to volatility, yellowness indes (YI) and Dehydrochlorination temperature (DHC) are listed in Table 1.

The object of the present invention was to provide stabilizers and costabilizers To develop the base of 1,3-diketones that contain reactive groups that have a covalent linkage with other organic residues - also costabilizer residues enable, which not only reduces volatility, but also that Long-term stability (e.g. the dehydrochlorination value (DHC)) is increased.  

It has now been found that this problem is solved with the help of 1,3-diketones may contain other functional groups in addition to the keto group.

To stabilize a chlorine-containing polymer contains the composition at least one 1,3-diketone derivative of the formula (I)

where m = 3-5
means in which either

• a) the same radicals -COZ stand for X and Y,
  where Z is OH or O1 / nMe ^{n +} , and Me ^{n + is} a metal ion with charge n = 1-4
  or
• b) for X the residues and Y represents the radicals -COOH, or -COO1 / nMe ^{n +} , in which R₁ denotes an alkyl radical having 1-20 C atoms and m and Me ^{n + have the} above meaning,
  or
• c) for X the rest is in which R₂ is an alkylene radical having 2 to 12 C atoms, R₃ is an alkylene radical having 2 to 12 C atoms, an m- or p-phenylene radical or the rest with A = CH₂, -O-, -S-, SO₂- and represents Y COOH or COO1 / nMe ^{n +} , where m and Me ^{n + have the} above meaning,
  or
• d) X and Y together the rest mean, wherein m, R₁ and R₃ have the above meaning.

The process for the preparation of the new 1,3-diketones is characterized in that to 1,3-diketones containing hydroxyl groups with trimellitic acid derivatives in Molar ratio esterified 1: 1 or 1: 2. As hydroxy-1,3-diketones, for example Products known from the literature from EP 346 279 (1989), namely 6,8-dioxo-1-hydroxy-8- phenyloctane or 4,6-dioxo-1-hydroxy-6-phenyl-hexane or 4,6-dioxo-1-hydroxy-1- methyl-6-phenyl-hexane can be used, which by esterification with z. B. Trimellitic acid anhydride chloride (in a molar ratio of 1: 1) with 1,3-diketone derivatives Carboxylic anhydride groups result. According to the invention, however, others can also 1,3-diketones and trimellitic acid derivatives are used for the esterification.

The 1,3-diketone derivatives thus obtained can either themselves or as stabilizers Costabilizers used for chlorine-containing polymers or others Products according to the invention are implemented. Here one advantageously uses the typical reactions of the carboxylic acid anhydride or carboxyl groups, whereby in a variety of other stabilizers is easily accessible. E.g. receives the free acids or theirs from the 1,3-diketone anhydrides by saponification Salts, by reaction with alcohols first half esters, which may be in the  Diesters can be transferred. The reaction with amines leads in the first stage to the amic acids, which can optionally be cyclized to the imides. An advantage of Esterification or amidation reactions with longer-chain alcohols or amines consists in the resulting reduction in the volatility of the Diketone stabilizers, which is further reduced if you use diols or polyvalent Alcohols or di- or more functional amines are used. Another advantage of Functional 1,3-diketone derivatives according to the invention is that by a suitable choice of Respondents the compatibility of the stabilizer formulations with the respective chlorine-containing polymer can be adapted.

The 6,8-dioxo-1-hydroxy-8- known from the prior art is preferred. phenyloctane with trimellitic anhydride chloride in a molar ratio of 1: 1 to 4- [6,8-dioxo-8- phenyl-octyl) -oxycarbonyl] phthalic anhydride (1), which itself as Stabilizer or co-stabilizer can be used, or as a reactive 1,3-diketone anhydride for the production of further stabilizers and Serves as costabilizers.

So you get by hydrolysis of (1) with ring opening of the cyclic anhydride corresponding 1,3-diketone dicarboxylic acid and therefrom with alkali or Alkaline earth metal hydroxides their salts, for example with Ca (OH) ₂ the Ca salt.

By reacting (1) with amines, such as. B. n-hexylamine initially arise Amidic acids, from which the corresponding imides are formed with elimination of water will. If you set diamines, such as B. 1,6-hexanediamine or methylene dianiline with 1 um, this gives bis- (1,3-diketone-amic acids) or imides.

By reacting (1) with alcohols, such as. B. n-butanol or 2-ethylhexanol the corresponding 1,3-diketone ester carboxylic acids, in which the carboxyl group can be converted into salts. By esterification with  polyhydric alcohols, such as. B. 1,4-butanediol, glycerol or trimethylolpropane the corresponding bis- or tris (1,3-diketone ester carboxylic acids).

According to the invention, the diketone anhydrides or acids can also be used with the 1,3-diketones originally used or other hydroxyl groups are esterified, for example (1) with 6,8-dioxo-1-hydroxy-8-phenyloctane.

The possibility of covalent linkage with others is particularly advantageous Stabilizers or costabilizers, which may have synergistic effects can be achieved.

Instead of trimellitic anhydride chloride, those containing hydroxyl groups can be used 1,3-diketones according to the invention but also with other, more accessible Trimellitic acid derivatives are converted to stabilizers and costabilizers. E.g. is obtained from 6,8-dioxo-1-hydroxy-8-phenyloctane and trimellitic anhydride Ring opening the corresponding 1,3-diketone dicarboxylic acid, the carboxyl groups such as can be further derivatized as described above.

In the case of the 1,3-diketone derivatives functionalized with the invention chlorine-containing polymers are preferably vinyl chloride homopolymers or copolymers. Other suitable chlorine-containing polymers are post-chlorinated PVC, chlorinated polyolefins, graft copolymers of PVC or mixtures of mentioned vinyl chloride homopolymers and copolymers with other thermoplastic and / or elastomeric polymers. The polymer containing chlorine is polyvinyl chloride particularly preferred.

The functional 1,3-diketones of the formula (I) according to the  known prior art incorporated into the chlorine-containing polymer. It is advantageous, the compounds of formula (I) together with known Use thermal stabilizers, such as. B. Me (II) carboxylates, Me (II) phenolates or Me (II) alkyl phenates. Me (II) means e.g. B. Approx. Mg or Zn. For the carboxylates it is preferably salts of carboxylic acids with 6 to 20 carbon atoms, for example. 2-ethylhexanoates, laurates, palmitates, stearates or oleates.

In addition, the chlorine-containing polymers can be conventional in conventional amounts PVC stabilizers contain such. B. epoxy compounds, alkyl or aryl phosphites, Polyols, organotin compounds, aminocrotonic acid esters.

The compositions to be stabilized preferably still contain additionally an epoxy compound, for example epoxidized soybean oil and at least one Me (II) carboxylate, for example a Ca, Zn or Ba carboxylate in the usual Concentrations. The compounds of formula (I) are, for example, in amounts from 0.05% to 1.5%, preferably from 0.2% to 0.8%, in the chlorine-containing polymer incorporated.

An advantageous basic approach includes, for example:

• a) 100 parts by weight of suspension PVC, K value 67
• b) 0.73 part by weight of 1,3-diketone according to Example 9
• c) 1.5 parts by weight of a fatty alcohol phthalate
• d) 1 part by weight of epoxidized triglyceride
• e) 0.8 parts by weight of hydrocarbon wax
• f) 0.3 part by weight of Ca stearate
• g) 0.2 part by weight of Zn stearate

Depending on the intended use of the polymers, other additives may be used be incorporated, such as B. antioxidants, lubricants, plasticizers, fillers, Modifiers, optical brighteners, light stabilizers, flame retardants, UV absorbers  or antistatic agents.

The following examples explain the preparation of the stabilizers and their Use in chlorine-containing polymers.

example 1 Preparation of 4- [6,8-dioxo-8-phenyloctyl) oxycarbonyl] phthalic anhydride

6 g (0.029 mol) of trimellitic anhydride chloride were placed in 60 ml of dry dioxane and cooled to 10 ° C. A mixture of 6.68 g (0.029 mol) of 6,8-dioxo-1-hydroxy-8-phenyloctane (EP 346 279 (1989)) and 2.25 g (0.029 mol) of dry pyridine was dissolved in 60 ml of dry dioxane , added dropwise so that 10 ° C were not exceeded. During the dropping, the pyridine hydrochloride formed precipitated out as a colorless precipitate. The reaction mixture was stirred for a further ten hours at room temperature to complete the reaction. The precipitate was then filtered off, washed twice with 20 ml of dry dioxane, and the solvent was removed from the reaction mixture by distillation. A light yellow precipitate remained as a crude product. It was recrystallized from dry toluene.
Yield: 8.12 g (0.02 mol = 70% Th.)
Mp: 121-123 ° C, TLC: R _f : 0.8 (eluent: petroleum ether / ethyl acetate = 1/1)
1H-NMR (DMSO): (in ppm):
16.30 (bs; 0.8H; diketone in enol form, enol-H);
8.50-7.38 (m; 8H; aromatic protons);
6.51 (s; 1H; olefin. H of the enol form);
4:32 (t; 2H; R-CO-OC H ₂-);
4.22 (s; traces of the keto form, -CO-C H₂ -CO-);
2.61 (t; traces of the keto form, -CO-C H₂ -CO-CH₂-);
2.49 (2t; 4H; -CH = COH-CH₂-; main amount as enol and R-CO-O-CH₂-CH₂-);
1.85-1.22 (2m; 4H; - (CH₂) ₂-).
Elemental analysis: C₂₃H₂₀0₇ (408.41)
calc .:
C 67.64; H 4.94%;
found:
C 67.37; H 5.06%.

Example 2 Preparation of 4- [6,8-dioxo-8-phenyloctyl) oxycarbonyl] phthalic acid

4.42 g (0.01 mol) of 4 - [(6,8-dioxo-1-hydroxy-8-phenyloctyl) oxycarbonyl] benzene-1,2- dicarboxylic acid anhydride are heated to 60 ° C in a mixture of 3.87 g (0.05 mol) pyridine and 20 ml dioxane dissolved. The clear yellow solution will be  Room temperature (20 ° C) added a total of 10 ml of water within 30 min, avoiding precipitation of the anhydride (add 2 ml portions).

After the addition has ended, the reaction mixture is stirred for a further 15 min at 30-35 ° C., then ice and 100 ml of 2N HCl are added, and the product is isolated by extraction twice with 50 ml of ethyl acetate each time. The combined organic phases are washed twice with water, dried over sodium sulfate, filtered and the solvent is distilled off. The remaining crystalline residue is digested in ether and dried at room temperature in a fine vacuum.
Yield: 3.44 g of white solid (82% of theory)

The course of the reaction can be monitored by means of thin layer chromatography in petroleum ether / ethyl acetate or in toluene / dioxane / glacial acetic acid 8: 1: 1.
Elemental analysis: C₂₃H₂₂O₈ (426.43)
calc .:
C 64.72; H 5.15%;
found:
C 64.40; 5.35%.

Example 3 Preparation of the Ca salt of 4- [6,8-dioxo-8-phenyloctyl) oxycarbonyl] phthalic acid

7 g (0.017 mol) of 2-4 - [(6,8-dioxo-1-hydroxy-8-phenyloctyl) oxycarbonyl] benzene-1,2-dicarboxylic acid anhydride were dissolved in 200 ml of 20% aqueous ethanol Heating dissolved and neutralized with 2N ammonia against phenolphthalein. This mixture was added dropwise to 200 ml of 0.15 molar CaCl₂ solution and then stirred with cooling (ice-water mixture, 5-10 ° C). The resulting precipitate was filtered off, washed with cold water and dried in a drying cabinet at 50 ° C.
Yield: 7.5 g
IR: 3424 cm ^-1 crystal water in the salt, no acid OH
2944-2848 cm ^-1 CH valence vibrations
1740 cm ^-1 ester CO band
1660-1596 cm ^-1 b-diketone in the enol form with H-bond or antisymmetric valence vibration of the carboxylate ions
1436 cm ^-1 symmetrical valence vibration of the carboxylate ions
1292, 1200 cm ^-1 2 strong bands due to (CO) -valence vibration.

Example 4 Preparation of 4- [6,8-dioxo-8-phenyl-octyl) -oxycarbonyl] -N-hexyl-phthalamide acid

4.42 g (0.011 mol) 2-4 - [(6,8-dioxo-1-hydroxy-8-phenyl-octyl) -oxycarbonyl] -benzene-1,2-dicarboxylic acid anhydride are suspended in 25 ml of methylene chloride and 2.19 g (0.022 mol) of hexylamine were slowly added dropwise at 20 ° C. in such a way that the temperature did not exceed 30 ° C. When the addition is complete - a clear yellow solution is formed - the solvent is distilled off and the remaining yellow oil is dissolved in 30 ml of ethyl acetate. The excess hexylamine is separated by extraction twice with 2N HCl (1 × 20 ml, 1 × 10 ml), the organic phase is washed twice with water, dried over sodium sulfate, filtered and the solvent is distilled off. The crystalline product thus obtained is dried at 25 ° C. under a fine vacuum.
Yield: 4.34 g of white solid (79% of theory), thin layer chromatography: R _f = 0.58 (toluene: dioxane: glacial acetic acid 8: 1: 1)
Elemental analysis: C₂₉H₃₅O₇N (509.6)
calc .:
C 68.29; H 6.87; N 2.74%;
found:
C 67.95; H 6.55; N 2.50%.

Example 5 Preparation of 4- [6,8-dioxo-8-phenyloctyl) oxycarbonyl] -N-hexyl phthalimide

8 g (0.0196 mol) of 4 - [(6,8-dioxo-1-hydroxy-8-phenyloctyl) oxycarbonyl] benzene-1,2-dicarboxylic acid anhydride were suspended in 200 ml of glacial acetic acid and treated with 1 , 98 g (19.6 mmol) of hexylamine were added. The reaction mixture was kept at reflux temperature for 12 hours, poured onto ice water, the precipitate was filtered off and recrystallized from ethanol.
Yield: 6.5 g (13.22 mmol = 68% Th.) Mp: 79-81 ° C, TLC: R _f : 0.4 (eluent petroleum ether / ethyl acetate = 3/1)
1H-NMR (DMSO): d in ppm:
16.30 (bs; 0.8 H; diketone in enol form, enol-H);
8.50-7.38 (m; 8H; aromatic protons);
6.30 (s; 1 H; olef. H of the enol form);
4.42 (t; 2H; R-CO-O-CH₂-);
4.22 (s; traces of the keto form, CO-CH₂-CO-);
3.75 (t; 2H; -CO-N (Cu₂-R) -CO-);
2.50 (t; 2H; -CH = COH-CH₂-, major amount as enol);
2.00-1.20 (2m; 12H; 6x-CH₂-);
0.92 (s; 3H; -CH₃).
Elemental analysis: C₂₉H₃₃O₆N (491)
calc .:
C 70.86; H 6.77; N 2.85%;
found:
C 70.49; H 6.58; N 2.82%.

Example 6 Preparation of bis-1,6- (4- (6,8-dioxo-8-phenyloctyl) oxycarbonyl phthalimido] hexane

10 g (0.0245 mol) of 4 - [(6,8-dioxo-1-hydroxy-8-phenyloctyl) oxycarbonyl] benzene-1,2-dicarboxylic acid anhydride were suspended in 200 ml of glacial acetic acid and mixed with 1.42 g (0.0122 mmol) of hexamethylene diamine are added. The reaction mixture was kept at reflux temperature for 12 hours, poured onto ice water, the precipitate was filtered off and recrystallized from ethanol.
Yield: 6.8 g (62% of theory), mp: 118-120 ° C, TLC: R _f : 0.6 (eluent petroleum ether / ethyl acetate = 1/1)
1H-NMR (DMSO): d in ppm:
16.20 (bs; 2H; diketone in enol form, enol-H);
8.62-7.15 (m; 16H; aromatic protons);
6.30 (s; 2H; olef. H of the enol form);
4.38 (t; 4 R-CO-OC H ₂-);
4.18 (s; traces of the keto form, CO-CH₂-CO-);
3.62 (t; 4H; 2x -CO-N (C H₂ -R) -CO-);
2.51 (t; 4H; 2 x CH = COH-C H ₂-, major amount as enol present);
2.10-1.10 (2m; 20H; 10x -CH₂-).
Elemental analysis: C₅₂H₅₂O₁ ₂N₂ (894.7)
calc .:
C 69.63; H 5.84; N 3.12%;
found:
C 69.58; H 5.79; N 3.04%.

Example 7 Preparation of bis-4,4 '- [4- (6,8-dioxo-1-hydroxy-8-phenyl-octyl) -oxycarbonyl phthalimido] diphenylmethane

4.12 g (0.01 mol) of 4 - [(6,8-dioxo-1-hydroxy-8-phenyloctyl) oxycarbonyl] benzene-1,2-dicarboxylic acid anhydride and 1 g (0.005 mol) 4,4'-diaminodiphenylmethane are suspended in 80 ml of glacial acetic acid and stirred overnight at 100 ° C, a clear yellow solution being formed. After cooling to room temperature, the product is precipitated in 1 liter of ice water, filtered off, washed with ethanol and dried at 60 ° C. under a fine vacuum.
Yield: 4.5 g of solid (91% of theory) TLC: R _f = 0.62 (petroleum ether / ethyl acetate 1: 1)
Elemental analysis: C₅₉H₅₀O₁₂N₂ (979.06)
calc .:
C 72.31; H 5.11; N 2.86%;
found:
C 72.58; H 5.29; N 2.64%.

Example 8 Preparation of bis-1,4 - [(2-carboxy-5- (6,8-dioxo-8-phenyloctyloxycarbonyl) benzoyl -] - butane

5.4 g (0.013 mol) of 4 - [(6,8-dioxo-1-hydroxy-8-phenyloctyl) oxycarbonyl] benzene-1,2-dicarboxylic acid anhydride, 1.0 g of pyridine and 30 ml Section. Dioxane are introduced and 0.54 g (0.906 mol) of butanediol are added dropwise at 55 ° C. The mixture is then stirred at 60 ° C. overnight and, after cooling to room temperature, the product is precipitated in hydrochloric acid ice water and isolated by extraction twice with ethyl acetate. The combined organic phases are washed three times with water, dried over sodium sulfate and the solvent is distilled off. The remaining cloudy and viscous residue is dried in a fine vacuum at 70 ° C without further purification.
Yield: 9.4 g (78%), TLC: R _f = 0.58 (toluene: dioxane: glacial acetic acid 18: 1: 1). The product, identified by 1 H NMR and IR, contains small amounts of unreacted anhydride and some mono-ester.

Example 9 Bis-2,4- (6,8-dioxo-8-phenyloctyloxycarbonyl) benzoic acid

2.4 g (0.010 mol) of 6,8-dioxo-1-hydroxy-8-phenyloctane are dissolved in 30 ml of anhydrous dioxane and at 50 ° C with a warm solution of 3.5 g (0.0086 mol) 4 - [(6,8-Dioxo-1-hydroxy-8-phenyloctyl) oxycarbonyl] benzene-1,2-dicarboxylic acid anhydride and pyridine in dioxane were added. The mixture is stirred at 50-60 ° C for 24h, poured onto ice water and extracted with ethyl acetate. The organic phase is dried with sodium sulfate and the solvent is distilled off. The yellowish oily product is dried in a fine vacuum at 50 ° C:
Yield: 4 g (72.6%) R _f = 0.63 eluent: petroleum ether / ethyl acetate = 1: 1. The product, which was identified by means of 1 H-NMR and IR, contains small amounts of unreacted 6,8-dioxo -1-hydroxy-8-phenyloctane.

Example 10 Preparation of 4- [4,6-dioxo-6-phenyl-hexyl) -oxycarbonyl] phthalic anhydride

6 g (0.029 mol) of trimellitic anhydride chloride were placed in 60 ml of dry dioxane and cooled to 10 ° C. A mixture of 6.00 g (0.029 mol) of 4,6-dioxo-1-hydroxy-6-phenyloctane and 2.25 g (0.029 mol) of dry pyridine, dissolved in 60 ml of dry dioxane, was added dropwise in the course of 30 minutes, that 10 ° C was not exceeded. During the dropping, the pyridine hydrochloride formed precipitated out as a colorless precipitate. The reaction mixture was stirred for a further ten hours at room temperature to complete the reaction. The precipitate was then filtered off, washed twice with 20 ml of dry dioxane, and the solvent was removed from the reaction mixture by distillation. A light yellow precipitate remained as a crude product. It was recrystallized from dry toluene.
Yield: 7.2 g (0.018 mol = 65% of theory)
Elemental analysis: C₂₁H₁₇O₇ (381.36)
calc .:
C 66.14; H 4.49%;
found:
C 66.30; H found 4.35%.

Volatility: 5.5%  

Example 11 Preparation of 4- [5,7-dioxo-7-phenyl-heptyl) -oxycarbonyl] phthalic anhydride

6 g (0.029 mol) of trimellitic anhydride chloride were placed in 60 ml of dry dioxane and cooled to 10 ° C. A mixture of 6.35 g (0.029 mol) of 5,7-dioxo-1-hydroxy-7-phenyloctane and 2.25 g (0.029 mol) of dry pyridine, dissolved in 60 ml of dry dioxane, was added dropwise in the course of 30 minutes, that 10 ° C was not exceeded. During the dropping, the pyridine hydrochloride formed precipitated out as a colorless precipitate. The reaction mixture was stirred for a further ten hours at room temperature to complete the reaction. The precipitate was then filtered off, washed twice with 20 ml of dry dioxane, and the solvent was removed from the reaction mixture by distillation. A light yellow precipitate remained as a crude product. It was recrystallized from dry toluene.
Yield: 7.8 g (0.019 mol = 68% of theory)
Elemental analysis: C₂₂H₁₉O₇ (395.38)
calc .:
C 66.83; H 4.84%;
found:
C 66.55; H 4.70%.

Volatility: 5.2%  

Example 12 Preparation of bis-4,4 ′ - [4- (6,8-dioxo-8-phenyloctyl) oxycarbonylphthalimido] - diphenyl sulfone

6.35 g (0.0156 mol) of 4 - [(6,8-dioxo-1-hydroxy-8-phenyloctyl) oxycarbonyl] benzene-1,2-dicarboxylic acid anhydride and 1.93 g (0.008 mol) 4,4'-diaminodiphenyl sulfone are suspended in 120 ml of glacial acetic acid and stirred overnight at 100 ° C, a clear orange-yellow solution being formed. After cooling to room temperature, the product is precipitated in 1 l of ice water, filtered off, washed with ethanol and dried at 70 ° C. under a fine vacuum.
Yield: 6.8 g of solid (85% of theory) TLC: R _f = 0.50 (petroleum ether / ethyl acetate 1: 1), mp. 96-98 ° C.
Elemental analysis: C₅₈H₄₈N₂O₁₄S (1029.09)
calc .:
C 67.69; H 4.7; N 2.72; S 3.12%;
found:
C 66.24; H 4.6; N 2.96; S 3.58%.

Volatility: 1.1%  

The results of the tests regarding volatility, YI and DHC of each individual Games are summarized in Table 1. They were made using the following methods averages:

The recipe components of the basic approach (see page 8) are quick in one laboratory mixer briefly mixed at room temperature and then open a two-roll mill at 160 ° C in the course of 5 minutes to 0.6 mm thick films processed.

Samples are used to test the thermostabilizing effect in the static heat test 5 × 5 cm in a convection oven at 174 ° C (⁺1 ° C). In Samples are taken every 10 minutes and their samples Color change - mostly assessed after 10 and 20 minutes of storage. The review is done visually and by determining the Yellowness Index (YI) according to ASTM D 1925. The volatility of the diketones was determined using thermogravimetry 200 ° C on a DuPont Instrument 990 Thermal Analyzer with 951 Thermogravimetric Analyzer.

Furthermore, the release of hydrogen chloride is checked by using test foils at 200 ° C be heated and the discoloration of indicator strips depending on the time is observed (DHC values).  

Table 1

Claims (4)

1. 1,3-diketone derivatives of the formula (I) where m = 3-5
means in which either

• a) the same radicals -COZ stand for X and Y,
  where Z is OH or O1 / nMe ^{n +} , and Me ^{n + is} a metal ion with charge n = 1-4
  or
• b) for X the residues and Y is the radicals -COOH, or -COO1 / nMe ^{n +} , in which R₁ is an alkyl radical having 1-20 C atoms and m and Me ^{n + have the} above meaning,
  or
• c) for X the rest is in which R₂ is an alkylene radical having 2 to 12 C atoms, R₃ is an alkylene radical having 2 to 12 C atoms, an m- or p-phenylene radical or the rest with A = CH₂, -O-, -S-, SO₂- and represents Y COOH or COO1 / nMe ^{n +} , wherein
  m and Me ^{n + have the} above meaning,
  or
• d) X and Y together the rest mean, wherein m, R₁ and R₃ have the above meaning.

2. 1,3-diketone derivatives of the formula I according to claim 1, wherein X and Y are the radicals -COOH, -COOMe ²⁺ or together the radical mean, and Me ^{2+ stands} for Ca ²⁺ or Mg ²⁺ . 3. A process for the preparation of 1,3-diketone derivatives according to claim 1, characterized in that with 1,3-diketones containing hydroxyl groups Trimellitic acid derivatives in a molar ratio of 1: 1 or 1: 2 esterified and the obtained Products, if appropriate, by reaction with water, metal hydroxides or salts, monohydric or polyhydric alcohols, amines or diamines in carboxylic acids, salts of Carboxylic acids, esters, amides or imides transferred.   4. Use of the 1,3-diketone derivatives of the formula I as claimed in claims 1-6 Stabilizers or stabilizer components for chlorine-containing polymers.