KR20070023716A - New isobenzoxazinones and their use as ultraviolet light absorbers - Google Patents

Abstract

The present invention relates to novel substituted isobenzoxazinones, in particular isobenzoxazinone of the formula (I) as indicated in claim 1, and in particular its use as ultraviolet absorbers for organic polymers.

Description

Isobenzoxazinone and its use as ultraviolet absorber {NEW ISOBENZOXAZINONES AND THEIR USE AS ULTRAVIOLET LIGHT ABSORBERS}

The present invention relates to novel isobenzoxazinones, in particular isobenzoxazinones of the formula (I) and their use as ultraviolet absorbers for organic materials, in particular organic polymers.

The usefulness and lifetime of plastic products are influenced by many parameters such as the mechanical properties, density, molar mass and mass distribution of the polymer. Depending on the end use and the space conditions (temperature, stress and environmental influences) during the service time, a life of up to several decades should be ensured, which can be reached by means of a suitable stabilizer and stabilizer mixture. The contribution of the stabilizer can be measured under accelerated test conditions. As an important technical criterion, optical properties such as color are measured, for example, as yellowness, and used to evaluate the stabilization of polymer products.

Influences in the polymer matrix, such as changes in crystallinity, free volume, form and diffusion coefficient, and reaction kinetics, result in changes in the mechanism of degradation. One of the decisive criteria for preventing rapid degradation of polymer products by light is the use of ultraviolet absorbers in combination with suitable light stabilizers. Ultraviolet absorbers help prevent polymer degradation by reducing the deleterious effects of ultraviolet radiation by absorption through chromophores and by slowing the onset rate through deactivation of excited states in the polymer matrix. In general, ultraviolet absorbers can dissipate the energy of photons absorbed in the polymer matrix in a harmless manner, for example as heat.

Other mechanical effects are also discussed regarding the chemical conversion of hydroperoxides by ultraviolet absorbers without the production of free peroxy radicals by photodegradable separation (F. Gugumus, "Plastics additives handbook", p. 206ff, editor H Zweifel, Hanser Publishers, Munich, 2001] as described in the chapter "Lightstabilizers").

Of all the absorbents used so far for the protection of the polymer matrix, phenolic and non-phenolic ultraviolet absorbers are distinguished which provide photostability in the 300-400 nm wavelength range. Phenolic absorbers act by photon transport mechanisms in excited-state molecules. For non-phenolic ultraviolet absorbers, the generation of photoexcitation charge-separating species is considered a mode of action. A more detailed description of the individual classes of ultraviolet absorbers and modes of action can be found in J.E. Pickett, titled "Permanence of UV absorbers in Plastics and Coatings", Technical Report 97CRD170 / General Electric, Dec. 1997].

Most ultraviolet absorbers, especially benzophenone derivatives, are effective in the UV-A (320-400 nm) and UV-B (290-320 nm) ranges.

Parameters such as appearance and long-term retention of properties, especially color, gloss and transparency, are very important properties of the technical polymer. Therefore, any improvement in this parameter can be considered an important step of innovation. There is still a need to improve properties over known ultraviolet absorbers such as hydroxybenzophenone, hydroxybenzotriazole, hydroxytriazine and unsubstituted benzoxazinone.

Unsubstituted benzoxazinones are known as versatile UV absorbers (US 3,989,698 and US 4,446,262) and are commercially available, for example 2,2'-p-phenylene-bis as shown below. (3,1-benzoxazin-4-one) is commercially available from Cytec as Cyasorb® 3638:

Improved methods for the preparation of these compounds and their use for transparent polymeric materials are disclosed in WO 03/035735.

WO 03/016292 discloses substituted benzoxazinone compounds of the formula and in particular their use as ultraviolet absorbers for organic polymers:

In EP 1 302 197 A1 and EP 1 317 918 A1, benzoxazinones, especially 2,2'-p-phenylene-bis- (3,1-benzoxazin-4-one), are the same as sunscreens. It is also disclosed as being suitable as an ultraviolet absorbent in cosmetic preparations.

EP 0 674 038 A1 discloses the use of 4H-3,1-benzoxazin-4-one compounds for improving the light fastness of textile materials. In particular, 2.2'-p-phenylene-bis- (3,1-benzoxazin-4-one) is disclosed.

Surprisingly, substituted benzoxazinones, such as isobenzoxazinone of the present invention, have been found to be particularly useful as ultraviolet absorbers superior to the state of the art in view of the relevant technical parameters.

The present invention therefore relates to novel substituted isobenzoxazinones of the general formula (I)

Where

R ₁ represents a long chain alkyl substituent, cycloalkyl substituent or isoalkyl substituent of C _n H _{2n + 1} , n is 8 to 30;

X represents a direct bond, -O-, an ester group (-COO-) or -S-;

R ₂ , R ₃ , R ₄ and R ₅ independently represent a substituent selected from hydrogen, halogen (F, Cl, Br, I) or C _1-12 alkyl.

In a preferred embodiment, the present invention provides that R ₁ represents a long chain alkyl or isoalkyl substituent of C _n H _{2n + 1} , n is from 8 to 18, X represents -O-, R ₂ , R ₃ , R ₄ and Novel isobenzoxazinones of formula (I) wherein R ₅ independently represent a substituent selected from hydrogen, fluorine, chlorine, bromine or C _1-4 alkyl.

More preferably, R ₂ , R ₃ , R ₄ and R ₅ independently represent a substituent selected from hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, iso-propyl or tert-butyl.

Most preferred compounds are those represented by the formulas Ia to Ig:

It has also been found that particularly preferred compounds of formula (I) wherein X is -O-, R ₁ is an unbranched alkyl substituent of C _n H _{2n + 1} and n is from 8 to 12, exhibit morphological phase transitions below the corresponding melting point. lost.

The novel compounds according to the invention provide excellent stability against damage by light and oxidation, thus protecting the polymeric material from degradation by lowering its environmental impact.

Another object of the present invention is the use of the novel compounds as ultraviolet absorbers which are very compatible in a wide variety of organic materials. In comparison to compounds known in the art, the novel compounds according to the invention are much more soluble in many organic substrates. The novel compounds according to the invention are used in organic substrates, most preferably in organic polymers, preferably in concentrations of 0.005 to 0.100% by weight. The novel compounds according to the invention are particularly suitable for organic polymers selected from the so-called engineering plastics group. Preferred organic polymers selected from the so-called engineering plastics group are polycarbonates, polyesters and polyamides, in particular polycarbonate (PC), polyethylene terephthalate (PET), polyamide-6 (PA6) and polyamide-6.6 (PA6.6) to be. In addition, depending on its substitution pattern, several novel compounds can also be used in polyolefin-based thermoplastic polymers.

In addition, the novel compounds can be incorporated into clay type nanocomposites, which are a class of laminated silicates that themselves have received considerable attention in basic research and industrial development. Nanoclays are described, for example, in M. Alexandre and P. Dubois, Polym. Mater. Sci. Eng ., 28 , 1-63, 2000; H. Quin, C. Zhao, S. Zhang, G. Chen and M. Yang, Polym. Degrad. Stab ., 81 , 497-500, 2003, as well as the improved thermal and oxidative stability of the incorporated compounds, as well as providing improved properties already at very low filler contents, typically below 5% by weight. .

The novel compounds are particularly suitable for cosmetic use.

Preparation of the compound

The compounds according to the invention can be obtained, for example, by etherifying 3-hydroxyisophthalic acid with halogenated alkanes according to the Williamson procedure and subsequently preparing the final compound. The last step is to react the corresponding diacid chloride with anthranilic acid and anthranilic acid derivatives to produce isobenoxoxazinone residues. The preparation of the corresponding isobenzoxazinone starting from hydroxyphthalic acid can be carried out basically according to the same procedure.

Suitable halogenated alkanes are, for example, 1-bromooctane, 1-bromononane, 1-bromodecane, 1-bromodecane and higher homologues, as well as the corresponding haloalkanes having branched or cyclic structures, Examples thereof include 1-bromo-2-ethylhexane or bromocyclooctane, 3-bromocyclooctene, 2- (6-bromohexyloxy) -tetrahydro-2H-pyran and the like. Haloalkanes are also saturated heterocycles, preferably 2- (2-bromoethoxy) tetrahydro-2H-pyran, 2- (2-bromoethyl) -1,3-dioxane, 2- An oxygen-containing heterocycle may be contained as shown by (2-bromoethyl) -2,5,5-trimethyl-1,3-dioxane or the like. Suitable starting materials are also haloalkyl substituted arenes and aromatic heterocycles, for example 3- (2-bromoethyl) indole, which also leads to a dimer structure, also dibromosubstituted, unbranched, branched and cyclic Alkanes. In haloalkanes, chlorine substitution can be used instead of bromine substitution.

As well as anthranilic (or 2-aminobenzo) acids, derivatives thereof, such as alkyl, dialkyl, trialkyl and tetraalkyl derivatives of anthranilic acid linked at the 3-6 positions can be used in the final step.

Alkyl, dialkyl, trialkyl and tetraalkyl substituents include linear, branched and cyclic structures, and 2-amino-3-chloro-benzoic acid, 2-amino-4-chloro-benzoic acid, 2-amino-5-chloro-benzoic acid, 2-amino-6-chloro-benzoic acid, 2-amino-3,4-dichloro-benzoic acid, 2-amino-3,5-dichloro-benzoic acid, 2-amino-3,6-dichloro-benzoic acid and again Other homologs may have a chain length of C _1-20 . Halogen substitutions may be fluorine or bromine and nitro- or cyano substitutions instead of chlorine.

The following compounds were prepared by the method described below.

Such compounds can be obtained, for example, by multistep synthesis starting from 5-hydroxyisophthalic acid (1) (see, eg, GJ Bodwell, JN Bridson, MK Cyranski, JWJ Kennedy, TM Krygowski, MR Mannion and DO Miller, J. Org. Chem ., 68 (6), 2089-2098, 2003).

The compound of formula 1 is first converted to its dimethyl ester 2 under standard conditions and in near quantitative yield:

Synthesis to the final compound (Ia) was continued, for example, by converting compound (2) with i-bromooctane according to the following procedure: 84.1 g (0.40 mole) of compound (2) and 81.1 g (0.42) Mole) 1-bromooctane was dissolved in 250 ml of dimethylformamide (DMF). 61 g (0.44 mole) of potassium carbonate was then added. The slightly yellow dispersion was heated at T = 120 ° C. for 4 hours. After cooling the solid precipitate was removed by filtration and washed with cold DMF. A 500 ml total amount of demineralized water was added to the filtrate with stirring to form a precipitate slowly. The precipitate was filtered and washed thoroughly with demineralized water until neutral pH was reached and no further bromide ions could be detected using silver nitrate for detection purposes. After drying the product in the presence of phosphorus pentoxide in a drier under vacuum, 127.0 g (98.6% yield) of solid product 3 were obtained:

The product was added to 500 mL of ethanol to hydrolyze 96.6 g (0.3 mole) of compound (3). After heating at a temperature of T = 65 ° C., an aqueous solution of sodium hydroxide (30% by weight) was added slowly over 90 minutes. The basic solution was neutralized with aqueous hydrogen chloride solution (35% by weight) under stirring. Under these conditions, diacid 4 precipitated out. The product was isolated by filtration, washed with demineralized water and dried in a vacuum oven at T = 95 ° C. After further drying over phosphorus pentoxide in a dryer, 82.9 g (94% of theory) of slightly yellow product remained.

150 mL of thionyl chloride and 82.0 g (0.279 mol) of product (4) and 1.5 mL of dimethylformamide were added under nitrogen in a vessel to further convert diacid (4) to diacid chloride (5). The reaction mixture was first heated at below T = 50 ° C. under increasing gas evolution under reflux. The mixture was then further heated to 75 ° C. After 3 hours, the heating medium was removed and excess thionyl chloride was removed by distillation. The residual product (5) was partially precipitated. The solid product was isolated by filtration and washed with cold anhydrous ethanol; Yield 73 g (79.7% of theory).

540 mL of water was added to the reaction vessel with 61.5 g (0.44 mole) of anthranilic acid (content 98 wt.%) To effect final conversion to product (Ia). 23.85 g (0.225 mol) of sodium carbonate were then incorporated under slow stirring while the solution was slowly produced (solution I). 73 g (0.22 mole) of product (5) was dissolved in 460 mL of acetone (solution II). The solution (II) was added to the aqueous solution (I) with anthranilic acid under vigorous stirring for 2.5 hours. Some exothermic reaction occurred. The reaction mixture was then heated to reflux for 2 hours. Cooling gave a pale beige precipitate which was filtered at ambient temperature, washed with water and dried under vacuum; 117.3 g of beige powder remained. The product was suspended in 350 ml of acetic anhydride and heated to reflux for 3 hours to give the final product which slowly precipitated out. 20 ml of acetone were added and the reaction mixture was filtered and washed thoroughly with acetone. After drying under vacuum 82.3 g (75.5% of theory) of nearly colorless final product (Ia) were obtained.

Application test in ethylene / methacrylic anion copolymer

An ethylene / methacrylic acid anionic copolymer (“ionomer”, containing Zn cation) of the type Surlyn® 9910 (commercially available from Du Pont) was used for processing and prolonged exposure. 100 parts of the polymer were mixed with 0.1 part of the corresponding ultraviolet absorber. The composition of the formulation for Examples 1-6 is shown in Table 2.

Examples 1 to 5 are comparative examples.

Pre-extrusion was carried out on a single screw extruder type T30 (producer Collin) (screw type NS, screw composition 1: 3, die diameter = 4 mm) at a screw speed of T = 210 ° C. and 80 rpm. The ionomer plaques (100 × 100 × 1 mm) were then treated using an injection molding machine T 18 (producer Arburg), screw speed 400 rpm, at a temperature of T = 210 ° C. and a pressure of up to 100 bar for a cycle time of 24.6 seconds. . Injection molding plaques of ionomers were placed in an air circulation oven at T = 60 ° C. to perform accelerated heat treatment. Yellowness was measured using a Minolta 3500d spectrophotometer mode CRIELL according to DIN 6167. Transparency was measured at the wavelength λ = 700 nm and measured with the same instrument. Finally the glossiness was measured at an angle of 60 ° using a glossmeter (Byk type).

The results after 24 hours of exposure time are shown in Table 3.

As a result of the oven test, the following may be mentioned:

In terms of the yellowness of the ionomer plaques containing the new compound (Ia), the color is superior to the commercial, state-of-the-art ultraviolet absorbers of Examples 1 to 3, and in particular to the benzoxazinones of Example 4.

Parameters such as transparency and glossiness are similar to ionomer plaques containing benzotriazole or triazine-based UV-absorbers.

Compared to conventional benzoxazinone type ultraviolet absorbers and the corresponding unsubstituted isobenzoxazinones, the substituted isobenzoxazinones according to the invention clearly show excellent performance.

Application test in polycarbonate

Lexan® 141 type (commercially available from GE Plastics) was used for processing and prolonged exposure. The polymer was dried for 4 h at T = 80 ° C. under vacuum before use. 100 parts of the polymer were mixed with 0.1 parts of the corresponding ultraviolet absorber. The compositions of the formulations of Examples 7-9 are shown in Table 4.

Examples 7 and 8 are comparative examples.

Mixing of the granular polymer and granule additives was carried out by dry blending in a polyethylene bag. Single screw extruder type T30 (producer choline) (screw type NS, L / C = 20, screw composition 1: 3, die diameter from T = 260 ° C (band 1) to 280 ° C (band 4) and at a screw speed of 80 rpm) = 4 mm) on a pre-extrusion. The polycarbonate plaque (thickness 1 mm) was then subjected to an injection molding machine T 18 (producer Arberg), a screw speed of 400 rpm, with a temperature of T = 265 to T = 275 ° C. and a pressure of up to 100 bar for a period of 20 seconds. Treatment at

Injection molded plaques were put in an air circulation oven at T = 120 ° C. to perform accelerated heat treatment (oven aging). Transparency was measured with a spectrophotometer type Minolta CM 3500d by measuring at wavelength λ = 700 nm. The results after the exposure time up to 10 days are shown in Table 5.

As a result of the oven test on polycarbonates, the following may be mentioned:

The transparency of the polycarbonate plaques with isobenzoxazinone is slightly better than the samples containing benzotriazole or benzylidene-bis-malonate UV absorbers.

Application test in polyethylene terephthalate (PET)

Arnite® D04 300 Natural type polyethylene terephthalate (PET) (available from DSM) was used for processing and prolonged exposure. The polymer was dried for 8 h at T = 120 ° C. under vacuum before use. 100 parts of the polymer were converted into 0.2 parts of phosphite type stabilizer Hostanox® PAR 24 and 0.05 parts of phenol type stabilizer Hostanox® O 16 (the latter two stabilizers were used as base stabilizers. Used and commercially available from Clariant) and additionally 0.25 parts of UV absorber. The compositions of the formulations of Examples 10-16 are shown in Table 6.

Examples 11-14 and 16 are comparative examples.

Mixing of the granular polymer and granule additives was carried out by dry blending in a polyethylene bag. Pre-extrusion is carried out on a single screw extruder type T30 (producer choline) (screw composition 1: 3, die diameter = 2 mm) from T = 275 ° C. (Band 1) to 285 ° C. (Band 5) and at a screw speed of 80 rpm. It was. The polyethylene terephthalate plaque (thickness 1 mm) was then subjected to an injection molding machine T 18 (producer Arberg) at a screw speed of 300 rpm at a temperature of T = 270 to 275 ° C. and a pressure of up to 85 bar for a period of 28 seconds. Treated.

Injection molded plaques were put in an air circulation oven at T = 80 ° C. to perform accelerated heat treatment (oven aging). Exposure device type atlas UV equipped with eight fluorescent tubes emitting alternating λ = 340 nm wavelength light for 20 hours at T = 50 ° C. and in the dark (4 hours) (condensation step) at a temperature of 40 ° C. Artificial exposure UV-A was performed at -CON (according to ASTM D5208 Cycle A).

Yellowness was measured with a Minolta CM 3500d type spectrophotometer according to DIN 6167. Glossiness measurement was performed using a BYK type glossmeter.

The results after an exposure time of up to 15 days in an oven at T = 80 ° C. are shown in Table 7, and the results of artificial exposure type UV-A are shown in Table 8.

As a result of the oven test using polyethylene terephthalate (PET) plaques:

In terms of yellowness, the color of the plaques containing the novel compounds (Ia) and (Ib) is superior to the latest commercial ultraviolet absorbers of the benzylidene-bis-malonate and oxanilide types by heat treatment.

Parameters such as glossiness for new isobenzoxazinones (Ia) and (Ib) are based on the polyethylene terephthalate plaques containing benzylidene-bis-malonate or oxanilides or conventional benzoxazinone based UV-absorbers. Better than the above parameters.

Application Tests in Polyamide-6.6 (PA6.6)

Polyamide-6.6 (PA6.6) of PA6.6 Frianyl® A63E (available from Frisetta) was used for processing and long-term exposure. The polymer was dried for 8 h at T = 80 ° C. under vacuum before use. 100 parts of the polymer (except blend 18) were added 0.1 parts of phosphonite type stabilizer Sandostab® P-EPQ (used as base stabilizer) and additionally 0.05 to 0.25 parts of various light stabilizers (mixture or single component). ). The composition of the formulations for Examples 18-21 is shown in Table 9.

Examples 18-20 are comparative examples.

Mixing of the granular polymer and granule additives was carried out by dry blending in a polyethylene bag. Pre-extrusion is carried out on a single screw extruder type T30 (producer choline) (screw composition 1: 3, die diameter = 2 mm) from T = 265 ° C (band 1) to 275 ° C (band 5) and at a screw speed of 60 rpm. It was. The polyamide-6.6 plaque (thickness 1 mm) was then subjected to an injection molding machine T 18 (producer Arberg) with a screw speed of 300 rpm at a temperature of T = 285 ° C. and a maximum of 80 bar (holding pressure 50 at 19 sec cycle time). Treatment at bar). Weather-O-Meter (D 4892 or ISO 11341-C): Xenon light, steady light, dry conditions, luminous intensity 0.47 W / m ² (340 nm), black panel temperature 63 The plaques were exposed using a C, a relative humidity of 50% and a borosilicate S filter. Yellowness was measured with a Minolta CM 3500d type spectrophotometer according to ISO 11341. Glossiness measurement was performed using a BYK type glossmeter.

The results for glossiness after exposure of 1250 hours and yellowness for ΔE after 4500 hours of exposure are shown in Table 10, respectively.

The above test results for polyamide-6.6 plaques include:

Blends containing isobenzoxazinone can improve performance with respect to color and gloss.

Claims (10)

Isobenzoxazinone of Formula I: Formula I

Where R ₁ represents a long chain alkyl substituent, cycloalkyl substituent or isoalkyl substituent of C _n H _{2n + 1} , n is 8 to 30; X represents a direct bond or -O-, an ester group (-COO-) or -S-; R ₂ , R ₃ , R ₄ and R ₅ independently represent a substituent selected from hydrogen, halogen (F, Cl, Br, I) or C _1-12 alkyl. The method of claim 1, R ₁ represents a long chain alkyl or isoalkyl substituent of C _n H _{2n + 1} , n is from 8 to 18, X represents -O-, Isobenzoxazinone wherein R ₂ , R ₃ , R ₄ and R ₅ independently represent a substituent selected from hydrogen, fluoro, chloro or C _1-4 alkyl. The method of claim 1, R ₁ represents a long chain alkyl or isoalkyl substituent of C _n H _{2n + 1} , n is from 8 to 18, X represents -O-, Isobenzoxazinone wherein R ₂ , R ₃ , R ₄ and R ₅ independently represent a substituent selected from hydrogen, fluoro, chloro, methyl, ethyl, n-propyl, iso-propyl or tert-butyl. The method of claim 1, Isobenzoxazinone wherein the compound of formula (I) is selected from compounds of formula (Ia) to (Ig)

5-hydroxyisophthalic acid is diesterized, the hydroxy group is reacted with bromo-R ₁ , the diester is hydrolyzed to diacid, the diacid is converted to diacid chloride, and the diacid chloride is anthranilic acid or a derivative thereof A method for producing isobenzoxazinone according to claim 1, characterized in that the step of reacting with. Use of the isobenzoxazinone according to claim 1 for stabilizing organic polymers against the damaging effects of light and heat. Use of isobenzoxazinone according to claim 1 for cosmetic use. A process for stabilizing an organic polymer, characterized in that at least one isobenzoxazinone according to claim 1 is incorporated into the organic polymer at a concentration of 0.005 to 0.100% by weight, based on the polymer weight. An organic polymer composition comprising isobenzoxazinone according to claim 1 at a concentration of 0.005 to 0.100% by weight, based on the weight of the polymer. The method of claim 9, The organic polymer composition wherein the organic polymer is selected from polycarbonates, polyesters or polyamides.