PHOSPHITE COMPOUND, METHOD FOR PRODUCING THE SAME AND USES THEREOF

Abstract

The present invention relates to a novel phosphite compound represented by the formula (I):

##STR00001##

wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, a process for producing the same, and uses thereof as a stabilizer for an organic material.

Claims

1. A phosphite compound represented by the formula (I) ##STR00017## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl cycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.

2. A hydroxy compound represented by the formula (II) ##STR00018## wherein R.sup.3 and R.sup.4 are as defined above.

3. A method for producing the phosphite compound according to claim 1, wherein the hydroxy compound represented by the formula (II), the bisphenol compound represented by the formula (III) ##STR00019## wherein R.sup.1 and R.sup.2 are as defined above, and a phosphorus trihalide are reacted.

4. A stabilizer for an organic material, comprising the phosphite compound according to claim 1.

5. The stabilizer according to claim 4, wherein the organic material is a thermoplastic resin.

6. The stabilizer according to claim 5, wherein the thermoplastic resin is a polyolefin or an engineering plastic.

7. A method for stabilizing an organic material, wherein the phosphite compound according to claim 1 is added to an organic material.

8. The method according to claim 7, wherein the organic material is a thermoplastic resin.

9. The method according to claim 8, wherein the thermoplastic resin is a polyolefin or an engineering plastic.

10. A stabilized organic material composition comprising an organic material and a phosphite compound according to claim 1.

11. The composition according to claim 10, wherein the organic material is a thermoplastic resin.

12. The composition according to claim 11, wherein the thermoplastic resin is a polyolefin or an engineering plastic.

Description

EXAMPLES

[0209] Hereinafter, the present invention will be described in more detail by showing examples, but the present invention is not limited by these examples. [0210] Measurement of .sup.1H-NMR

[0211] Apparatus: manufactured by bruker, AV-600 600 MHz

[0212] Measurement solvent: CDCl.sub.3 [0213] Measurement of MFR

[0214] The measurement of MFR was carried out at 190° C. under a load of 2.16 kg using “Melt Indexer L 246-3537” manufactured by Technol Seven Co., Ltd.

Synthesis Example 1

Preparation of Compound 1A

[0215] Fifty g of ethyl acrylate, 200 ml of 1,4-dioxane as a solvent and 200 ml of distilled water were added under a nitrogen stream to a flask equipped with a thermometer, a stirrer and a cooling tube. 14.95 g of paraformaldehyde and 5.6 g of 1,4-diazabicyclo[2.2.2]octane were added, hydroquinone was further added as a polymerization inhibitor, and the mixture was stirred at room temperature for 6 days. Using an evaporator at 40° C., 1,4-dioxane as a reaction solvent was distilled off. Subsequently, the extraction operation, in which 100 ml of methyl t-butyl ether was added, and the mixture was shaken, followed by liquid separation, was performed three times. After washing the methyl t-butyl ether layer twice with 50 ml of water, methyl-t-butyl ether was distilled off using an evaporator to obtain 64.9 g of a crude product. The product was purified with a silica gel column using a mixed solvent of ethyl acetate and hexane (ethyl acetate: hexane=10:90 (volume ratio)) to obtain 35 g of Compound 1A. The yield was 43%. The same operation was repeated again to obtain the target product in a yield of 41.5%.

##STR00009##

Synthesis Example 2

Preparation of Compound 2A

[0216] One hundred fifty ml of diethyl ether and a catalytic amount of hydroquinone were added to a 500 ml flask containing 20.0 g of the compound 1A obtained in Synthesis Example 1 at room temperature. After cooling to 0 to −5° C., 5.2 g of PBr.sub.3 was added dropwise. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for 20 hours. 50 ml of ice water was added to the reaction mixture, and the mixture was washed three times with 50 ml of water. The obtained diethyl ether solution was dried by adding anhydrous sodium sulfate. Diethyl ether was distilled off from the solution using an evaporator at 35° C. to obtain 24 g of Compound 2A. The same operation was repeated again to obtain the target product in a yield of 70 to 80%.

##STR00010##

Synthesis Example 3

Preparation of Compound 1B

[0217] Two hundred fifty ml of dichloromethane was added to a 1 L flask containing 25.0 g of 2-methyl-6-t-butylphenol at room temperature. After cooling to 0 to −5° C., 24.35 g of bromine was slowly added at room temperature, then the ice bath was removed and the mixture was stirred at room temperature for 10 hours. 187.5 ml of 1 M sodium sulfate was added at room temperature, the mixture was cooled to 0 to −5° C. and stirred for 30 minutes. The organic layer was washed with 250 ml of water and 250 ml of brine and then dried by adding anhydrous sodium sulfate. The obtained organic layer was concentrated with an evaporator to obtain 36 g of a crude product of Compound 1B. The yield was 98%. The same synthesis was carried out to obtain 145.0 g of the target product.

##STR00011##

Synthesis Example 4

Preparation of Compound 2B

[0218] To a 1 L flask containing 35.0 g of Compound 1B obtained in Synthesis Example 3, 350 ml of N,N-dimethylformamide was added at room temperature. 39.81 g of potassium carbonate was added at room temperature, the mixture was stirred for 15 minutes, and then cooled to 0 to −5° C. 40.46 g of methyl iodide was gradually added at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 20 hours. 350 ml of ice water was added to the reaction mixture, which was stirred for 20 minutes, and extraction was carried out three times with 400 ml of ethyl acetate. The obtained organic layer was washed four times with 400 ml of water, washed with 400 ml of brine, and dried by adding anhydrous sodium sulfate. The organic layer was concentrated using an evaporator to obtain 36.9 g of a crude product. The product was purified with a silica gel column using a mixed solvent of ethyl acetate and hexane (ethyl acetate: hexane=5:95 (volume ratio)) to obtain 33.0 g of Compound 22. The synthesis was repeated to obtain 121 g of Compound 22 in a yield of 78.1%.

##STR00012##

Synthesis Example 5

Preparation of Compound 1C

[0219] Three point three g magnesium and a catalytic amount of iodine were added to a 500 ml flask. The mixture was heated from room temperature to 50° C. and stirred for 15 minutes. 30 ml of tetrahydrofuran (hereinafter referred to as THE) was added at room temperature, and then 5 ml of a solution prepared by dissolving 28.13 g of Compound 2A obtained in Synthesis Example 2 in 70 ml of THF was added. After the mixture was heated to 60° C. and stirred for 20 minutes, the remaining 65 ml was slowly added at room temperature and the resulting Grignard reagent was stirred at 60° C. for 2 hours and allowed to cool.

[0220] To a 500 ml flask, 19.2 g of Compound 22 obtained in Synthesis Example 4 and 95 ml of THF were added. After cooled to −78 to −80° C., the mixture was stirred for 20 minutes, and the Grignard reagent obtained above was dropped by syringe. After completion of the dropwise addition, the mixture was stirred at room temperature overnight. 100 ml of 10% hydrochloric acid was added, and the mixture was stirred at 0 to −5° C. for 20 minutes. THF was distilled off using an evaporator, and extraction was carried out three times with 350 ml of ethyl acetate. The organic layer was washed three times with 300 ml of water and once with 300 ml of brine and then dried by adding anhydrous sodium sulfate. The organic layer was concentrated with an evaporator to obtain 29.0 g of a crude product. The product was purified with a silica gel column using a mixed solvent of ethyl acetate and hexane (ethyl acetate: hexane=10:90 (volume ratio)) as a mobile phase to obtain 18.0 g of Compound 1C. The yield was 65%. Synthesis was performed again using 19.5 g of Compound 2A to obtain Compound 1C.

##STR00013##

Synthesis Example 6

Preparation of Compound 2C

[0221] Nineteen point five g of Compound 1C obtained in Synthesis Example 5 and 195 ml of dichloromethane were added to a 2 flask, and the mixture was cooled to −78 to −80° C. and stirred for 30 minutes. Then, 343.78 ml of 25% diisobutylaluminum hydride-toluene solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature overnight. After the completion of the reaction was confirmed, the mixture was cooled to 0 to −5° C. and 100 ml of a 10% water-methanol solution was added dropwise. 800 ml of dichloromethane was added at room temperature, and the mixture was stirred for 30 minutes. The solution was filtered and the residue was washed three times with 400 ml of warmed dichloromethane. The filtrate was concentrated with an evaporator to obtain 13.5 g of Compound 2C. The yield was 85%. The synthesis was repeated to obtain the target product in a yield of 75.7%.

##STR00014##

Example 1

Production of Hydroxy Compound (2-t-butyl-4-(2-hydroxylmethyl-allyl)-6-methyl-phenol) of Formula (II-1)

[0222] Three g of Compound 2C obtained in Synthesis Example 6, equivalents of ethyl sodium sulfide and 30 ml of N,N-dimethyl formamide were added to a 250 ml reactor capable of being capped, and the reactor was capped and heated at 140° C. in an oil bath for 2.5 hours. The reaction mixture was cooled to room temperature and diluted by adding 50 ml of ethyl acetate. The obtained organic layer was washed with 50 ml of a 10% hydrochloric acid aqueous solution, and the organic layer was separated. Subsequently, the organic layer was washed with 100 ml of brine, and N,N-dimethylformamide was completely removed. The organic layer was dried by adding anhydrous sodium sulfate and concentrated with an evaporator. The product was purified with a silica gel column using a mixed solvent of hexane and dichloromethane (hexane: dichloromethane=30:70 (volume ratio)) to obtain 0.94 g of the target product. The yield was 25%. The synthesis was repeated several times to obtain the target product in a yield of 20 to 25%.

##STR00015##

[0223] .sup.1H-NMR (600 MHz, CDCl.sub.3) δ: 6.95 (d, 4J=2.4 Hz, 1H-g), 6.82 (d, 4J=2.4 Hz, 1H-g), 5.09, 4.90 (s, 2H-f), 4.67 (s, 1H-e), 4.05 (s, 2H-d), 3.30 (s, 2H-c), 2.22 (s, 3H-b), 1.40 (s, 9H-a)

Example 2

Production of Phosphite Compound Represented by Formula (I-1): 2-t-butyl-6-methyl-4-(2-{[(2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]methyl}prop-2-en-l-yl)phenol

[0224] To a 500 ml flask containing 4.8 g of 2,2′-di-hydroxy-3,3′,5,5′-tetra-t-butylbiphenyl and 48 ml of xylene was added 1.76 g of phosphorus trichloride at room temperature. After stirring the mixture at 50° C. for 30 minutes, 30 ml of N,N-diisopropylethylamine was slowly added dropwise at room temperature to the mixture, which was then heated to 55° C. and stirred at 55° C. for 1 hour. After cooling to room temperature, 30 ml of N, N-diisopropylethylamine was further added to the mixture, which was then stirred for 25 minutes. 3 g of the hydroxy compound obtained in Example 1 was dissolved in 48 ml of xylene and the solution was added dropwise to the 500 ml flask at a temperature of room temperature to 55° C. Then, the mixture was heated to 80° C. and stirred for 12 hours. After the completion of the reaction was confirmed by thin layer chromatography (ethyl acetate: hexane=5:95 as a mobile phase), the mixture was cooled to room temperature, 100 ml of ethyl acetate was added thereto, and the mixture was washed three times with 150 ml of water. The organic layer was separated and then dried by adding anhydrous sodium sulfate. The resultant organic layer was concentrated with an evaporator to obtain 8.1 g of a crude product. The crude product was purified with a silica gel column using a mixed solvent of ethyl acetate: hexane=5:95 (volume ratio) to obtain 5.2 g of white crystals. The yield was 69%. The synthesis was repeated several times to obtain the target product in a yield of 65 to 69%.

##STR00016##

[0225] .sup.1‘H-NMR (600 MHz, CDCl.sub.3) δ: 7.41 (d, 4J=2.3 Hz, 2H, Ar—H, (1)), 7.15 (d, 4J-2.3 Hz, 2H, Ar—H, (k)), 6.86 (d, 4J=2.3Hz, 1H, Ar—H, (j)), 6.71 (d, 4J=2.3 Hz, 1H, Ar—H, (i)), 5.00, 4.82 (s, 2H, CH.sub.2, (h)), 4.60 (s, 1H, OH, (g)), 4.13 (d, 3J-7.5Hz, 2H, OCH.sub.2, (f)), 3.19 (s, 2H, Ar—CH.sub.2, (e)), 2.15 (s, 3H, Ar—Me, (m)), 1.46 (s, 18H, t-Bu, (c)), 1.35 (s, 27H, t-Bu, (a,b))

Example 3

[0226] Zero point one zero part by mass of the phosphite compound obtained in the same manner as in Example 2 and 0.05 part by mass of calcium stearate were added to 100 parts by mass of polyethylene (LLDPE) (GA 401 manufactured by Sumitomo Chemical Co., Ltd.), and the mixture was dry blended. Subsequently, the obtained blend was granulated at 190° C. using a single screw extruder to obtain pellets. Thereafter, the operation of placing the pellets again in a single screw extruder and extruding at 230° C. was repeated five times. The MFR value of the pellets was measured before (0 time) extrusion at 230° C. and after 1, 3, 5 extrusion operations. Table 1 shows MFR value after 5 extrusion operations and the ratio of MFR values between 0 and 5 times (5 times/0 time). Here, it is known that polyethylene degrades as crosslinking progresses by extrusion. This phenomenon can be observed as a decrease in MFR value. Therefore, the fact that the MFR value is maintained without decreasing even when the extrusion operation is repeated indicates that crosslinking of the polyethylene is suppressed and thus the processing stability of the polyethylene is high.

Comparative Example 1

[0227] The MFR of polyethylene was measured in the same manner as in Example 3 except that the phosphite compound represented by the formula (I-1) was not added to the polyethylene pellets. The obtained results are shown in Table 1.

Comparative Example 2

[0228] The MFR of polyethylene was measured in the same manner as in Example 3 except that 0.10 part by mass of 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]−2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxapnosphepin, (Sumilizer® GP manufactured by Sumitomo Chemical Co., Ltd.) instead of the phosphite compound represented by the formula (I-1) was added to 100 parts by mass of polyethylene pellets. The obtained results are shown in Table 1.

TABLE-US-00001 TABLE 1 MFR value Ratio of MFR [g/10 minutes] values 5 times 5 times/0 time EXAMPLE 3 0.93 0.45 COMPARATIVE 0.33 0.22 EXAMPLE 1 COMPARATIVE 0.82 0.42 EXAMPLE 2

Example 4

[0229] Zero point one zero part by mass of the phosphite compound obtained in the same manner as in Example 2 and 0.05 part by mass of calcium stearate were added to 100 parts by mass of a powder of polypropylene (Homo-PP) (HS200, manufactured by Sumitomo Chemical Co., Ltd.), and the mixture was dry blended. Subsequently, the obtained blend was granulated at 230° C. using a single screw extruder to obtain pellets, and the MFR value was measured. Table 2 shows the MFR value. Here, it is known that polypropylene degrades due to extrusion and deteriorates. This phenomenon can be observed as an increase in MFR value. Therefore, the low MFR value indicates that polypropylene decomposition is suppressed and the processing stability of polypropylene is high.

Comparative Example 3

[0230] The MFR of polypropylene was measured in the same manner as in Example 4 except that the phosphite compound represented by the formula (I-1) was not added to the polypropylene powder. The obtained results are shown in Table 2.

TABLE-US-00002 TABLE 2 MFR value EXAMPLE 4 3.52 COMPARATIVE EXAMPLE 3 9.66