3-ARYL-BENZOFURANONE COMPOUND AND COMPOSITION FORMED THEREFROM

Abstract

The present invention discloses a 3-aryl-benzofuranone compound in which R.sub.1-R.sub.6, in the formula are mutually independent H or C.sub.1-C.sub.20 alkyls, and R.sub.7 is C.sub.7-C.sub.20 alkyl or C.sub.7-C.sub.20 mixed alkyl. The present invention also discloses a composition of 3-aryl-benzofuranone compound and the preparation method. The 3-aryl-benzofuranone compound and the composition thereof has the superiority in application due to the characteristics of less proneness to volatilize, less proneness to be extracted, higher resistance to migration and less proneness to bloom and precipitate on the surface of organic materials, and with a wide range of application, it is effective during the application.

Claims

1. A 3-aryl-benzofuranone compound represented by Formula (I): ##STR00009## R.sub.1-R.sub.5 are each independently one another H or C.sub.1-C.sub.4 alkyl, R.sub.6 is C.sub.1-C.sub.5 alkyl and R.sub.7 is C.sub.7-C.sub.20 alkyl.

2. The 3-aryl-benzofuranone compound according to claim 1, wherein, R.sub.1-R.sub.5 are not simultaneously H, and R.sub.7 is C.sub.7-C.sub.18 alkyl.

3. A composition formed by the 3-aryl-benzofuranone compound according to claim 1, comprising: component a: at least one organic material prone to be degraded as induced by oxidation, heat and/or light; and component b: at least one 3-aryl-benzofuranone compound represented by the Formula (I) in claim 1, wherein the component (b) is added to the component (a) in a range of 0.0001%-10% weight percent.

4. The composition according to claim 3, wherein, the organic material is natural organic polymer, semi-synthetic organic polymer or synthetic organic polymer.

5. (canceled)

6. The composition according to claim 3, further comprising at least one other additive selected from the group consisting of phenolic antioxidant, phosphite ester or phosphinate ester, amine antioxidant, light stabilizer, acid-scavenger, anti-hydrolytic reagent, processing stabilizer and flame retardant, wherein a weight ratio of said one other additive to the component (b) is 10:1-1:20.

7. (canceled)

8. (canceled)

9. A method of the preparation of 3-aryl-benzofuranone compound according to claim 1, comprising following steps: reacting C.sub.7-C.sub.20 alkanols or a mixture thereof with a compound represented by Formula (II) at 5˜200° C., using acid catalyst in a solvent or solvents without hydroxyl group, wherein R.sub.1-R.sub.5 are each independently H or C.sub.1-C.sub.4 alkyl, R.sub.6 is C.sub.1-C.sub.5 alkyl, R.sub.8 is methyl, a ratio of said alkanols to said compound represented by Formula (II) is 1-10:1 ##STR00010##

10. The method of the preparation of 3-aryl benzofuranone compound according to claim 9, R.sub.8 is methyl.

11. The 3-aryl-benzofuranone compound according to claim 1, wherein, R.sub.7 is C.sub.7-C.sub.9 alkyl.

12. The 3-aryl-benzofuranone compound according to claim 2, wherein, R.sub.7 is C.sub.7-C.sub.9 alkyl.

13. The 3-aryl-benzofuranone compound according to claim 1, wherein, R.sub.1-R.sub.5 are each independently one another H or methyl, R.sub.6 is 1,1-dimethylethyl, and R.sub.7 is octyl or 2-ethylhexyl or 6-methyl heptyl.

14. The 3-aryl-benzofuranone compound according to claim 1, wherein, for using in the preparation of heat stabilizers to organic materials susceptible to oxidation, heat and/or light-induced degradation.

Description

DETAILED DESCRIPTION

[0025] A detailed description is given on this invention according to the specific examples.

Example 1

[0026] Preparation of the mixture of methyl 3-(7-tert-butyl-3-(2,3-dimethylphenyl)-2-oxo-2,3-dihydrobenzofuran-5-yl) propanoate and methyl 3-(7-tert-butyl-3-(3,4-dimethylphenyl)-2-oxo-2,3-dihydrobenzofuran-5-yl)propanoate.

[0027] In a 1000 mL four-neck round-bottom flask equipped with mechanical stirrer, heat controller and reflux condenser, add 300 g of 1,2-dichloroethane and 118 g of methyl 3-(3-teriarybutyl-4-hydroxyphenyl) propionate, stir fully to such an extent that the methyl 3-(3-teriarybutyl-4-hydroxyphenyl) propionate is dissolved into 1,2-dichloroethane, Then add 89 g of ethanol acid (50% ethanol acid aqueous solution) and 0.9 g of para-toluenesulfonic acid monohydrate. At 85° C., heat the mixture and perform reflux for 6 hours. Subsequently, steam the 1,2-dichloroethane out under the condition of decompression. Then add 300 ml of methyl tertiary butyl ether to dissolve the crude product, and wash with water. Separate the organic phase, and remove the methyl tertiary butyl ether under the condition of decompression. Vacuum dehydrate the obtained product at 60° C., and obtain 175 g of crude product.

[0028] In another 1000 mL four-neck round-bottom flask equipped with mechanical stirrer, heat controller and reflux condenser, cool the suspension of 30 g of anhydrous aluminum chloride and 50 g of o-xylene to 0° C., and then add the above suspension to the solution in which 200 g dimethylbenzene dissolves 85 g of the above obtained crude product within 60 minutes. Subsequently, continue the stirring for 4 hours, and gradually elevate the temperature to 40° C. 16 hours thereafter, add 25 g of anhydrous aluminum chloride at 40° C., and continue stirring for 8 hours at 40° C. Add ice when cooled to 0° C., and then add 37% HCl aqueous solution until the PH value reaches 1. Extract aqueous phase with methyl tertiary butyl ether, wash with sodium carbonate solution three times after the organic phase is separated, extract the excessive o-xylene to obtain red oily crude product under the condition of decompression after the anhydrous sodium sulfate is dried, and use the rapid chromatography method to further purify (silica gel; n-hexane/acetic ether gradient solvent system) 38 g of the mixture of products 2,3- and 3,4-isomers as shown in formula (II-1). (II-1) Analytic data of compound: 1H NMR (methine chemical shift 4.8) MS (m/z: 380.20),

##STR00003##

Example 2

[0029] Preparation of the mixture of 6-methylheptyl 3-(7-(tert-butyl)-3-(2,3-dimethylphenyl)-2-oxo-2,3-dihydrobenzofuran-5-yl)propanoate and 6-methylheptyl 3-(7-(tert-butyl)-3-(3,4-dimethylphenyl)-2-oxo-2,3-dihydrobenzofuran-5-yl)propanoate

[0030] In a 1000 mL four-neck round-bottom flask equipped with mechanical stirrer, heat controller and reflux condenser, mix 140 g (0.4 mol) of the product prepared according to the formula (II-1) in Example 1, and 104 g of isooctanol (0.8 mol of EXXAL8 isooctyl alcohol of ExxonMobil Chemical), 40 g of methylbenzene and 2 g of aluminum isopropoxide. Stir the reaction mixture and heat to 85° C. at the nitrogen environment for 5 hours. When the reaction is completed, add 8.8 g of citric acid aqueous solution (50%), stir for 20 minutes continuously, and then add 180 g of water at 75° C. and stir for 20 minutes. Separate the organic phase, then wash with saline twice, and then dry with sodium sulfate. Extract the methylbenzene and excessive isooctanol from the organic phase under the condition of depression, vacuum dry the residues (2 mb, 60° C.) and obtain 188 g of light yellow viscous liquid such as compound (II) in formula I, which is the mixture of 2,3-isomer and 3,4-isomer. Formula (I-1) Analytic data of compound: MS (m/z: 478.31), 1H NMR (methine chemical shift 4.8),

##STR00004##

Example 3

[0031] Preparation of the mixture of octyl 3-(7-(tert-butyl)-3-(2,3-dimethylphenyl)-2-oxo-2,3-dihydrobenzofuran-5-yl)propanoate and octyl 3-(7-(tert-butyl)-3-(3,4-dimethylphenyl)-2-oxo-2,3-dihydrobenzofuran-5-yl)propanoate.

[0032] The preparation method is basically the same with Example 2, and the difference lies in that the n-octyl alcohol is used to replace the isooctanol in Example 2. The 180 g compound (I-2) obtained from separation is the light yellow viscous liquid. Formula (I-2) Analytic data of compound: MS (m/z: 478.31), 1H NMR (methine chemical shift 4.8),

##STR00005##

Example 4

[0033] Preparation of the mixture of 2-ethylhexyl-3-(7-tert-butyl-3-(2,3-dimethylphenyl)-2-oxo-2,3-dihydrobenzofuran-5-yl)propanoate and 2-ethylhexyl 3-(7-tert-butyl-3-(3,4-dimethylphenyl)-2-oxo-2,3-dihydrobenzofuran-5-yl)propanoate.

[0034] The preparation method is basically the same with Example 2, and the difference lies in that the ethylhexyl alcohol is used to replace the isooctanol in Example 2. The 178 g compound (I-3) obtained from separation is the light yellow viscous liquid. Analytic data of compound in formula (I-3): MS (m/z: 478.31), 1H NMR (methine chemical shift 4.8),

##STR00006##

Example 5

[0035] Preparation of the mixture of octadecyl 3-(7-tert-butyl-3-(2,3-dimethylphenyl)-2-oxo-2,3-dihydrobenzofuran-5-yl)propanoate and octadecyl 3-(7-tert-butyl-3-(3,4-dimethylphenyl)-2-oxo-2,3-dihydrobenzofuran-5-yl) propanoate.

[0036] The preparation method is basically the same with Example 2, and the difference lies in that the propionic acid octadecyl ester is used to replace the isooctanol in Example 2. Obtain 190 g of compound (I-4), separate it and use methanol for recrystallization, and obtain white crystalline powder. Formula I-4 analytic data of compound: MS (m/z: 618.46), 1H NMR (methine chemical shift 4.8),

##STR00007##

[0037] Thermostability of Polyether Polyol

Example 6

[0038] The resistance to oxidation of polyether polyol samples is determined through differential scanning calorimetry (DSC). The initial temperature of sample heating is 50° C.; with the presence of oxygen, the temperature elevation rate is 5° C./min until 200° C. is reached. The appearance of exothermic peak means the start of thermal oxidation and attention should be paid to the initial temperature of exothermic peak. A sample with a good thermostability is characterized by the possession of a relatively high initial temperature of thermal oxidation.

[0039] Arcol F-3022 (Bayer trade name) is a multifunctional polyether polyol with a hydroxyl value of 56 mg KOH/g, moisture of less than 0.1%, and an acid value of less than 0.04 mg KOH/g.

[0040] Irganox 1135 (Bayer trade name) is a kind of liquid phenolic antioxygen with its component of 3-(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid isooctyl ester.

[0041] Irganox 5057 (BASF trade name) is a kind of amine antioxidant, a mixture obtained from the reaction from diphenylamine and diisobutylene. Comprising: [0042] a) ≦5% diphenylamine; [0043] b) 8 to 15% 4-butyl diphenylamine; [0044] c) 24 to 32% compound of the following components: [0045] i) 4-tert-octyl diphenylamine, [0046] Ii) 4,4′-2-tert-butyl diphenylamine, [0047] Iii) 2,4,4′-3-tert-butyl diphenylamine; [0048] d) 23 to 34% compound of the following components: [0049] i) 4-tert-octyl-4′-tert-octyl diphenylamine, [0050] ii) ortho, ortho′-, meta, meta′, - or dyad, dyad′-2-tert-octyl diphenylamine, [0051] iii) 2,4-tert-butyl-4′;-tert-octyl diphenylamine [0052] e) 21 to 34% compound of the following components: [0053] i) 4,4-2-tert-octyl diphenylamine, [0054] ii) 2,4-tert-octyl-4′;-tert-butyl diphenylamine.

[0055] Irganox HP 136 (BASF trade name) is a 3-aryl-benzofuranone antioxidant and its component is the mixture of 5,7-di-tert-butyl-3 (3,4-dimethyl phenyl)-3H-benzofuran-2-ketone and 5,7-di-tert-butyl-3-(2,3,-dimethyl phenyl)-3H-benzfuran-2-ketone.

##STR00008##

[0056] Table 1 shows the mixture of 100 portions of Arcol F-3022 polyether polyol and stabilizer composition

TABLE-US-00001 TABLE 1 Initial temperature of thermal oxidation Example Testing samples [° C.] Examples 100 portions of polyether polyol, without 134 6-1 any additive added. Example 100 portions of polyether polyol, and a 189 6-2 stabilizer composition, comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of Irganox HP 136. Examples 100 portions of polyether polyol, and a 196 6-3 stabilizer composition, comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of stable compound as shown in formula (I-1). Examples 100 portions of polyether polyol, and a 193 6-4 stabilizer composition, comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of stable compound as shown in formula (I-2). Examples 100 portions of polyether polyol, and a 193 6-5 stabilizer composition, comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of stable compound as shown in formula (I-3).

[0057] Thermostability of Polyether Polyol Containing Fire Retardant

Example 7

[0058] The resistance to oxidation of polyether polyol samples is determined through differential scanning calorimetry (DSC) according to the method in Example 6.

[0059] FYROL FR-2 LV (ICL trade name) is an additive and liquid fire retardant that contains 3-(1,3-dichlone-2-propyl phosphate ester) commercially uses soft and hard polyurethane foams.

[0060] Table 2 shows the mixture of 100 portions of Arcol F-3022 FYROL polyether polyol, FYROL FR-2 LV liquid fire retardant (based on 100 weight portions of polyether polyol) and stabilizer composition (based on 100 weight portions of polyether polyol).

TABLE-US-00002 TABLE 2 Initial temperature of thermal oxidation Example Testing samples [° C.] Examples 100 portions of polyether polyol, without the 134 7-1 addition of FYROL FR-2 LV and any stabilizer. Examples 100 portions of polyether polyol and 16 portions 129 7-2 of FYROL FR-2 LV, without the addition of any stabilizer. Examples 100 potions of polyether polyol, 16 portions of 189 7-3 FYROL FR-2 LV, and a stabilizer composition comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox5057 and 0.03 portion of Irganox HP136. Examples 100 portions of polyether polyol, 16 portions of 196 7-4 FYROL FR-2 LV, and a composition comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of the stabilizer as shown in formula (II-1). Examples 100 portions of polyether polyol, 16 portions of 193 7-5 FYROL FR-2 LV, and a composition comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of the stabilizer as shown in formula (II-2). Examples 100 portions of polyether polyol, 16 portions of 193 7-6 FYROL FR-2 LV, and a composition comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of the stabilizer as shown in formula (II-3).

[0061] Thermostability of Polyether/Polyurethane Soft Foams (Resistance to Burning)

Example 8

[0062] The resistance to burning is determined through static heat deterioration (static aluminium block test) The foaming blocks are cut into thin tubes (2 cm thick, with a diameter of 1.5 cm). As for each foaming block, the thin tube is the foam sample. Put the foam sample into the aluminium block and heat it.

[0063] Maintain the status at 180, 190, 200 and 210° C. for 30 minutes. Resistance to burning is evaluated through the measurement of the colors after the foam samples have heat aging. The measured color value is recorded according to the yellowness index (YI) measured on the foam sample using the ASTM 1926-70 yellowness testing method. A low YI value means a low discoloration, and a high YI value means the severe discoloration of samples. A high whiteness in the foam sample means a better thermostability of foam sample.

[0064] Dissolve the stabilizer composition (on the basis of 100 weight portions of polyether polyol) as in Table 3 in the 150.8 g of Arcol F-3022. Add 9.8 g of solution comprising 1.8 g of TEGOSTAB BF 2370 (Evonik trade name; surface activator based on the polysiloxane) and 0.2 g of Tegoamin 33 (Evonik trade name; gelatinized catalytic agent based on triethylenediamine), add 7.8 g of deionized water, and intensely stir this reaction mixture for 15 seconds. Then add 0.3 g of Kosmos 29 (Evonik trade name; the catalytic agent based on stannous octoate), and intensely stir this reaction mixture for 20 seconds continuously. Add 92.2 g of the solution in Demodur T80 (Bayer trade name, mixture of methylbenzene-2,4- and methylbenzene-2,6-diisocyanate), and stir it for 10 seconds continuously. Pour the mixture into a 20×20×20 cm box, and an increase in temperature means that the foaming and heat release should be happening. Cool the foaming blocks and maintain the status at room temperature for 24 hours. All the prepared foaming blocks display the initial white of the corresponding degrees.

TABLE-US-00003 TABLE 3 Yellowness Yellowness Yellowness Yellowness index (YI) index (YI) index (YI) index (YI) Exposed at Exposed at Exposed at Exposed at 180° C. for 190° C. for 200° C. for 210° C. for Example Testing samples 30 minutes 30 minutes 30 minutes 30 minutes Examples 100 portions of polyether 19.3 24.9 45.6 53.9 8-1 polyol, without any additive added. Examples 100 portions of polyether −0.9 −2.1 4.2 25.1 8-2 polyol, and a kind of stabilizer composition, comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of Irganox HP 136. Examples 100 portions of polyether −1.3 −2.5 3.6 23.8 8-3 polyol, and a kind of stabilizer composition, comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of stable compound as shown in formula (I-1). Examples 100 portions of polyether −1.3 −2.3 3.8 24.2 8-4 polyol, and a kind of stabilizer composition, comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of stable compound as shown in formula (I-2). Examples 100 portions of polyether −1.3 −2.5 3.8 24.0 8-5 polyol, and a kind of stabilizer composition, comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of stable compound as shown in formula (I-3).

[0065] Thermostability of Fire Retardant Containing Polyether/Polyurethane Soft Foams (Anti-Scorching)

Example 9

[0066] The test of anti-scorching is based on the method described in Example 8.

[0067] Dissolve 6.8 g of stabilizer composition (0.45 portion, with 100 portions of polyether polyol) as shown in Table 4 into the 150.8 g of Arcol F-3022. Add 24.1 g of FYROL FR-2 LV (16 portions, on the basis of 100 weight portions of polyether polyol), and 9.8 g of solution comprising 1.8 g of TEGOSTAB BF 2370 (Evonik trade name; surface activator based on the polysiloxane) and 0.2 g of Tegoamin 33 (Evonik trade name; gelatinized catalytic agent based on triethylenediamine), add 7.8 g of deionized water, and intensely stir this reaction mixture for 15 seconds. Then add 0.3 g of Kosmos 29 (RTM Evonic; the catalytic agent based on stannous octoate), and intensely stir this reaction mixture for 20 seconds continuously. Add 92.2 g of the solution in Demodur T80 (Bayer trade name, mixture of methylbenzene-2,4- and methylbenzene-2,6-diisocyanate), and stir it for 10 seconds continuously. Pour the mixture into a 20×20×20 cm box, and an increase in temperature means that the foaming and heat release should be happening. Cool the foaming blocks and maintain the status at room temperature for 24 hours. All the prepared foaming blocks display the initial white of the corresponding degrees.

TABLE-US-00004 TABLE 4 Yellowness Yellowness Yellowness Yellowness index (YI) index (YI) index (YI) index (YI) Exposed at Exposed at Exposed at Exposed at 180° C. for 190° C. for 200° C. for 180° C. for Example Testing samples 30 minutes 30 minutes 30 minutes 210 minutes Example 100 portions of polyether 35.2 48.1 59.9 68.5 9-1 polyol, without any additive added. Example 100 portions of polyether 3.7 11.7 35.9 58.2 9-2 polyol, and a kind of stabilizer composition, comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of Irganox HP 136. Example 100 portions of polyether 2.1 9.2 30.6 52.8 9-3 polyol, and a kind of stabilizer composition, comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of stable compound as shown in formula (I-1). Example 100 portions of polyether 2.1 9.3 30.9 53.4 9-4 polyol, and a kind of stabilizer composition, comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of stable compound as shown in formula (I-2). Example 100 portions of polyether 2.1 9.2 30.8 53.2 9-5 polyol, and a kind of stabilizer composition, comprising 0.32 portion of Irganox 1135, 0.10 portion of Irganox 5057 and 0.03 portion of stable compound as shown in formula (I-3).

[0068] Thermostability of ABS (Acrylonitrile-Butadiene-Styrene)

Example 10

[0069] Irganox 1076 (Bayer trade name) is a kind of phenolic antioxidant, which contains n-octadecane 3-(3,5-ditert-butyl-4-hydroxyphenyl) propionate. Irgafos 168 (BASF trade name) is a phosphite ester antioxidant that contains 3-(2,4-ditert-butylphenyl) phosphite ester.

[0070] 100 portions of polymer (comprising 33.3 portions of ABS graft polymer and 66.7 portions of SAS polymer), 1.05 portion of N,N′-ethylene-bis-stearic amide [relative to 100 portions of polymers] and one stabilizer composition according to Table 5 (on the basis of 100 portions of polymer) are mixed in a roller mixing machine for 15 hours. Then, compound the obtained dry mixture in a double-screwed extruder (at 220° C., 110 r and 12 kg/hour). After drying at 80° C. for 3 hours, perform injection molding at 240° C. (machine circulation time: 35.8 seconds; injection speed: 25 mm/second, mold temperature: 60° C.), and obtain the natural ABS test piece with a dimension of 67×64×2 mm.

[0071] Measure the initial color of these test pieces, then perform acceleration anti-weathering steel 1000-hour test on the test pieces using the Weather-O-Meter at the following conditions: 340 nm, 0.35 W/m.sup.2; internal and external filters of borosilicate; black panel temperature; 63° C.; dark free stage; relative humidity 60%, dry circulation (no rain). Determine the yellowness index (YI) according to DIN 6167. A low YI value means a low discoloration, and a high YI value means the severe discoloration of test pieces. A low discoloration means an effective thermal stability.

TABLE-US-00005 TABLE 5 Yellowness Example Testing samples index (YI) Examples 100 portions of polymers, without any additive >100 10-1 added. Examples 100 portions of polymers, comprising 0.057 50.8 10-2 portion of Irganox 1076, 0.113 portion of Irganos 168 and 0.03 portion of Irganox HP 136. Examples 100 portions of polyether polyol, and a kind of 46.8 10-3 stabilizer composition, comprising 0.057 portion of Irganox 1076, 0.113 portion of Irganos 168 and 0.03 portion of stable compound as shown in formula (I-4).

[0072] According to an embodiment of the present invention that has been described, it should be understood that the above embodiments of the present invention are not limited in any way, and any use or equivalent conversion method equivalents acquired technology solutions are within the scope of the invention as inside.