COMPOSITION

Abstract

The present invention concerns a stabilising antioxidative composition comprising tris(2-t-butylphenyl) phosphite in the absence of tris(2,4-di-t-butylphenyl) phosphite.

Claims

1-25. (canceled)

26. A stabilizing antioxidative composition, comprising tris(2-t-butylphenyl) phosphite, with the proviso that the composition does not contain any tris(2,4-di-t-butylphenyl) phosphite.

27. The stabilizing antioxidative composition according to claim 26, with the proviso that the composition does not contain any arylphosphite having a t-butyl group in the para-position, with respect to the phosphite group.

28. The stabilizing antioxidative composition according to claim 27, with the proviso that the composition does not contain any arylphosphite having an alkyl group in the para-position, with respect to the phosphite group.

29. The stabilizing antioxidative composition according to claim 26, with the proviso that the composition does not contain any di(2-t-butylphenyl) monophenyl phosphite.

30. A stabilizing antioxidative composition comprising tris(2-t-butylphenyl) phosphite, prepared by adding 2-t-butyl phenol to a phosphorus trihalide.

31. The stabilizing antioxidative composition according to claim 30, with the proviso that the composition does not contain any di(2-t-butylphenyl) monophenyl phosphite.

32. The stabilizing antioxidative composition according to claim 30, wherein the 2-t-butyl phenol is added to the phosphorus trihalide by subsurface addition.

33. The stabilizing antioxidative composition according to claim 30, wherein the addition of 2-t-butyl phenol to the phosphorus trihalide is conducted stepwise or continuously, such that 2-t-butyl phenol is added to a bulk quantity of the phosphorus trihalide.

34. The stabilizing antioxidative composition according to claim 30, wherein the reaction temperature during addition of the 2-t-butyl phenol to the phosphorus trihalide is maintained at or below 150° C. for at least a portion of the period of time during which the 2-t-butyl phenol is added to the phosphorus trihalide.

35. The stabilizing antioxidative composition according to claim 30, wherein the addition of the 2-t-butyl phenol to the phosphorus trihalide is conducted in the presence of a catalyst.

36. The stabilizing antioxidative composition according to claim 35, wherein the catalyst has the formula NR.sup.1R.sup.2R.sup.3, wherein R.sup.1 is H or an optionally substituted hydrocarbyl group, and R.sup.2 and R.sup.3, which may be the same or different, are both optionally substituted hydrocarbyl groups of carbon chain length >1; or wherein the catalyst has a cation and an anion, the cation having the formula N.sup.+R.sup.1R.sup.2R.sup.3R.sup.4, wherein R.sup.1 to R.sup.4, which may be the same or different, are optionally substituted hydrocarbyl groups having >1 carbon atoms.

37. Tris(2-t-butylphenyl) phosphite having a purity of at least about 98%.

38. The tris(2-t-butylphenyl) phosphite according to claim 37, having a purity of at least about 99%.

39. The tris(2-t-butylphenyl) phosphite according to claim 37, prepared by a single chemical reaction, followed by a single crystallization step.

40. The tris(2-t-butylphenyl) phosphite according to claim 39, wherein the single chemical reaction is adding 2-t-butyl phenol to a phosphorus trihalide.

41. A stabilizing antioxidative composition comprising the tris(2-t-butylphenyl) phosphite according to claim 37.

42. An antidegradant blend comprising the stabilizing antioxidative composition according claim 26.

43. The antidegradant blend according to claim 42, further comprising one or more of the following: i. a phenolic antioxidant; ii. a further organic phosphite antioxidant other than: x. tris(2,4-di-t-butylphenyl) phosphite; y. any arylphosphite having a t-butyl group in the para-position with respect to the phosphite group; and/or z. any arylphosphite having an alkyl group in the para-position with respect to the phosphite group; iii. a sulphur-containing antioxidant; and/or iv. an aminic antioxidant.

44. The antidegradant blend according to claim 42, further comprising one or more of the following: i. a buffering agent having the capacity to buffer in an aqueous solution at a pH range from 4 to 8; ii. a metal carboxylate; iii. an inorganic antioxidant or reducing agent; and/or iv. an inorganic acid scavenger.

45. The antidegradant blend according to claim 44, comprising: a. a buffering agent selected from one or more metal phosphates and/or one or more metal pyrophosphates; b. a buffering agent selected from the one or more amino acids and/or the alkali metal salts thereof; c. a metal carboxylate selected from the group consisting of a metal stearate, a metal lactate, a metal benzoate, and combinations thereof; d. a secondary inorganic antioxidant selected the group consisting of a metal hypophosphite, a metal thiosulphate, a metal bisulphite, a metal metabisulphite, a metal hydrosulphite, and combinations thereof; and/or e. an inorganic acid scavenger selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal salts, hydrotalcite-like compounds, and combinations thereof.

46. The antidegradant blend according to claim 42, further comprising one or more of the following: a. an organic phosphite antioxidant other than TOTBP selected from the group consisting of distearylpentaerythritol diphosphite; tris(dipropyleneglycol) phosphite, C.sub.18H.sub.39O.sub.9P; poly(dipropyleneglycol) phenyl phosphite; diphenyl isodecyl phosphite, C.sub.22H.sub.31O.sub.3P; phenyl diisodecyl phosphite; heptakis (dipropyleneglycol) triphosphite; and combinations thereof. b. a semi-hindered phenolic antioxidants selected from the group consisting of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-trione; triethyleneglycol-bis-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate]; the butylated reaction product of p-cresol and dicyclopentadiene; 2,2′-methylenebis(6-t-butyl-4-methylphenol); and combinations thereof; c. a hindered phenolic antioxidants selected from tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane; 2,2′thiodiethylene bis[3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; C13-C15 linear and branched alkyl esters of 3-(3′5′-di-t-butyl-4′-hydroxyphenyl) propionic acid; octadecyl 3-(3′,5′-di-t-butyl-4′-hydroxyphenyl) propionate; 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate; 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene; N,N′-hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide]; 1,2-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamoyl)hydrazine; C9-C11 linear and branched alkyl esters of 3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionic acid; 2,2′-ethylidenebis[4,6-di-t-butylphenol]; butylated hydroxytoluene; and combinations thereof; d. sulphur-containing antioxidants selected from the group consisting of dilauryl-3,3′-thiodipropionate; distearyl-3,3′-thiodipropionate; ditridecylthiodipropionate; pentaerythritol tetrakis (β-laurylthiopropionate); 2,2′thiodiethylene bis[3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; dimyristyl thiodipropionate; distearyl-disulfide; 4,4′-thiobis(2-tert-butyl-5-methylphenol); 2,2′-thiobis(6-t-butyl-4-methylphenol); and combinations thereof; and/or e. aminic antioxidants selected from the group consisting of acetone diphenylamine; reaction products of diphenylamine and acetone; N,N′-diphenyl-p-phenylenediamine; benzeneamine, N-phenyl-, reaction products with 2,4,4-trimethylpentene; bis[4-(2-phenyl-2-propyl)phenyl]amine; poly(1,2-dihydro-2,2,4-trimethylquinoline); dioctyldiphenylamine; N,N-bis-(1,4-dimethylpentyl)-p-phenylenediamine; 1,4-benzenediamine, N,N′-mixed phenyl and tolyl derivatives; N,N′,N″-tris[4-[(1,4-dimethylpentyl)amino]phenyl]-1,3,5-triazine-2,4,6-triamine; N-isopropyl-N′-phenyl-1,4-phenylenediamine; diphenylamine; (1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine; poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-butanedioic acid); bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate; bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate; poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][2,2,6,6-tetramethyl-4-piperidiyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidiyl)imino]]); 1,5,8,12-tetrakis[4,6-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidylamino)-1,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane; and combinations thereof.

Description

FIGURES

[0185] FIG. 1 depicts a graph of melt flow rate comparison of a polypropylene homopolymer compounded with the additives of Examples 1, 2 and 3 at compounding and after first, third and fifth multipass at 260° C. The results demonstrate comparable melt flow protection at equal phosphorus loading.

[0186] FIG. 2 depicts a graph of colour comparison (yellowing by YI) of a polypropylene homopolymer compounded with the additives of Examples 1, 2 and 3. TOTBP shows better performance than A240.

[0187] FIG. 3 depicts a graph of gas fading performance of a polypropylene homopolymer compounded with the additives of Examples 1, 2 and 3. TOTBP shows better performance than A240.

EXAMPLES 20 TO 22 (METHODS OF PREPARATION)

Standard Procedure (Example 20—Comparative)

Equipment

[0188] A 1 l jacketed vessel equipped with an overhead stirrer, condenser, nitrogen line and addition port. The vessel is vented via the condenser to a caustic scrubber.

Method

[0189] 2-t-butyl phenol was dried in the lab before use.

[0190] 2-t-butyl phenol (100 g; 0.666 mol; 1.00 eq) was charged to an inerted vessel at 100° C. and dimethyl-laurylamine (1.58 g; 7.4 mmol, 0.011 eq) was charged. PCl.sub.3 (29.9 g, 0.22 mol, 0.33 eq) was charged over 1.5 hours, while warming the reaction mass to 180° C. The reaction mass was then degassed under vacuum at 180° C. for 3 hours.

TABLE-US-00011 Property Data Mass yield Not determined Phosphite (.sup.31P NMR) 97.11% De-butylated phosphite (.sup.31P NMR)  2.89% Phosphates (.sup.31P NMR) n/d 1H acid (.sup.31P NMR) n/d

[0191] The reaction mass temperature was adjusted to 155° C. and run into iso-propanol (300 ml), with stirring and further isopropanol (100 ml) was added. This was cooled to 5-10° C. and held for 1 hour. After filtration the filter cake was washed with further isopropanol (3×50 ml). The product was then dried under vacuum.

TABLE-US-00012 Property Data Mass yield 73.5 g (69.8% from TBP) Phosphite (HPLC area %) 99.55%  De-butylated phosphite (HPLC area %) 0.39% Phosphates (HPLC area %) n/d 1H acid (HPLC area %) n/d TBP (HPLC area %) 0.02%

Procedure Based on DE 2490548 (Example 21—Comparative)

Method

[0192] 2-t-butyl phenol (100.17 g; 0.67 mol) was charged to a jacket flask and warmed to 50° C. with stirring. Phosphorous trichloride (25.5 g; 0.19 mol) was added dropwise over 1 hour to the stirred reaction mass. The temperature was increased to approximately 150° C. over 1 hour and held at this temperature for a total of 5 hours. Vacuum was then applied using an oil pump and 28.4 g (0.19 mol) 2-t-butyl phenol was collected. A sample of the crude reaction product had the following properties:

TABLE-US-00013 Property Data Phosphite (.sup.31P NMR) 74.3% De-butylated phosphite (.sup.31P NMR) 19.9% Phosphates (.sup.31P NMR) n/d 1H acid (.sup.31P NMR)*  1.2% *2H acid also present at 4.5%

[0193] The temperature was adjusted to ˜90° C. and isopropanol (120 g) charged in one portion.

[0194] Crystallisation started at 20° C. and was then cooled to 10° C. before filtration, washing and drying.

[0195] In order for the results to be comparable to those of the procedure of the invention (Example 22), the recrystallisation step was not carried out—the procedure of the invention involves only a single crystallisation.

[0196] A sample of the isolated reaction product had the following properties:

TABLE-US-00014 Property Data Mass yield 29.3 g (0.061 mol; 32.2% th based on PCl.sub.3) Phosphite (HPLC area %) 97.2% De-butylated phosphite (HPLC area %) 2.0% Phosphates (HPLC area %) n/d 1H acid (HPLC area %) <0.1 2-TBP (HPLC area %) 0.1

EXAMPLE 22—PROCEDURE OF THE INVENTION

Method

[0197] PCl.sub.3 (34.0 g; 0.248 mol; 0.358 eq) was charged to a thoroughly inerted vessel and heated to ˜50° C., with the condenser set at 0.4° C. N,N-di-octylamine (1.65 g; 6.83 mmol; 0.0098 eq) was charged to 2-t-butyl phenol (104.2 g; 0.694 mol; 1.00 eq). The phenol/catalyst mix was then charged sub-surface over 1 hour maintaining the temperature at 50-58° C. At the end of the addition, the temperature was raised to 140° C. over 1 hour and then vacuum applied. The HCl off gas was scrubbed as it was evolved. The temperature was then raised to 183° C. over 30 minutes and the batch held for 3 hours prior to cooling.

TABLE-US-00015 Property Data Mass yield 109.0 g (98.9% based on TBP) Phosphite (.sup.31P NMR) 94.7% De-butylated phosphite (.sup.31P NMR) 0.22% Phosphates (.sup.31P NMR) n/d 1H acid (.sup.31P NMR) 3.8%

[0198] Isopropanol (94.5 g) was charged to an inerted vessel and heated to 30° C. Crude molten TOTBP (59.1 g) was the added over ˜5 minutes maintaining the reaction mass temperature below 50° C. The reaction mass was then cooled, with stirring to 10° C. over ˜75 minutes. The reaction mass was filtered and the solids washed with cold isopropanol (50 g), before drying under vacuum.

TABLE-US-00016 Property Data Mass yield 49.8 g (84.3% recovery; 83.3% from TBP) Phosphite (HPLC area %) 99.40% De-butylated phosphite (HPLC area %) n/d Phosphates (HPLC area %) 0.40% 1H acid (HPLC area %) 0.03% TBP (HPLC area %) 0.15%

[0199] It will be seen that the process of the invention gives rise to significantly less debutylation than the prior art processes, allowing the production of tris(2-t-butylphenyl) phosphite in the absence of di(2-t-butylphenyl) monophenyl phosphite.

[0200] In addition, it will be seen that the process of the invention gives rise to a significantly greater mass yield than the prior art processes and a much higher purity TOTBP product.

[0201] Without wishing to be bound by any such theory, it is believed that adding 2-t-butyl phenol to phosphorus trichloride (i.e. a reverse addition) and carrying out the addition in the presence of a catalyst, contributes to the improvements seen over the prior art processes. In the DE 2490548 procedure, for example, phosphorus trichloride is added to 2-t-butyl phenol (i.e. a standard addition) and no catalyst is used. A recrystallisation step is required in the DE 2490548 procedure to improve the purity of the product, whereas the procedure of the invention requires only a single crystallisation.