Hydrolytically stable phosphite compositions

The present invention relates to new compositions of phosphite antioxidants that are hydrolytically stabilized with an amine. It also relates to stabilized polymers and stabilizer concentrates containing new hydrolytically stable liquid phosphite antioxidant compositions.

BACKGROUND OF THE INVENTION [0002] Organic phosphites are known in the art as secondary antioxidants for polymeric resins such as polyolefins and elastomers. As antioxidants, these phosphites are oxidized to phosphates to prevent polymer oxidation. Examples of such phosphites are disclosed in H. Zweifel (ed.) Plastics Additives Handbook, ed. 5, Hanser Publishers, Munich, 2000. A common problem with most phosphites is the tendency to undergo unfavorable hydrolysis under the influence of moisture or water, even in trace amounts, during storage or handling. Initially, phosphite hydrolysis produces the acidic protons P-OH and PH = O, which are good reducing agents that react directly with oxygen or hydroperoxides. However, if the hydrolysis extends beyond this initial stage, stronger acids are produced that greatly accelerate the formation of oxidized products. In addition, other acids from impurities arising from polymerization catalyst residues may further catalyze phosphite hydrolysis. These oxidized products reduce the overall ability of the phosphite stabilizer to act as an antioxidant. As a result of exposure to water, hydrolyzed phosphites become a lumpy, viscous mass that corrodes production equipment.

[0003] Conventionally, to prevent hydrolysis, manufacturers are looking for phosphite that hydrolyzes slowly and adds various hydrolysis stabilizers to the phosphite. US Patent 3,787,537 describes an ester, triisopropylphenyl phosphite, which is slowly hydrolyzed in combination with a heavy amine to further increase hydrolysis stability.

[0004] Stabilizers, trialkylaryl phosphites containing bonded alkyl groups in ortho and para positions are resistant to hydrolysis due to steric hindrance. One of the most widely used phosphite is tris (2,4-di-t-butylphenyl) phosphite, which is commercially available under the trade name Alkanox ™ 240, Irgafos ™ 168 or Doverphos ™ S-480. This phosphite is solid and is commercially available without a hydrolysis stabilizer.

[0005] Other stabilizers, trialkylaryl phosphites, such as the commonly used tris (p-nonylphenyl) phosphite (TNPP), are susceptible to hydrolysis. TNPP is liquid at room temperature. Commercially available TNPP grades, such as Weston ™ 399 (Chemtura Corporation), typically contain up to 1 wt. triethanolamine or triisopropanolamine, which acts as a hydrolysis stabilizer.

[0006] US Patent 5561181 discloses a highly ortho-substituted TNPP that is more hydrolytically stable than para-substituted TNPP.

[0007] EP0167969 discloses a phosphite that is hydrolytically stabilized by a long chain aliphatic amine such as cocoalkyldiethanolamine. EP0143464 discloses pentaerythritol diphosphite which is hydrolytically stabilized by a long chain aliphatic amine such as octyldecyldiethanolamine.

[0008] However, there is a need to replace TNPP due to concerns arising from its attributed nonylphenol-related estrogen, which is used in the synthesis of TNPP.

[0009] Thus, there is a need for safe and effective liquid phosphite compositions for use as secondary antioxidants in polymers that can be hydrolytically stabilized.

[0010] In addition, there is a need for amine compounds that are suitable for the hydrolytic stabilization of a wider range of phosphite antioxidants.

SUMMARY OF THE INVENTION [0011] In a first aspect, the invention relates to a composition comprising: (a) a liquid phosphite composition and (b) an amine of formula:

<img file="PL2459575T3_D0001.tif" />

wherein x is 1, 2 or 3; R1 is selected from the group consisting of hydrogen and straight or branched C1-C6 alkyl, and R2 is selected from the group consisting of straight or branched C1-C30 alkyl. Preferably, x is 1 or 2. The amine may be present in an amount of from 0.01 to 3% by weight, based on the total weight of the composition. The liquid phosphite composition contains at least two different phosphites from the following: (i) tris (dialkylaryl) phosphite, (ii) tris (monoalkylaryl) phosphite, (iii) bis (dialkylaryl) monoalkylaryl phosphite, and (iv) bisl (monoalkyl) phospharyl ; and is liquid at ambient conditions (25 ° C, 1.01325 bar).

[0013] In a second aspect, the present invention relates to a composition comprising: (a) a liquid phosphite composition and (b) bis (2-alkanol) mono-C8-C20-alkylamine. The liquid phosphite composition contains at least two different phosphites from the following: (i) tris (dialkylaryl) phosphite, (ii) tris (monoalkylaryl) phosphite, (iii) bis (dialkylaryl) monoalkylaryl phosphite, and (iv) bisl (monoalkyl) phospharyl ; and is liquid at ambient conditions.

[0014] In a third aspect, the present invention is directed to a method of hydrolytic stabilization of a secondary antioxidant comprising adding an amine to the secondary antioxidant in an amount of from 0.01 to 3 wt. Amina has a formula

<img file="PL2459575T3_D0002.tif" />

r₂d-χ χ (η where x is 1, 2 or 3; R1 is selected from the group consisting of hydrogen and straight or branched C1-C6 alkyl, and R2 is selected from the group consisting of straight or branched C1-C30 alkyl. Preferably, x is 1 or 2. The liquid phosphite composition contains at least two different phosphites from the following: (i) tris (dialkylaryl) phosphite, (ii) tris (monoalkylaryl) phosphite, (iii) bis (dialkylaryl) monoalkylaryl phosphite, and (iv) bisl (monoalkyl) phospharyl ; it is liquid under ambient conditions.

EP 2 459 575 B1

DETAILED DESCRIPTION OF THE INVENTION [0015] The present invention relates to stabilized phosphite compositions comprising one or more phosphite compounds and one or more amine compounds that are capable of hydrolytically stabilizing a phosphite compound. The phosphite compounds of the present invention are stabilized with one or more amines, e.g. one or more alkanolamines, preferably one or more alkan-2-olamines, i.e. those in which the hydroxyl group or groups are at the carbon atom β. The amine compound may contain a primary, secondary or tertiary nitrogen atom. In one embodiment, the nitrogen is substituted with at least one alkanol group and optionally one or more alkyl groups that preferably facilitate the dispersion or dissolution of the amino compound in a phosphite compound or a mixture of phosphite compounds.

[0016] Phosphites and phosphonites are well known and include, for example, triphenyl phosphites, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (nonylphenyl) phosphites, trilauryl phosphites, trioctadecyl phosphites, di-toluaryl phosphoryl phosphite butylphenyl), diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonine; specific phosphite compounds include, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, 2,4-di-tert-phosphite diphosphite di-tert-butylphenyl) pentaerythritol, tristearyl sorbitol triphosphite, tris (dipropylene glycol) phosphite and tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphite. Preferably, the phosphite is a liquid phosphite composition.

[0017] In one embodiment, the phosphite is a liquid ester, tris (mono-alkyl) phenyl phosphite or a liquid mixture of liquid esters, tris (monoalkyl) phenyl phosphite, as described in US Patent No. 7,468410, the entire contents and disclosures of which are incorporated herein principle of reference. For example, the phosphite is tris (monoalkylphenyl) phosphite or a liquid mixture of two or more tris (monoalkylphenyl) phosphites, for example tris (monoalkylphenyl) phosphite, in which the alkyl substituent is a straight or branched chain alkyl containing from 1 to 20 carbon atoms, for example from 1 to 8 carbon atoms. In one particular embodiment, the phosphite includes one or more of tris (3-t-butylphenyl) phosphite, tris (2-sec-butylphenyl) phosphite and tris (4-sec-butylphenyl) phosphite. In one embodiment, the liquid mixture comprises various phosphites, one of which is tris (3-t-butylphenyl) phosphite, tris (2-sec-butylphenyl) phosphite or tris (4-sec-butylphenyl) phosphite, and one of the others is tris phosphite (3-t-butylphenyl), tris (2-sec-butylphenyl) phosphite, tris (4-sec-butylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris (4-t-butylphenyl) phosphite or tris phosphite (2,4-di-tbutylofenylu).

Amine stabilizers [0018] In one aspect, the amine stabilizer has formula I:

<img file="PL2459575T3_D0003.tif" />

Wherein x is 1, 2 or 3, preferably x is 1 or 2; R1 is selected from the group consisting of hydrogen and straight or branched C1-C6 alkyl, and R2 is selected from the group consisting of straight or branched C1-C30 alkyl. Preferably R1 is selected from the group consisting of straight or branched C1-C4 alkyl, e.g. methyl or ethyl. Preferably R2 is selected from the group consisting of straight or branched C5-C20 alkyl, e.g. straight or branched C10-C20 alkyl or straight or branched C12-C18 alkyl. In one embodiment, x is 1 and R2 is straight or branched C5-C20 alkyl, e.g. C12-C18 alkyl. In one embodiment, x is 2 and R 2 is straight or branched C 10 -C 20 alkyl, e.g. C 12 -C 18 alkyl.

[0019] Thus, in a particularly preferred aspect, the amine has formula (II):

<img file="PL2459575T3_D0004.tif" />

wherein R1 is independently selected from the group consisting of hydrogen and straight or branched C1-C6 alkyl, preferably methyl, and R2 includes a straight or branched C8-C20 alkyl group, e.g. a straight or branched C10-C18 alkyl group or a straight or branched group C12-C18 alkyl.

[0020] In one embodiment, the amine comprises bis (2-alkanol) mono-C8-C20-alkylamine. Bis (2-alkanol) mono-C8-C20-alkylamine is selected from the group consisting of, for example: octyl-bis (2-ethanol) amine, nonyl-bis (2-ethanol) amine, decyl-bis (2-ethanol) amine, undecyl-bis (2-ethanol) amine, dodecyl-bis (2-ethanol) amine, tridecyl-bis (2-ethanol) amine, tetradecyl-bis (2-ethanol) amine, pentadecyl-bis (2-ethanol) amine, hexadecyl-bis (2-ethanol) amine, heptadecyl-bis (2-ethanol) amine, octadecyl-bis (2-ethanol) amine, octyl-bis (2-propanol) amine, nonyl-bis (2-propanol) amine, decyl-bis (2-propanol) amine, undecyl-bis (2-propanol) amine, dodecyl- bis (2-propanol) amine, tridecyl-bis (2-propanol) amine, tetradecyl-bis (2-propanol) amine, pentadecyl-bis (2-propanol) amine, hexadecyl-bis (2-propanol) amine, heptadecyl-bis (2-propanol) amine, octadecyl bis (2-propanol) amine and their isomers. Suitable commercially available amines include Armostat ™ 300 and Armostat 1800.

[0021] In another aspect, the amine has formula (III):

<img file="PL2459575T3_D0005.tif" />

wherein each R1 is independently selected from the group consisting of hydrogen, straight or branched C1-C6 alkyl. In preferred aspects, R1 is a straight or branched C1-C3 alkyl group, preferably methyl.

[0022] Exemplary amine compounds of formula (III) include compounds selected from the group consisting of triethanolamine, triisopropanolamine (TIPA), tributanolamine and tripentanolamine.

[0023] Other exemplary amines suitable for stabilizing the phosphite composition include diethanolamine, diisopropanolamine and tetraisopropanolethylenediamine.

[0024] The amount of stabilizer needed for effective stabilization of the phosphite composition may vary widely depending on the number of hydroxyl groups in each amine molecule, compatibility, e.g. miscibility, amine with the phosphite composition, and specific phosphite compounds incorporated in the phosphite composition that has be stabilized. In some exemplary embodiments, the stabilized phosphite composition comprises one or more amines in an amount in the range of from 0.01 to 3 wt.%, E.g., from 0.1 to 1.5 wt.%. or from 0.2 to 0.8% by weight, based on the total weight of the stabilized phosphite composition. In one embodiment, the stabilized phosphite composition comprises 0.7 wt. one or more amines.

[0025] It should be noted that the combination of certain phosphites with certain alkanolamines results in a turbid mixture. For example, triisopropanolamine is effective in the hydrolytic stabilization of phosphites, but does not always result in a clear mixture. On the other hand, as can be seen from the attached examples, octadecylbis (2-hydroxyethyl) amine will provide the same stability as triisopropanol, but will generally not cause turbidity.

Liquid phosphite composition [0026] Although almost any phosphite may be present in the present phosphite composition, for example those discussed above, in various embodiments, the liquid phosphite composition that is amine stabilized contains at least two different phosphites. Suitable liquid phosphite compositions are described, for example, in US Application No. 11/787531, entitled LIQUID PHOSPHITE BLENDS AS STABILIZERS.

[0027] In some preferred embodiments, the phosphite composition comprises at least two different phosphites of formula V:

R3CN --OR4 Ρ

AND

OR₅ , -γ) wherein R3, R4 and R5 are independently selected alkylated aryl groups, wherein the liquid phosphite composition is liquid at ambient conditions. By "ambient conditions" is meant room temperature, e.g. 25 ° C, and a pressure of 1 atmosphere.

[0028] The aryl residue R3, R4 and R5 is preferably an aromatic residue containing from 6 to 18 carbon atoms, e.g., phenyl, naphthyl, phenanthryl, anthracyl, biphenyl, terphenyl, o-cresyl, m-cresyl, p-cresyl and the like similar, preferably phenyl. Each aromatic residue is substituted with at least one C 1 -C 18 alkyl group, e.g. C 4 -C 10 alkyl or C 4 -C 5 alkyl. Preferably, no aromatic residues are substituted with any C9 alkyl groups. Aromatic residues can be mono-, di- or tri-substituted in ortho and / or para positions, but in many of these mixtures, the phosphites themselves are not exclusively mono-substituted, are not only di-substituted and are not only tri-substituted.

[0029] For example, the invention relates to a stabilized liquid phosphite composition comprising a liquid phosphite composition and an amine compound, wherein the liquid phosphite composition comprises at least

Two of the following: tris (dialkylaryl) phosphite, tris (monoalkylaryl) phosphite, bis (dialkylaryl) monoalkylaryl phosphite, and bis (monoalkylaryl) dialkylaryl phosphite, and the ambient phosphite composition. Thus, the liquid phosphite composition contains at least one phosphite, which contains at least one aromatic residue that is multiple substituted, such as bis (dialkylaryl) monoalkylaryl phosphite, bis (monoalkylaryl) dialkylaryl phosphite or tris (dialkylaryl) phosphite. The liquid phosphite composition preferably contains at least one phosphite compound in which each aryl residue is exclusively monosubstituted, e.g., tris (monoalkylaryl) phosphite. The alkyl group in the alkylaryl phosphite compounds preferably includes a C 3 -C 5 alkyl group, e.g. a C 4 -C 5 alkyl group, more preferably t-butyl and / or t-amyl, and the aryl group preferably includes phenyl or cresyl, e.g. o-, m- and / or p-cresyl.

More generally, the alkyl substituent (s) of the aryl residues of formula (V) are selected from straight or branched chain C 1 -C 18 alkyl, e.g. C 1 -C 8 alkyl, C 4 -C 6 alkyl or C 4 -C 5 alkyl, preferably C 4 alkyl or C5 alkyl. In a preferred embodiment, the alkyl substituent is not C8-C10 alkyl, it is not, e.g., C9 alkyl. The alkyl substituent may include, for example, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl (although less preferred), decyl, undecyl, dodecyl, tridecyl, t etradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and their isomers . Most preferably, the alkyl group (alkyl groups) is selected from butyl (especially sec-butyl and / or tert-butyl) and an amyl group (especially sec-amyl, tert-amyl and / or isoamyl). As indicated above, in one embodiment, the alkyl residues do not include nonyl, which means that the phosphite composition preferably contains less than 50 wppm, e.g., less than 10 wppm or less than 5 wppm, nonyl substituted aryl phosphite compounds, and most preferably no detectable nonyl substituted compounds arylofosforynowych. In addition, the phosphite composition preferably comprises less than 50 wppm, e.g. less than 10 wppm or less than 5 wppm, of nonylphenol. Most preferably the phosphite composition does not contain detectable nonylphenol.

[0031] In one embodiment, R3, R4, and R5 are, independently selected, alkylated aryl groups of formula (VI):

<img file="PL2459575T3_D0006.tif" />

wherein R6, R7, and R8 are independently selected from the group consisting of hydrogen and straight or branched C1-C8 alkyl, e.g. methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl and their isomers, e.g. isopropyl, sec-butyl, tert-butyl, tert-amyl, sec-amyl etc., wherein at least one of R6, R7 and R8 is not hydrogen.

[0032] In one embodiment, R6 and R7 are independently selected from the group consisting of methyl, ethyl, propyl, butyl, amyl, hexyl and their isomers, and R8 is hydrogen. In another embodiment, R6 and R8 are hydrogen and R7 is independently selected from the group consisting of methyl, ethyl, propyl, butyl, amyl, hexyl and their isomers. In one aspect of these embodiments, at least one of R6, R7 and R8 is C4 or C5 alkyl, often tert-butyl or tert-amyl.

[0033] In one embodiment, R3, R4, and R5 are independently selected alkylated aryl groups of formula (VII):

EP 2 459 575 B1

<img file="PL2459575T3_D0007.tif" />

wherein R6, R7, and R8 are as defined above and R9 is hydrogen or methyl, one of R6, R7, R8 and R9 being methyl and at least two of R6, R7, R8 and R9 are not hydrogen. Such phosphites can be prepared, for example, by reacting one or more alkylated cresol compounds, e.g. one or more alkylated ortho-, meta- and / or para-cresols, with PCl3.

In some preferred embodiments, the liquid phosphite composition comprises at least two phosphites selected from the group consisting of tris (4-t-butylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris (2,4-di-t phosphite) -butylphenyl), bis (4-t-butylphenyl) -2,4-di-t-butylphenyl phosphite, bis (2,4-di-t-butylphenyl) -4-t-butylphenyl phosphite, bis (2-t-phosphite -butylphenyl) -2,4-di-t-butylphenyl, bis (2,4-di-t-butylphenyl) -2-t-butylphenyl phosphite, tris (4-t-amylphenyl) phosphite, tris (2-t-amylphenyl) phosphite, tris (2,4-di-t-amylphenyl) phosphite, bis (4-t-amylphenyl) -2,4-di-t-amylphenyl phosphite, bis (2,4-phosphite) -di-t-amylphenyl) -4-tamylphenyl, bis (2-t-amylphenyl) -2,4-di-t-amylphenyl phosphite and bis (2,4-di-t-amylphenyl) -2-t- amylofenylu. In one embodiment, the phosphite composition does not contain only phosphites that would form a solid composition when incorporated into the composition. An example of a phosphite that would produce a solid composition is the reaction product of 2,4-di-t-butylphenol and 2,4-di-t-amylphenol with phosphorus trioxide, as described in US Patent 5,254,709.

In many embodiments, the phosphite composition has a total phosphorus content that is greater than or equal to the TNPP content, e.g. at least 4.5 mol%, e.g. at least 4.8 mol% or at least 5.1 mol% . Regarding ranges, the total phosphorus content of the phosphite composition ranges from 4.5 to 10.0 mol%, e.g. from 4.8 to 8.0 mol%. or from 5.1 to 6.0 mole%, based on the sum of moles of all phosphorus-containing compounds in the phosphite composition.

[0036] As indicated above, the phosphite composition often contains at least two of the following: tris (dialkylaryl) phosphite, tris (monoalkylaryl) phosphite, bis (dialkylaryl) monoalkylaryl phosphite, and bis (monoalkylaryl) dialkylaryl phosphite. ambient conditions. The relative amounts of the individual phosphite components contained in the phosphite composition may vary slightly as long as the phosphite composition itself is liquid at ambient conditions. In these embodiments, the phosphite composition contains at least two of these compounds, at least three of these compounds, or all four of these compounds, in an amount greater than 80 wt.%, 90 wt. or 95 wt. based on the total weight of all phosphite compounds in the phosphite composition. Of course, a smaller amount of other compounds, phosphite or non-phosphite, e.g. one or more of tris (2-tert-amylphenyl) phosphite, bis (2-tert-amylphenyl) -2,4-di-phosphite may be present in these compositions. tert-amylphenyl, bis (2,4-di-tert-amylphenyl) -2-tert-amylphenyl phosphite and the like.

[0037] The relative amounts of the individual phosphite components contained in the liquid phosphite composition may vary slightly as long as the phosphite composition is liquid at ambient conditions. For example, one particular phosphite composition includes tris (monoalkylaryl) phosphite, e.g., tris phosphite (47

T-amylphenyl) in an amount of 20 to 70 wt.%, E.g. 15 to 55 wt. or from 37 to 54% by weight and bis (monoalkylaryl) dialkylaryl phosphite, e.g. bis (4-t-amyl-phenyl) -2,4-di-t-amyl-phenyl phosphite, in an amount from 15 to 60% by weight, e.g. from 31 to 50 wt. or from 34 to 45% by weight Optionally, the phosphite composition further comprises tris (dialkylaryl) phosphite and / or bis (dialkylaryl) monoaryl phosphite. If present, tris (dialkylaryl) phosphite, e.g. tris (2,4-di-tert-amylphenyl) phosphite is preferably present in an amount of from 0.1 to 20% by weight, e.g. from 0.3 to 5% by weight or from 0.5 to 1% by weight If present, bis (dialkylaryl) monoaryl phosphite, e.g. bis (2,4-di-tert-amylphenyl) -4-t-amylphenyl, is preferably present in an amount of from 2 to 20% by weight, e.g. 4 to 20 wt. or from 5 to 10% by weight Unless otherwise indicated, the weight percent (wt.%) Is based on the total weight of the phosphite composition.

[0038] In these embodiments, in the phosphite composition, the weight ratio of tris (monoalkylaryl) phosphites to a combination of bis (monoalkylaryl) dialkylaryl phosphites, bis (dialkylaryl) monoalkylaryl phosphites and tris (dialkylaryl) phosphites is often from 1 to: from 2: 5 to 3: 2 or from 3: 5 to 6: 5. Optionally, in the phosphite composition, the weight ratio of bis (monoalkylaryl) dialkylaryl phosphite to the combination of tris (monoalkylaryl) phosphite, bis (dialkylaryl) monoalkylaryl phosphite and tris (dialkylaryl) phosphite is from 1: 6 to 3: 2, e.g. 1: 1 or 1: 2 to 2: 3. Optionally, in the phosphite composition, the weight ratio of bis (dialkylaryl) monoalkylaryl phosphite to the combination of tris (monoalkylaryl) phosphite, bis (monoalkylaryl) dialkylaryl phosphite and tris (dialkylaryl) phosphite is from 1:50 to 2: 5, e.g. 1: 5 or 1:20 to 1: 9 or possibly less than 0.2: 1, less than 0.1: 1, less than 0.05: 1 or less than 0.02: 1.

[0039] Often, the liquid phosphite composition contains at least two of the following: tris (di-C3-C5 alkylaryl) phosphite, tris (C3-C5 alkylaryl) phosphite, bis (di-C3-C5 alkylaryl) C3-C5 alkylaryl phosphite and phosphite bis (C3-C5 alkylaryl) di-C3-C5 alkylaryl. Preferably, the composition contains each of these phosphites in the following amounts: 1-5 wt. tris (di-C3-C5 alkylaryl) phosphite, 10-70 wt. tris (C3-C5 alkylaryl) phosphite, 1-35 wt. bis (di-C3-C5 alkylaryl) C3-C5 alkylaryl phosphite and 5-70 wt. bis (C3-C5 alkylaryl) di-C3-C5 alkylaryl phosphite.

[0040] Liquid mixtures of phosphites can be characterized on the basis of how aryl residues, e.g. phenyl residues, are substituted, e.g. substituted with alkyl (e.g. t-butyl or t-amyl) as a whole. For example, in one embodiment, most aryl residues are monosubstituted in the para position, e.g. at least 50%, at least 70%, or at least 90% are monosubstituted in the para position, optionally from 50 to 95%, e.g. from 55 to 90 or 60 to 85% are monosubstituted in the para- position, relative to the number of aryl residues in the phosphite composition. In other embodiments, some of the aryl residues are disubstituted, e.g., ortho- and para-disubstituted, at least in part, e.g. at least 10% of the aryl residues are ortho- and para-disubstituted, e.g. at least 20% is ortho- and para-disubstituted or at least 50% ortho- and para-is disubstituted, optionally from 5 to 50% ortho and para- is disubstituted, e.g. from 10 to 45% is ortho and para -disubstituted, or from 15 to 40% are ortho- and para-disubstituted, relative to the total number of aryl residues in the phosphite composition. In other embodiments, the ratio of monoalkylaryl residues to dialkylaryl residues ranges from 5: 1 to 1: 1, e.g. from 4: 1 to 1: 1 or from 3.5: 1 to 2: 1.

[0041] In many embodiments in which liquid phosphite compositions include phosphite compounds containing aryl residues that are monoalkylated and dialkylated, there are few, if any, aryl residues. For example, tri-substituted aryl residues are less than 3 wt.%, E.g., less than 2 wt.% or less than 1 wt. Similarly, in these mixtures, there are very few aryl residues, if any,

Monosubstituted in ortho position. Preferably, aryl residues are monosubstituted in ortho position, if any, in an amount of less than 3 wt%, e.g. less than 2 wt% or less than 1 wt.

Other Stabilizers [0042] As discussed above, a stabilizing amount or effective amount of a hydrolytically stabilized phosphite composition of the invention can be used as a secondary antioxidant for various types of polymers. In the present specification, "stabilizing amount" and "effective amount" is understood to mean a situation in which a polymer composition comprising a hydrolytically stabilized phosphite composition of the invention exhibits improved stability of any of its physical properties or color compared to an analogous polymer composition that does not contain hydrolytically stabilized phosphite composition. Examples of improved stability include improved stabilization in, for example, molecular weight loss, color loss and the like, as a result of, for example, melt processing, atmospheric aging and / or long-term exposure to open air, heat, light and / or other factors. In one example, improved stability is obtained based on one or both of the following criteria - less change in the original color and mass melt flow rate of the polymer, or additional weathering resistance - determined, for example, by the yellowness index (YI) or by resistance to yellowing and color change compared to compositions without the addition of a stabilizer.

[0043] The additives and stabilizers described herein are preferably present in an amount effective to improve the stability of the composition. When one of the above-mentioned hydrolytically stabilized phosphite compositions is used, the composition is generally present in an amount of from about 0.001 to about 5% by weight, e.g. from about 0.0025 to about 2% by weight. or from about 0.005 to about 1% by weight, based on the total weight of the polymer comprising the weight of the phosphite composition, amines and any other stabilizers or additives. The hydrolytically stabilized phosphite compositions of the present invention stabilize the resins, especially when processed at high temperature, with a relatively small change in the melt index and / or color, even after repeated extrusion.

[0044] The invention further relates to stabilized thermoplastics comprising a base polymer (e.g. a polymer resin) and any of the above-mentioned hydrolytically stabilized phosphite compositions of the invention. The polymer may be a polyolefin and the phosphite may be a liquid phosphite composition in combination with a co-stabilizer, for example sterically hindered phenolic compounds, aromatic amines, hydroxylamines, lactones and thioethers. Thus, a thermoplastic that is stabilized using the hydrolytically stabilized phosphite according to the present invention may optionally contain one or more additional stabilizers or mixtures of stabilizers selected from the group consisting of phenolic antioxidants, sterically hindered amine stabilizers (HALS), ultraviolet light absorbers, phosphites, phosphites , salts with alkali metals of fatty acids, hydrotalcites, metal oxides, epoxidized soybean oils, hydroxylamines, tertiary amine oxides, lactones, thermal reaction products of tertiary amine oxides and thiosynergics.

[0045] Table 3 shows the percentage of each component in the stabilizing mixture relative to the total weight of the polymer or polymer resin in one embodiment.

EP 2 459 575 B1

<td colspan="3">Table 3</td>

<td>Ingredient</td><td>Range</td><td>Favorable range</td>

<td>Liquid phosphite compositions</td><td>0.001-5.0 wt.</td><td>0.005-1.0 wt.</td>

<td>Primary antioxidant</td><td>0-5.0 wt.</td><td>0.005-2.0 wt.</td>

<td>UV or light stabilizers</td><td>0-3.0 wt.</td><td>0.001-2.0 wt.</td>

<td>Metal deactivators</td><td>0-3.0 wt.</td><td>0.001-2.0 wt.</td>

<td>Other secondary antioxidants</td><td>0-3.0 wt.</td><td>0.001-2.0 wt.</td>

<td>Peroxide scavengers</td><td>0-3.0 wt.</td><td>0.001-2.0 wt.</td>

<td>Polyamide stabilizers</td><td>0-3.0 wt.</td><td>0.001-2.0 wt.</td>

<td>Alkalic stabilizers</td><td>0-3.0 wt.</td><td>0.001-2.0 wt.</td>

<td colspan="2">Nucleating agents or clarifiers 0-3.0 wt.</td><td>0.001-2.0 wt.</td>

<td>Aminoksypropionian</td><td>0-3.0 wt.</td><td>0.001-2.0 wt.</td>

[0046] Primary antioxidants include:

(i) Alkylated monophenols, for example: 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,

2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl- 4-methylphenol, 2,6-bis- (α-methylbenzyl) -4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6 , -tricyclohexylphenol and 2,6-di-tert-butyl-4-methoxymethylphenol. Commercially ankylated monophenols include Linovox ™ 624 and Naugard ™ 431. Commercially available other phenols such as BHEB.

(ii) Alkylated hydroquinones, e.g. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,

2,5-di-tert-amylhydroquinone and 2,6-diphenyl-4-octadecyloxyphenol. Commercially available alkylated hydroquinones include Lowinox AH25 manufactured by Chemtura.

(iii) Hydroxylated thiodiphenyl ethers, e.g. 2,2'-thio-bis- (6-tert-butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 4,4'-thio -bis- (6-tert-butyl-3-methylphenol) and 4,4'-thio-bis- (6-tert-butyl-2-methylphenol). Commercially available hydroxylated thiodiphenyl ethers include Lowinox TBM6 and Lowinox TBP6.

(iv) Alkylidene-bisphenols, e.g. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis- (615 fe / f-butyl-4-ethylphenol ), 2,2'-methylene-bis- (4-methyl-6- (α-methylcyclohexyl) phenol), 2,2'-methylene-bis (4-methyl-6-cyclohexylphenol), 2,2'-methylene -bis- (6-nonyl-4-methylphenol), 2,2'-methylene-bis- (6-nonyl4-methylphenol), 2,2'-methylene-bis- (6- (α-methylbenzyl) -4- nonylphenol), 2,2'-methylene-bis- (6- (alpha, alphadimethylbenzyl) -4-nonyl-phenol), 2,2'-methylene-bis- (4,6-di-te / t-butylphenol) . 2,2'-ethylidene-bis- (6-te / t-butyl-4-isobutylphenol), 4,4'-methylene-bis- (2,6-di-te / t-butylphenol), 4,4'-methylene -bis- (6-te / t-butyl-2-methylphenol), 1,1-bis- (5-te / t-butyl-4-hydroxy-2-methylphenol) butane, 1,1-bis (2 -methyl-4-hydroxy-5-te / t-butylphenyl) butane, 2,2'-isobutylidene-bis (4,6-dimethylphenol), 2,6-di- (3-te / t-butyl-5- methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris- (5-te / t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis- (5-te / t-butyl-4-hydroxy-2-methylphenyl) -3-dodecyl-mercaptobutane, bis- (3,3-bis- (3'-te / t-butyl-4'- ethylene glycol hydroxyphenyl) butyrate), di- (3-te / t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene and di- (225 (3'-te / t-butyl-2'-hydroxy-5) terephthalate 'methylbenzyl) -6-te / t-butyl-4-methylphenyl). Commercially available alkyliden 10

Bisphenols include Lowinox 22M46, Lowinox WSP, Lowinox 44B25, Naugard 536, Naugawhite ™ and Lowinox 22IB46.

(v) Benzyl compounds, e.g. 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, bis- (3,5-di- tert-butyl-4-hydroxybenzyl), 3,5-di-tert-butyl-4-hydroxybenzylomercaptoacetate, isooctyl, bis- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate, isocyanurate 1,3 , 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione , Dioctadecyl, 5-ditert-butyl-4-hydroxybenzylphosphonate, monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate calcium salt, 1,3,5-tris- (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate. Commercially available benzyl compounds include Anox ™ IC-14, Anox 330 and Lowinox 1790.

(vi) Acylaminophenols, e.g. 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, 2,4-bis-octylmercapto-6- (3,5-tert-butyl-4-hydroxyanilino) -s-triazine and n- ( Octyl 3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

(vii) E- (3,5-di-fe / Y-butyl-4-hydroxyphenol) propionic acid esters with monohydric or polyhydric alcohols, e.g. methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol , neopentyl glycol, tris-hydroxyethyl isocyanurate, thiodiethylene glycol and dihydroxyethyl oxalic acid diamide. Such phenols also include tetrakis [methylene {3,5-di-te / t-butyl-4-hydroxycinnamate}] methane. Commercially available esters include Anox 20, Anox 1315, Lowinox GP45, Naugalube 38, Naugalube 531, Anox PP18, Naugard PS48 and Naugard XL-1.

(viii) E- (5-fe / f-butyl-4-hydroxy-3-methylphenyl) propionic acid thioesters with monohydric or polyhydric alcohols, for example methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol neopentyl glycol, tris-hydroxyethyl isocyanurate, thiodiethylene glycol and dihydroxyethyl oxalic acid diamide. Commercially available thioesters include Naugalube ™ 15 and Anox 70.

(ix) β- (3,5-di-ίe / f-butyl-4-hydroxyphenol) propionic acid amides, e.g. N, N'-di- (3,5-di-fe / f-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-di- (3,5-di-te / t-butyl-4-hydroxyphenylpropionyl) trimethyldiamine, N, N'-di- (3,5-di-te / t-butyl-4- hydroxyphenylpropionyl) hydrazine, N, N'hexamethylene-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide and 1,2-bis (3,5-di-te / t-butyl-4 -hydroksyhydrocynamoilo) hydrazine. Commercially available amides include Lowinox HD98 and Lowinox MD24.

(x) Other phenolic antioxidants include the following phenols. Polymeric phenols, such as the reaction product of 4-methylphenol with dicyclopentadiene and isobutylene, commercially available as Lowinox CP. Alkylidene poly phenols such as 1,3-tris (3-methyl-4-hydroxyl-5-t-butylphenyl) butane (Lowinox CA22). Thiophenols such as 2,6-di / t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol (Irganox ™ 565), 4.6 bis (octylthiomethyl) o-cresol (Irganox 1520); 4,6-bis (dodecylthiomethyl) o-cresol (Irganox 1726). Hydroxylamines such as bis (octadecyl) hydroxylamine (Irgastab ™ FS 042).

Phenol esters include bis [3,3-bis (4-hydroxy-3-t / butylphenyl) butanoic acid] and glycol ester (Hostanox ™ 03). Still other phenols include 2- [1- (2-hydroxy-3,5-di-te / t-pentylphenyl) ethyl] 4,6-di-te / t-pentylphenyl acrylate (Sumilizer GS). In one embodiment, the stabilizing composition comprises one phenolic compound selected from the group consisting of tetrakismethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane (Anox 20), 1,3,5-tris isocyanurate (3,5- di-t-butyl-4-hydroxybenzyl) (Anox IC-14),

1,3,5-tris (4th / t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Lowinox

EP 2 459 575 B1

1790), octyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Anox PP18), bis (octadecyl) hydroxylamine (Irgastab FS-042), 1,3,5-trimethyl-2, 4,6-tris (3,5-di-tert-4-hydroxybenzyl) benzene (Anox 330),

2,6-bis (α-methylbenzyl) -4-methylphenol (Naugalube 431), 3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenopropanoic acid (Anox 1315), 2,6-di-t-butyl -4-ethylphenol (BHEB) and mixtures thereof, and the liquid phosphite composition as defined herein.

[0047] Hydrolytically stabilized phosphites and / or subsequent stabilized polymer resin compositions also optionally include one or more UV absorbers and / or photostabilizers, such as the following:

(i) 2- (2'-hydroxyphenyl) benzotriazoles, e.g. 5'-methyl-, 3'5'-di-tert-butyl-, 3'5'-di-tert-amyl-, 5'tert-butyl -, 5'-tert-amyl-, 5 '- (1,1,3,3-tetramethylbutyl) -, 5-chloro-3', 5'-di-tert-butyl-, 5-chloro-3'- tert-butyl-5'-methyl-, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy-, 3 ', 5'-di-tert-amyl-3', 5'-bis - (a, a-dimethylbenzyl) derivatives. Commercially available 2- (2'-hydroxyphenyl) benzotriazoles include Lowilite ™ 26, Lowilite 27, Lowilite 28, Lowilite 29, Lowilite 35, Lowilite 55 and Lowilite 234.

(ii) 2-hydroxybenzophenones, e.g. 4-hydroxy, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 2,4-dihydroxy-, 4.2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives. Exemplary 2-hydroxybenzophenones include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-ethoxybenzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-propoxybenzophenone. Commercially available 2- (2'-hydroxyphenyl) benzotriazoles include Lowilite 20, Lowilite 22, Lowilite 20S and Lowilite 24.

(iii) Estersubstituted and unsubstituted benzoic acids, e.g. phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis- (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl 2,4-di-tert-butylphenyl and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate -hydroxybenzoate.

(iv) UV absorbers and photostabilizers can also include acrylates, e.g. ethyl or α-cyano-e, e-diphenylacrylic acid, iso-octyl ester, α-carbomethoxycinnamic acid methyl ester, methyl ester or α-cyano-β-methyl butyl ester -p-methoxycinnamic acid, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester and N- (β-carbomethoxy-β-cyano-vinyl) -2-methylindoline.

(v) Nickel compounds are also suitable UV absorbers and photostabilizers. Exemplary compounds include nickel complexes with 2,2'-thio-bis (4- (1,1,1,3-tetramethylbutyl) phenol), e.g. 1: 1 or 1: 2 complexes, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl diethanolamine, nickel dibutyl dithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzyl phosphonic acid monoalkyl esters, such as ethyl ester nickel complexes with ketoximes such as 2-hydroxy-4-methylphenyloundecylketoxime, nickel complexes with 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands. Commercially available nickel compounds include Lowilite Q84 (2,2'-thio-bis (4-tert-octylphenolane)) - n-butylaminonickel (II).

(Vi) sterically hindered amines can be used as UV absorbers and photostabilizers. Hindered amines, e.g. bis- (2,2,6,6-tetramethylpiperidyl) sebacate, bis- (1,2,2,6,6-pentamethylpiperidyl) sebacate, bis ester (1,2,2,6, 6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid, 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensation product, N, N 'condensation product - (2,2,6,6-tetramethylpiperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris- (2,2,6,6-tetramethylpiperidyl) nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetrabycarbonate, 1.1 ' (1,2-ethanediyl) bis (3,3,5,5-tetrametylopiperazynon). These amines include sterically hindered hydroxylamines such as di (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 1-hydroxy 2,2,6,6-tetramethyl-4-benzoxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4- (3,5-di-tert-butyl-4-hydroxyhydrocinoyloxy) piperidine and N- (1-hydroxy-2,2,6,6-tetramethyl-piperidine) 4-yl) -epsilonkaprolaktam. Commercially hindered amines include Lowilite 19, Lowilite 62, Lowilite 77, Lowilite 92 and Lowilite 94.

(vii) Oxalic acid diamides, e.g. 4,4'-dioctyloxyoxanilide, 2,2'-di-octyloxy-5 ', 5'-di-tert-butyloxanilide, 2,2'-di-dodecyloxy-5', 5'di -tert-butyloxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy -2'-ethyl-5,4-di-tert-butyloxyanilide and mixtures of o- and p-methoxy- as well as o- and p-ethoxy disubstituted oxanilides.

[0048] The polymer resins and phosphite compositions of the invention may also contain one or more further additives, including, for example, one or more of the following:

(i) Metal deactivators, e.g. N, N'-diphenyl oxalic acid diamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis-salicyloyl hydrazine, N, N'-bis- (3,5-di-tert -butyl-4-hydrophenylpropionyl) hydrazine, salicylamino-1,2,4-triazole and bis-benzylidene oxalic acid dihydrazide.

(ii) Additional secondary antioxidants, such as additional phosphites and / or phosphonites, e.g. triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di-diphosphorite phosphite tert-butylphenyl), diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, Bis (2,4-dicumylphenyl) pentaerythritol diphosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite. Commercially available secondary antioxidants include Naugalube TPP, Alkanox ™ 240, Ultranox ™ 626, Naugard P, Weston ™ 399, Weston TNPP, Weston 430, Weston 618F, Weston 619F, Weston DPDP, Weston DPP, Weston PDDP, Weston PTP, Weston TDP , Weston TLP, Weston TPP, and Weston TLTTP (trilauryl trithiophosphite); Doverphos ™ 4, Doverphos 4-HR, Doverphos 4-HR Plus, Doverphos HiPure 4 and Doverphos S-9228 and Hostanox PEPQ.

(iii) Peroxide scavengers, e.g.

(Iv) Polyamide stabilizers, for example copper salts in combination with iodides and / or phosphorus compounds, and divalent manganese salts may also be included in the polymer resin and / or phosphite composition.

(v) Basic co-stabilizers, e.g. melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, e.g. Ca stearate, calcium lactate calcium stearate, Zn stearate, Mg stearate, Na ricinolate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate. Commercially available co-stabilizers include Mark ™ 6045, Mark 6045ACM, Mark 6055, Mark 6055ACM, Mark 6087ACM, Mark 6102, Mark CE 345, Mark CE 350 and Mark CE 387 and DHT-4A ™.

(vi) Nucleating agents or clarifiers, e.g. metal salts of 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sorbitol and its derivatives, sodium benzoate and benzoic acid.

(vii) Aminooxypropionate derivatives such as methyl 3- (N, N-dibenzylaminoxy) propionate; Ethyl 3- (N, N-Dibenzylamino) propionate; 1,6-hexamethylene bis (3-N, N-dibenzylamino) propionate); Methyl 2 (methyl) -3 (N, N-dibenzylamino) propionate; octadecyl-3- (N, N-dibenzylamino) propanoic acid; tetrakis (N, N-dibenzylaminoxy) etylokarbonyloksymetylo) methane; Octadecyl 3- (N, N-diethylaminoxy) propionate; potassium salt of 3- (N, N-Dibenzylamino) propanoic acid and 1,6-hexamethylene bis (3- (N-allyl-n-dodecylaminoxy) propionate).

(viii) Other additives, for example plasticizers, glidants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents and thiosynergics, such as dilauryl thiopropionate or distearyl dipropionate.

[0049] Optionally, the polymer or polymer resins may comprise 5-50 wt.%, E.g. 10-40 wt. or 1530 wt. fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, soot and graphite.

Polymers [0050] The invention further relates to a stabilized polymer in which one component comprises the liquid phosphite composition described herein and the other polymer such as polyolefin, polyvinyl chloride, etc., or polymeric resins.

[0051] The polymers stabilized with these liquid phosphite compositions may be any known polymers in the art, such as polyolefin homopolymers and copolymers, thermoplastics, rubbers, polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, polyimides, poly (phenylene ethers) styrene copolymers, polycarbonates, acrylic polymers, polyamides, polyacetals, halide containing polymers and biodegradable polymers. Mixtures of different polymers such as poly (phenylene ether) / styrene resin, poly (vinyl chloride) / ABS or other impact-modified polymers such as

ABS containing methacrylonitrile and α-methylstyrene, polyester / ABS or polycarbonate / ABS and polyester with some other impact modifier. These polymers are commercially available or can be prepared by methods well known in the art. However, the stabilizer compositions of the present invention are particularly useful for thermoplastic polymers such as polyolefins, polycarbonates, polyesters, poly (phenylene ethers) and polymers

Styrene, due to the extreme temperatures at which thermoplastic polymers are often processed and / or used.

[0052] The polymers used in combination with the liquid phosphite compositions described herein are prepared by various polymerization processes, including solution, high pressure, slurry and gas phase polymerization using various catalysts, including Ziegler-Natta catalysts, SSC (Single-Site Catalyst) ), metallocene or Phillips. Non-limiting examples of polymers useful with liquid phosphite compositions include ethylene based polymers such as linear low density polyethylene, elastomers, plastomers, high density polyethylene, substantially linear polymers containing long chain branching and low density polyethylene, and propylene based polymers such like polypropylene polymers including atactic, isotactic and syndiotactic polypropylene polymers, and propylene copolymers, such as random, block or high impact propylene copolymers. [0053] Polymers, usually ethylene-based polymers, have a density in the range of 0.86 g / cm² up to 0.97 g / cm², 2 2 2 preferably in the range of 0.88 g / cm² up to 0.965 g / cm², more preferably in the range of 0.900 g / cm² up to 0.96 2 2 2 g / cm², even more preferably in the range of 0.905 g / cm² up to 0.95 g / cm², even more preferably in the range of from 0.910 g / cm² up to 0.940 g / cm², even more preferably greater than 0.915 g / cm²even more preferably greater than 0.920 g / cm²and most preferably greater than 0.925 g / cm². Polymers prepared according to the invention typically have a molecular weight distribution, weight average molecular weight to number average molecular weight (Mw / Mn) greater than 1.5 to about 15, preferably greater than 2 to about 10, more preferably greater than from about 2.2 to less than about 8, even more preferably from about 2.2 to less than 5, and most preferably from 2.5 to 4. The Mw / Mn ratio can be measured by gel chromatography techniques well known in the art. The polymers of the present invention, in one embodiment, have a melt index (Melt Index, MI) or (I2) measured according to ASTM-D-1238-E in the range from 0.01 dg / min to 1000 dg / min, more preferably from about 0.01 dg / min to about 100 dg / min, even more preferably from about 0.1 dg / min to about 50 dg / min, and most preferably from about 0.1 dg / min to about 10 dg / min . The polymers of the invention, in one embodiment, have a Melt Index Ratio (I21 / I2) (I21 is measured according to ASTM-D-1238-F) from 10 to less than 25, more preferably from about 15 to less than 25 . The polymers of the invention, in a preferred embodiment, have a melt flow index (I21 / I2) (I21 is measured according to ASTM-D-1238-F) greater than 25, more preferably greater than 30, even more preferably greater than 40, even more preferably greater than 50 and most preferably greater than 65.

[0054] The polymers used with the liquid phosphite compositions of the invention are useful in forming operations such as film, sheet and fiber extrusion and coextrusion, as well as blow molding, injection molding and rotomoulding. Films include blown or cast films, formed by coextrusion or lamination, useful as heat-shrinkable film, adhesive film, stretch film, sealing films, oriented films, snack packaging, strong bags, shopping bags, packaging for baked and frozen food , medical packaging, industrial lining materials, membranes, etc. in food contact or non-food contact applications. Fiber forming includes melt spinning, solution spinning and melt blowing of fibers used in the form of woven or nonwovens for the production of filters, diaper materials, medical clothing, geotextiles, etc. Extruded articles include coatings for pipes, medical wires and cables, geomembranes and materials for the bottom of the water tank. Cast products include single and multi-layer constructions in the form of bottles, tanks, large hollow products,

Rigid food containers, toys, etc. In addition to the above, liquid phosphite compositions are used in various rubber-based products such as tires, partitions and the like.

[0055] In one embodiment, the liquid phosphite compositions are suitable and / or approved for use in polymers, preferably polyolefins, which are used in contact with beverages, food and other articles consumed by man.

[0056] Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example cyclopentene or norbornene, polyethylene (which may optionally be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE). Mixtures of these polymers, for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (e.g. PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (e.g. LDPE / HDPE) can also be used. Also copolymers of monoolefins and diolefins with each other or with other vinyl monomers are useful, such as, for example, ethylene / propylene copolymers, LLDPE and mixtures thereof with LDPE, propylene / butene 1, ethylene / hexene, ethylene / ethyl pentene, ethylene / heptene, ethylene / octene , propylene / isobutylene, ethylene / butane-1, propylene / butadiene, isobutylene, isoprene, ethylene / alkyl acrylates, ethylene / alkyl methacrylates, ethylene / vinyl acetate (EVA) or ethylene / acrylic acid (EAA) and their salts (ionomers) and terpolymers of ethylene with propylene and diene such as hexadiene, dicyclopentadiene or ethylidene norboren; as well as mixtures of these copolymers and mixtures thereof with the polymers mentioned above, e.g. polypropylene / ethylene-propylene copolymers, LDPE / EVA, LDPE / EAA, LLDPE / EVA, and LLDPE / EAA.

[0057] Olefin polymers can be prepared, for example, by polymerizing olefins in the presence of Ziegler-Natta catalysts, optionally supported on supports, such as, for example, MgCl2, chromium salts and their complexes, silica, silica-alumina and the like. Olefin polymers can also be prepared using chromium catalysts or SSC catalysts, e.g. metallocene catalysts, such as for example cyclopentadiene metal complexes such as Ti and Zr. As will be apparent to those skilled in the art, polyethylene polymers used herein, e.g., LLDPE, may contain various comonomers, such as, for example, 1-butene, 1-hexene and 1-octene comonomer.

[0058] Polymers may also include styrene polymers such as polystyrene, poly (p-methylstyrene), poly-methylstyrene), copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene / butadiene (SBR), styrene / acrylonitrile, styrene / methyl methacrylate, styrene / maleic anhydride, styrene / maleimide, styrene / butadiene / ethyl acrylate, styrene / acrylonitrile / methyl acrylate, mixtures with high impact strength of styrene copolymers and other polymer such as for example, polyacrylate, diene polymer or ethylene / propylene / diene terpolymer and styrene block copolymers such as, for example, styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene. [0059] Styrene polymers may additionally or alternatively include grafted copolymers of styrene or α-methylstyrene, such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene and its copolymers; styrene and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and methyl methacrylate for polybutadiene, styrene and acrylates or alkyl methacrylates for polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile napoliacrylates or polymethacrylates, styrene and acrylonitrile and copolymer copolymer styrenics indicated above.

[0060] Suitable rubbers include both natural rubber and synthetic rubbers and combinations thereof. Synthetic rubbers include, but are not limited to, for example, thermoplastic rubbers, ethylene / α-olefin / unconjugated polyene (EPDM) rubbers, ethylene / α-olefin (EPR) rubbers, styrene / butadiene rubbers, acrylic rubbers, nitrile rubbers, polyisutadrene rubbers , polychloroprene, acrylonitrile / butadiene (NBR) rubbers, polychloroprene rubbers, polybutadiene rubbers, isobutylene isoprene copolymers etc. Thermoplastic rubbers include SIS, solutions and SBS emulsion etc.

[0061] Nitrile polymers are also useful in the polymer composition of the invention. These include homopolymers and copolymers of acrylonitrile and its analogs, such as polymethacrylonitrile, polyacrylonitrile, acrylonitrile / butadiene polymers, acrylonitrile / alkyl acrylate polymers, acrylonitrile / alkyl methacrylate / butadiene polymers and various ABS compositions mentioned above with respect to styrene.

[0062] Polymers based on acrylic acids such as acrylic acid, methacrylic acid, methyl methacrylic acid and ethacrylic acid may also be used, and their esters. Such polymers include poly (methyl methacrylate) and ABS type graft copolymers in which all or part of the acrylonitrile type monomer has been replaced with acrylic acid ester or acrylic acid amide. Polymers including other acrylic type monomers such as acrolein, metacrolein, acrylamide and methacrylamide may also be used.

[0063] Hydrolytically stabilized phosphites can also stabilize halogen-containing polymers. These include polymers such as polychloroprene, epichlorohydrin homo- and co-polymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, fluorinated polyvinylidene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinyl chloride terpolymer vinyl, vinyl chloride-acrylic acid ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymer internally plasticized poly (vinyl chloride).

[0064] Other useful polymers include homopolymers and copolymers of cyclic ethers, such as poly (alkylene glycols), poly (ethylene oxide), poly (propylene oxide) or copolymerization thereof with bisglycidyl ethers; polyacetals such as polyoxymethylene and those polyoxymethylenes that contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or containing methacrylonitrile ABS; poly (phenylene oxides) and polyphenylene sulfides and mixtures of poly (phenylene oxides) with polystyrene or polyamides; polycarbonates and polyester carbonates; polysulfones, polyethersulfones and polyetherketones; and polyesters that are derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, poly (butylene terephthalate), poly (1,4-dimethylol cyclohexane terephthalate), poly (2- (2-terephthalate) , 2,4 (4-hydroxyphenyl) propane) and polyhydroxybenzoates, as well as block copolyesters derived from polyethers containing hydroxyl end groups.

[0065] Polyamides and copolyamides that are derived from bisamines and dicarboxylic acids and / or aminocarboxylic acids or suitable lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 may be useful and 4/6, polyamide 11, polyamide 12, aromatic polyamides obtained by condensation of m-xylene bisamine and adipic acid; polyamides made from hexamethylene bisamine and isophthalic or / and terephthalic acid and, optionally, an elastomer as a modifier, e.g. poly-2,4,4-tri17

Methylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide. Further copolymers of polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers may be used; or with polyethers, such as, for example, poly (ethylene glycol), poly (propylene glycol) or poly (tetramethylene glycols), and polyamides or copolyamides modified with EPDM or ABS.

[0066] In another embodiment, the polymer comprises a biodegradable polymer or a compostable polymer. Biodegradable polymers are polymers whose decomposition is caused by the action of naturally occurring microorganisms such as bacteria, fungi and algae. Compostable polymers degrade in the biological process during composting, producing CO2, water, inorganic compounds and biomass, at the same rate as other compostable materials. Usually, biodegradable or compostable polymers are of plant origin or are obtained synthetically. Examples of biodegradable or compostable polymers include poly (glycolic acid) (PGA), poly (lactic acid) (PLA) and copolymers thereof. Biodegradable or compostable polymers can also be derived from a mixture of plant starch and conventional petroleum-based polymer. The biodegradable polymer can be mixed, for example, with a polyolefin.

[0067] More preferred are polyolefin, polyalkylene terephthalate, poly (phenylene ether) and styrene polymers and mixtures thereof, and particularly preferred: polyethylene, polypropylene, polyethylene terephthalate, homopolymers and copolymers of poly (phenylene ether), polystyrene , high impact polystyrene, polycarbonates and graft copolymers type ABS and mixtures thereof.

[0068] In one embodiment, liquid phosphite compositions are added to stabilize natural and synthetic waxes, such as n-paraffin waxes, chloroparaffins, α-olefin waxes, microcrystalline waxes, polyethylene waxes, amide waxes and Fisher-Tropsch waxes. These waxes may be suitable for making candles.

[0069] The present stabilizers can easily be introduced into the polymer by conventional techniques at any convenient stage, before making shaped articles therefrom. For example, the stabilizer can be mixed with the polymer in the form of a dry powder or the suspension or emulsion of the stabilizer can be mixed with the polymer solution, suspension or emulsion. The stabilized compositions of the invention may optionally also contain from about 0.001 to about 5% by weight, e.g. from about 0.0025 to about 2% by weight. or from about 0.05 to about 0.25 wt. various conventional additives as described above or mixtures thereof.

[0070] The stabilizers of the present invention advantageously support the stabilization of polymer compositions, especially during high temperature processing, counteract changes in melt index and / or color, although the polymer may be repeatedly extruded. The stabilizers of the present invention can easily be introduced into the polymer by conventional techniques at any convenient stage before making shaped articles therefrom. For example, the stabilizer can be mixed with the polymer in the form of a dry powder or the suspension or emulsion of the stabilizer can be mixed with the polymer solution, suspension or emulsion.

[0071] The compositions of the present invention can be made in a variety of ways, such as those that consist in uniformly mixing ingredients with additional substances that are desirable in formulations. Suitable procedures include solution mixing and melt mixing. Due to the availability of melt mixing equipment in commercial polymer processing facilities, melt processing procedures are usually preferred. Examples of equipment used in such methods

Mixing components include: co-rotating and counter-rotating extruders, single screw extruders, compactors and various other types of extrusion equipment. In some cases, the mixed substance leaves the extruder through the small exit holes in the matrix, the obtained melt resin strands are cooled by passing them through a water bath. Chilled strands can be cut into small pellets for packaging and further processing etc.

[0072] All components can be added to the process system at the beginning, or some additives can be mixed with each other or with a portion of polymer resin to form a stabilizer concentrate. In addition, it is also sometimes preferred to use at least one vent hole to allow venting (atmospheric or vacuum) of the alloy. The specialist will be able to choose the time and temperature of mixing, as well as the moment and sequence of adding ingredients, without the additional need for excessive experimentation.

[0073] Although the stabilizers of the present invention may conveniently be incorporated into polymers by conventional techniques prior to making shaped articles therefrom, the present stabilizers may also be used by topical application to finished products. The articles may include the present stabilizing compounds and polymers and can be manufactured from them, for example, car headlight covers, roof sheets, telephone housings, aircraft interior components, building interior components, computer cases and office equipment, automotive parts and home appliances. Products can be made by extrusion, injection molding, rotomoulding, compacting and other methods. This may be particularly useful for fiber applications in which the present stabilizers are applied topically to the fibers, for example, as a spin finish during the melt spinning process. In one embodiment, the liquid phosphite compositions should be approved for use in polymer resins, preferably polyolefins, which are used in contact with beverages, foods and other articles consumed by man.

[0074] The hydrolytically stabilized phosphite composition of the invention may have other uses besides polymer stabilization. For example, it may be desirable to react the phosphite composition to produce a new derivative product that may have additional uses. A transesterification process may also be used, for example such as disclosed in Hechenbleikner et al., US Patent 3056823. Specifically, the method described by Hechenbleikner et al. involves transesterification of triaryl phosphite using monohydrohydrocarbon in the presence of a small but catalytically effective amount of metal alkoxide or metal phenolate. To prevent pollution, the alcoholate of the transesterified alcohol is used. Instead of using the previously prepared alkoxide, the alkoxide can be prepared in situ by adding a metal, e.g., sodium, potassium or lithium, to the alcohol prior to the addition of triaryl phosphite. Monoalcohol and triaryl phosphite are reacted in a molar ratio of three moles of alcohol to one mole of triaryl phosphite.

[0075] It is believed that one skilled in the art can, using the present description, utilize the present invention to its fullest extent, without further elaboration. In order to provide those skilled in the art with additional guidance on the practical implementation of the claimed invention, the following examples are included in the description. These examples are only illustrative of the work that contributes to the understanding of this application. Thus, these examples are not intended to limit the invention as defined in the appended claims in any way.

[0076] The present invention will now be described by the following non-limiting examples.

Example 1 [0077] Table 4 shows the improved hydrostability of phosphites and liquid phosphite compositions used with various hydrolysis stabilizers. The hydrolytic stabilizers used in Example 1 included: A = epoxidized soybean oil (e.g., Drapex 6.8), B = triisopropanolamine (TIPA), C = ethoxylated tallowalkylamine (Armostat 300) and D = octadecylbis (2-hydroxyethyl) amine (Armostat 1800). The liquid phosphite composition analyzed included trinonylphenyl phosphite (TNPP) and a mono- / di-t-amylphenyl phosphite composition (designated Liquid X) which contained the following phosphites: 30-50 wt. tri (4-t-amylphenyl) phospho-tenne; 30-50 wt. bis (4-t-amylphenyl) (2,4-di-t-amylphenyl) phosphite; 5-15 wt.

(4-t-amylphenyl) bis (2,4-di-t-amylphenyl) phosphite and less than 4 wt. tris (2,4-di-t-amylphenyl) phosphite. [0078] Approximately 0.025 g of TNPP and Liquid X sample with and without additions was weighed into GC vials, and these vials were stored in a humidity chamber at 50 ° C, 80% relative humidity. The vials were removed from the chamber daily and analyzed by 31P {1H} NMR to make sure when the phosphite degraded. The test was conducted for a maximum of 14 days.

<td rowspan="2">Course</td><td rowspan="2">Phosphite</td><td colspan="2">TABLE 4 Hydrolysis stabilizer</td><td rowspan="2">Survival Time (days)</td>

<td>Type</td><td>wt%</td>

<td> 1</td><td>TNPP</td><td> --</td><td> --</td><td> 0,5</td>

<td> 2</td><td>TNPP</td><td>AND</td><td>5 wt.</td><td> 1</td>

<td> 3</td><td>TNPP</td><td>B</td><td>0.8 wt.</td><td> &gt; 14</td>

<td> 4</td><td>TNPP</td><td>C</td><td>2 wt.</td><td> 4</td>

<td> 5</td><td>TNPP</td><td>D</td><td>1 wt.</td><td> 4</td>

<td> 6</td><td>Liquid X</td><td> --</td><td> --</td><td> 1</td>

<td> 7</td><td>Liquid X</td><td>AND</td><td>5 wt.</td><td> 2</td>

<td> 8</td><td>Liquid X</td><td>B</td><td>0.8 wt.</td><td> &gt; 14</td>

<td> 9</td><td>Liquid X</td><td>C</td><td>2 wt.</td><td> 13</td>

<td> 10</td><td>Liquid X</td><td>D</td><td>1 wt.</td><td> 12</td>

[0079] As shown in Table 4, for both TNPP and Liquid X, the amine stabilizers of the present invention (Type BD) resulted in a significant improvement in the hydrostability of liquid phosphite compositions. Especially ethoxylated tallowalkylamine and octadecylbis (2-hydroxyethyl) amine caused increased hydrostability of the liquid phosphite composition (Runs 9 and 10) in relation to TNPP (Runs 4 and 5).

Example 2 [0080] The effect of TIPA and octadecylbis (2-hydroxyethyl) amine (Armostat 1800) on the hydrostability and appearance of Liquid X (described above) was studied.

[0081] About 0.025g of Liquid X sample was combined with either 0.8 wt. TIPA, or with 2 wt. Armostat 1800. Samples were weighed into GC vials and the vials were stored in a humidity chamber at 50 ° C and 80% relative humidity. Liquid X vials combined with 0.8 wt. TIPA and Liquid X vials combined with 2 wt. Armo20

EP 2 459 575 B1

1 stat 1800 was removed daily for 1 week. Analysis³¹P {¹H} NMR showed that Liquid X did not decompose. However, during the course of the test, the Liquid X sample combined with 0.8 wt. TIPA became cloudy, while the Liquid X sample combined with 2 wt. Armostat 1800 remained clear and free from turbidity at all times, and as such it still resembled the starting substance.

[0082] Thus, Armostat 1800 provides similar hydrolytic stability as TIPA, however, Armostat 1800 does this without causing turbidity.

[0083] In an analogous TNPP experiment combined with 0.8 wt% TIPA, the samples did not become cloudy.

Example 3 - Adapted static test [0084] To 12 ml of a mixture of water and bromothymol blue indicator was added 4 ml of phosphite, indicated in Table 5, optionally with 1 wt. TIPA. The resulting mixture was heated to 60 ° C. The hydrolytic degradation of phosphite, which produces acid, was detected by changing the color of the indicator, bromothymol blue. The assumed minimum for color change was 8 hours and the test was conducted for 100 hours.

TABLE 5

<td> #</td><td>Phosphite</td><td>Amine</td><td>Hours</td>

<td> 1</td><td>TNPP</td><td> --</td><td> 0</td>

<td> 2</td><td>Liquid X</td><td> --</td><td> 2</td>

<td> 3</td><td>TNPP</td><td>TIPA</td><td> 15</td>

<td> 4</td><td>Liquid X</td><td>TIPA</td><td> 100</td>

[0085] The combination of Liquid X and TIPA shows good hydrolytic stability over the combination

TNPP and TIPA. This is clearly surprising and unexpected because TIPA was expected to have similar effects on both TNPP and Liquid X.

Example 4 - Adapted dynamic test [0086] To 60 ml of a mixture of water and phenolphthalein indicator was added 20 g of phosphite as indicated in Table 6, optionally with 1 wt% TIPA. The resulting mixture was heated to 60 ° C under vigorous stirring. The hydrolytic degradation of phosphite, which produces acid, was detected by changing the color of the indicator, phenolphthalein. The assumed minimum for color loss was 20 min and the test was carried out for 120 hours.

<td colspan="4">TABLE 6</td>

<td> #</td><td>Phosphite</td><td>Amine</td><td>Hours</td>

<td> 1</td><td>TNPP</td><td> --</td><td> 1</td>

<td> 2</td><td>Liquid X</td><td> --</td><td> 1,5</td>

<td> 3</td><td>TNPP</td><td>TIPA</td><td> 120</td>

<td> 4</td><td>Liquid X</td><td>TIPA</td><td> 120</td>

[0087] The combination of Liquid X and TIPA and a combination of TNPP and TIPA show good hydrolytic stability.

EP 2 459 575 B1

<td colspan="4">TABLE 7</td>

<td> #</td><td>Phosphite</td><td>Amine</td><td>Hours</td>

<td> 1</td><td>TNPP</td><td> --</td><td> 120</td>

<td> 2</td><td>Liquid X</td><td> --</td><td> 13</td>

<td> 3</td><td>TNPP</td><td>TIPA</td><td> 120</td>

<td> 4</td><td>Liquid X</td><td>TIPA</td><td> 120</td>

Example 5 - heating of cyclohexane under reflux [0088] 25 ml of water and bromothymol blue and 25 ml of cyclohexane were combined and the mixture was heated to reflux. 0.5g of phosphite as indicated in Table 7, optionally with 1 wt% TIPA, was added to the boiling mixture with a syringe. The test was carried out for 120 hours.

[0089] As shown in Table 7, TNPP with or without TIPA survived for a period of 120 hours. However, the survival of Liquid X has greatly improved the addition of TIPA.

[0090] Due to the many changes and modifications that can be made without departing from the basics of the invention, to understand the scope of protection of the invention, reference should be made to the appended claims.