Stabilizer composition

Abstract

The present invention provides a stabilizing composition for polyols and / or polyurethanes, comprising: a) a first derivatized phenolic antioxidant having a molecular weight of at least about 400 g / mol and a melting point of less than about 100° C.; b) a second derivatized phenolic antioxidant having less steric hindrance than the first derivatized phenolic antioxidant and being solid at ambient conditions; and c) a secondary antioxidant comprising a phosphite and / or a thioester. A flame retardant blend comprising the stabilizing composition and a flame retardant is also disclosed.

Description

【Technical Field】 【0001】 【0001】The present invention relates to a stabilizing composition. The stabilizing composition is particularly useful for the stabilization of polyols and polyurethanes containing polyurethane foams. 【Background Art】 【0002】 【0002】Polyurethanes constitute a class of polymers having various structures, properties, and uses. All of them have a carbamic acid or urethane bond, i.e., -NH-C(=O)-O-, and can be produced by reacting an isocyanate with a polyol. Polyurethanes can be made according to the selection of isocyanates and polyols, the presence of other components, and reaction conditions. Polyurethanes include thermoplastic materials and thermosetting materials, and are used, among other products, to produce flexible and rigid foams, coatings, fibers, molded products, elastomeric components, sealants, and adhesives. 【0003】 【0003】Polyurethane foams can be produced by reacting an isocyanate with a polyol and water, and the carbon dioxide generated internally simultaneously brings about polymerization and expansion. Both the polymerization reaction of the isocyanate and the polyol and the reaction of the isocyanate and water to produce carbon dioxide are accompanied by a large amount of heat generation. Polyurethane foams are themselves insulating, and as a result, a large amount of heat is trapped inside the foam, which may cause or enhance the degradation of the foam by a free radical auto-oxidation cycle. Free radicals can react with oxygen to form peroxy radicals. The peroxy radicals can then react with further polymer species to produce hydroperoxides, which themselves decompose into further reactive free radical species. 【0004】 【0004】This type of degradation is often called scorch. Scorch can be detected in polyurethane foams by the appearance, i.e., discoloration, which is a darker-colored region in the foam. 【0005】

[0005] Antioxidants can be used to break the polymer degradation cycle, thereby reducing the amount of scorching. Some antioxidants known as primary antioxidants act by reacting with peroxyl radicals. Other antioxidants known as secondary antioxidants act by reacting with hydroperoxides. 【0006】

[0006] Types of primary antioxidants include sterically hindered phenol and amine compounds, particularly secondary arylamines, such as those described in US4,824,601. For the stabilization of polyurethanes, it is known to use a combination of these two types of primary antioxidants, for example, as described in WO2015 / 132087. 【0007】

[0007] Stabilizing compositions containing phenolic antioxidants and amine antioxidants have demonstrated effective in-process stabilization of polyurethanes, particularly good scorching performance. However, amine antioxidants such as alkylated diphenylamines tend to have poor performance in terms of discoloration when exposed to light and / or polluting gases such as nitrogen oxides. 【0008】

[0008] Phenolic antioxidants alone tend not to perform as well in terms of scorch reduction as stabilization compositions containing both phenolic and amine antioxidants. Therefore, alternatives to amine antioxidants in stabilization compositions have been investigated. 【0009】

[0009] One alternative considered in the prior art is a stabilizing composition having a phenolic antioxidant and a benzofuranone component, such as that described in EP1291384. The benzofuranone component acts as a "booster," i.e., a component that improves the scorching performance of the stabilizing composition beyond the base stabilization of the phenolic component. However, such stabilizing compositions tend to exhibit poor oxidation onset temperature (OOT) performance compared to stabilizing compositions containing amine antioxidants. 【0010】

[0010] Another alternative considered in the prior art is a stabilizing composition having a phenolic antioxidant and 4-tert-butylcatechol. 【0011】 US6,676,849 describes a scorch inhibitor composition for use as an additive in the manufacture of polyurethane foams, comprising derivatized di-tert-butylphenol; 4-tert-butylcatechol; and optionally phenothiazine, which are optionally dimerized and substituted with C2 or more aromatic, aliphatic, or aromatic-aliphatic moieties (the moieties optionally having a combination of heteroatoms).

[0011] 【0012】 However, such stabilized compositions tend to be highly volatile when tested according to VDA278. 【0013】 WO2017 / 037204 is formula (I):

[0012] [ka]

[0013] [In the formula, R1 is a linear or branched alkyl group having 12 to 20 carbon atoms, and one or more second phenolic antioxidants are independently selected from mono-hydroxybenzene; di-hydroxybenzene; and / or tri-hydroxybenzene having less steric hindrance than the first phenolic antioxidant.] This document describes a stabilizing composition comprising one or more phenolic compounds having the structure described above. 【0014】

[0014] However, WO2017 / 037204 does not discuss the use of secondary antioxidants due to concerns regarding the hydrolysis stability of such antioxidants. 【0015】WO2017 / 037205 describes the use of a stabilizing composition for stabilizing polyols and / or polyurethanes, the stabilizing composition comprising a phenolic antioxidant and a compound of formula I: 【0015】 【Chemical formula】 【0016】 [wherein R1, R2, and R3 are of the structure: 【0017】 【Chemical formula】 【0018】 (wherein R4, R5, and R6 are independently selected from the group consisting of hydrogen and C1-C6 alkyl, provided that at least one of R4, R5, and R6 is not hydrogen) and are independently selected alkylated aryl groups of the structure] and comprises one or more phosphite antioxidants having the structure of. However, WO2017 / 037205 states that the use of booster components is excluded. 【0019】 【0016】One industrially applicable stabilizing composition consists of a hindered phenolic antioxidant having CAS number 125643-61-0, a phosphite antioxidant having CAS number 145650-60-8, and a benzofuranone (3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one) having CAS number 216698-07-6. 【0020】 【0017】However, when this stabilizing composition was tested according to VDA278, it showed a large amount of emissions, especially with regard to FOG. Currently, there is a strong demand, especially from the automotive industry, to significantly reduce or eliminate the volatile emissions from stabilizing compositions. 【0021】 【0018】US2015 / 315465 describes a stabilizer composition comprising an ortho-hydroxyl tris-aryl-s-triazine compound; a hindered amine light stabilizer compound; a hindered hydroxybenzoic acid compound; a phosphite compound, an acid scavenger and / or a thioester; and a hindered phenol antioxidant compound. 【0022】 【0019】CN104327368 describes a self-crosslinking expandable flame retardant material. 【0020】EP1041582 describes a composition comprising polyethylene; a substituted hydroquinone or 4,4'-thiobis(2-t-butyl-5-methylphenol) as a first scorch inhibitor; distearyl disulfide as a second scorch inhibitor; and an organic peroxide. 【0023】 【0021】EP0965998 describes a composition comprising a low density homopolymer of ethylene prepared by a high pressure process; a substituted hydroquinone in an amount of about 0.02 to about 0.07 parts by weight of a scorch inhibitor per 100 parts by weight of the homopolymer; 4,4'-thiobis(2-methyl-6-t-butylphenol); 2,2'-thiobis(6-t-butyl-4-methylphenol); a scorch inhibitor selected from the group consisting of 4,4'-thiobis(2-t-butyl-5-methyl-phenol); a curing booster; and an organic peroxide. 【0024】 【0022】CN103709713 describes a light diffusing material comprising a polycarbonate resin, a light diffusing agent, a light stabilizer, a composite antioxidant, and a composite flame retardant. 【0023】However, the antioxidant compositions described in EP1041582, EP0965998, and CN103709713 have a relatively high melting point and are not stable liquids at temperatures below 100°C. 【Summary of the Invention】 【Problems to be Solved by the Invention】 【0025】

[0024] Therefore, there remains a need for an antioxidant stabilization composition that overcomes the problems associated with the prior art stabilization compositions revealed above and satisfies the requirements for an antioxidant stabilization composition with respect to physical state, shelf life, susceptibility to hydrolysis, in-process stabilization, scorch protection, color properties, volatility, and protection against light and polluting gases. [Means for solving the problem] 【0026】

[0025] According to one aspect of the present invention, a stabilizing composition for polyols and / or polyurethanes. a) A first derivatized phenolic antioxidant having a molecular weight of at least about 400 g / mol and a melting point of less than about 100°C, b) A second derivatized phenolic antioxidant having less steric hindrance than the first derivatized phenolic antioxidant and being solid under ambient conditions, c) Secondary antioxidants including phosphites and / or thioesters A stabilizing composition containing the following is provided. 【0027】

[0026] According to another aspect of the present invention, a stabilizing composition for polyols and / or polyurethanes, a) A first derivatized phenolic antioxidant having a molecular weight of at least about 400 g / mol and a melting point of less than about 100°C, which is effective in providing a contribution to VOCs of less than about 10 ppm and / or a contribution to FOG of less than about 100 ppm. b) A second derivatized phenolic antioxidant having less steric hindrance than the first derivatized phenolic antioxidant and being solid under ambient conditions, c) Secondary antioxidants comprising phosphite and / or thioesters A stabilizing composition containing the following is provided. 【0028】

[0027] According to another aspect of the present invention, a stabilizing composition for polyols and / or polyurethanes, a) A first derivatized phenolic antioxidant having a contribution to VOCs of less than approximately 10 ppm and / or a contribution to FOG of less than approximately 100 ppm, as determined according to the standard test method VDA278, and a melting point of less than approximately 100°C, b) A second derivatized phenolic antioxidant having less steric hindrance than the first derivatized phenolic antioxidant and being solid under ambient conditions, c) Secondary antioxidants comprising phosphite and / or thioesters A stabilizing composition containing the following is provided. 【0029】

[0028] In this context, and throughout this specification, “ambient conditions” means atmospheric pressure (101.325 kPa) and a temperature of 25°C.

[0029] The stabilizing composition of the present invention may be in the absence of diphenylamine and / or alkylated diphenylamine. 【0030】

[0030] The stabilizing composition of the present invention may be free of diarylamines and / or alkylated diarylamines. 【0031】 The stabilizing composition of the present invention may be free of diarylamines and / or their derivatives.

[0031] 【0032】 The stabilizing composition of the present invention may be free of amine-based primary antioxidants. 【0033】 In this context, “absence” means that the component is not present at all in the stabilizing composition, or that the stabilizing composition contains only a small amount of the component, such that it is not effective enough to cause significant discoloration of the polyol and / or polyurethane to which the stabilizing composition of the present invention is added, and / or is not effective enough to violate regulatory standards with respect to the presence of residual diphenylamine. [Modes for carrying out the invention]

[0032] 【0034】To their surprise, the inventors of the present invention found that polyols and / or polyurethanes, particularly polyurethane foams, can be stabilized using the stabilizing composition of the present invention.

[0033] 【0035】 Advantageously, the stabilizing compositions of the present invention have a low contribution to volatile organic compounds (VOCs) and low condensable gas release (FOG). This can be attributed, at least in part, to minimal volatile release (VOCs and FOG) from the first derivatized phenolic antioxidant.

[0034] 【0036】 The contribution of the stabilized composition to VOCs may be less than approximately 20 ppm, less than approximately 15 ppm, less than approximately 10 ppm, or less than approximately 5 ppm. The contribution of the stabilized composition to FOG may be less than approximately 200 ppm, less than approximately 150 ppm, less than approximately 100 ppm, or less than approximately 50 ppm.

[0035] 【0037】 The values ​​of contributions to VOCs and FOGs are determined according to the standard test method VDA278 for polyurethane foams. This standard test method, published by "Verband Der Automobilindustrie" in October 2011, is an internationally recognized and standardized test procedure for the quantitative analysis of volatile compounds.

[0036] 【0038】 The polyurethane foam for VDA278 has the following precursors and / or parameters: i. A polyol having a molecular weight of approximately 3500 g / mol, for example, CARPOL® GP3510. ii. 35-40 kg / m 3 2.5 php of water for the density of the target polyurethane foam. iii. Isocyanate index of 105 It may be formed by a process using or employing.

[0037] 【0039】 Polyurethane foam is "high density (40 kg / m²) 3The polyurethane foam may be formed by a process, as outlined in the following example titled "Preparation of Polyurethane Foam."

[0038] 【0040】 As mentioned above, there is currently a strong demand, particularly from the automotive industry, to significantly reduce or eliminate volatile emissions from stabilized compositions. The stabilized compositions of the present invention have been found to comply with the automotive standard test method VDA278 for volatile emissions (VOCs and FOGs).

[0039] 【0041】 In addition, the stabilizing composition of the present invention has a high level of scorch protection. Although we do not wish to be bound by any such theory, it is thought that the presence of a second derivatized phenolic antioxidant increases the activity of the stabilizing composition with respect to scorch protection. This component is thought to have higher activity with respect to scorch protection than the first derivatized phenolic antioxidant, which is more sterically hindered. Therefore, when the second derivatized phenolic antioxidant is added to the first derivatized phenolic antioxidant, it increases the activity of the stabilizing composition with respect to scorch protection.

[0040] 【0042】 The presence of secondary antioxidants provides good long-term stability to the stabilized composition and helps reduce discoloration, particularly discoloration caused by the second derivatized phenolic antioxidant.

[0041] 【0043】 The aforementioned advantages, particularly the high level of anti-scorch performance, were unexpectedly discovered to be achievable without the use of amine-based primary antioxidants such as diphenylamines and alkylated diphenylamines. This is beneficial because these types of antioxidants tend to perform poorly in terms of discoloration when exposed to light and / or polluting gases such as nitrogen oxides.

[0042] 【0044】The entire stabilization composition preferably has a melting point of less than about 100°C. The entire stabilization composition may have a melting point of less than about 90°C, less than about 80°C, less than about 70°C, less than about 60°C, or less than about 50°C. A relatively low melting point may provide the advantage of the stabilization composition that it can be mixed with polyols and / or polyurethanes, particularly polyurethane foams, without heating to high temperatures.

[0043] 【0045】 In some cases, it is preferable that the entire stabilizing composition be liquid under ambient conditions, i.e., atmospheric pressure (101.325 kPa) and a temperature of 25°C. Liquid stabilizing compositions can be readily dispersed in polyols and / or polyurethanes, and some polyol / polyurethane manufacturers require stabilizing compositions that are liquid under ambient conditions.

[0044] 【0046】 The essential elements of the present invention will now be described in detail. These will be applied to any aspect of the present invention as needed. 【0047】 The compounds designated under the trade names ISONOX®, NAUGARD®, ANOX®, LOWINOX®, and WESTON® are available from SI Group USA (USAA), LLC, 4 Mountainview Terrace, Suite 200, Danbury, CT06810.

[0045] First derivatized phenolic antioxidant 【0048】Advantageously, the first derivatized phenolic antioxidant has a low contribution to VOCs and FOGs. The first derivatized phenolic antioxidant may have a lower contribution to VOCs and FOGs than other known phenolic antioxidants, such as 2,6-di-tert-butyl-4-sec-butylphenol (ISONOX® 132-CAS17540-75-9), 2,6-di-tert-butyl-4-nonylphenol (ISONOX® 232-CAS4306-88-1), and benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-,C7-C9 branched alkyl ester (NAUGARD® PS48-CAS125643-61-0).

[0046] 【0049】 The contribution of the first derivatized phenolic antioxidant to VOCs may be less than about 10 ppm, less than about 5 ppm, less than about 2 ppm, or less than about 1 ppm. The contribution of the first derivatized phenolic antioxidant to FOG may be less than about 100 ppm, less than about 50 ppm, less than about 20 ppm, or less than about 10 ppm.

[0047] 【0050】 The values ​​of contributions to VOCs and FOGs are determined according to the standard test method VDA278 for polyurethane foams. 【0051】 The first derivatized phenolic antioxidant has a molecular weight of at least about 400 g / mol. The first derivatized phenolic antioxidant may have a molecular weight of at least about 410 g / mol, at least about 420 g / mol, at least about 430 g / mol, at least about 440 g / mol, at least about 450 g / mol, at least about 460 g / mol, at least about 470 g / mol, or at least about 480 g / mol.

[0048] 【0052】 The relatively high molecular weight of the first derivatized phenolic antioxidant can, at least in part, explain its low contribution to VOCs and FOGs. 【0053】The first derivatized phenolic antioxidant may consist of a single derivatized phenolic antioxidant or a blend of two or more derivatized phenolic antioxidants.

[0049] 【0054】 The first derivatized phenolic antioxidant is given by formula (I):

[0050] [ka]

[0051] [In the formula, n is either 1 or 2. R1 is a linear or branched alkyl group having 1 to 30 carbon atoms, optionally substituted with one or more ether groups. R2 and R3 are each independently selected from linear or branched alkyl groups having 1 to 5 carbon atoms. It may also contain one or more derivatized phenolic antioxidants.

[0052] 【0055】 R2 and R3 may be selected from methyl, ethyl, propyl, n-butyl, t-butyl, and t-amyl. 【0056】 Preferably, R2 and R3 contain the same substituent. More preferably, both R2 and R3 are t-butyl groups.

[0053] 【0057】As a specific, non-limiting example, the first derivatized phenolic antioxidant is 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, C13-15 alkyl ester (ANOX(trademark) 1315-CAS171090-93-0); benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, isotridecyl ester (CAS847488-62-4); a bisphenolic stabilizer of formula (II) where n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 (WO2017125291). The disclosed materials may include one or more of the following, and / or mixtures thereof: octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate (ANOX® PP18-CAS2082-79-3); 2,2'thiodiethylenebis[3(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (ANOX® 70-CAS41484-35-9); n-hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate (CAS67845-93-6).

[0054] [ka]

[0055] 【0058】 The first derivatized phenolic antioxidant has a melting point of less than about 100°C. The first derivatized phenolic antioxidant may have a melting point of less than about 90°C, less than about 80°C, less than about 70°C, less than about 60°C, or less than about 50°C.

[0056] 【0059】 In this context, and throughout this specification, the term “melting point” encompasses both the exact melting point and the melting range. If the first derivatized phenolic antioxidant (or other component) has a melting range, the entire melting range must be within the defined temperature range.

[0057] 【0060】In some cases, it may be preferable that the first derivatized phenolic antioxidant be liquid under ambient conditions, i.e., at atmospheric pressure (101.325 kPa) and a temperature of 25°C.

[0058] 【0061】 If the first derivatized phenolic antioxidant is liquid under ambient conditions, it may be able to dissolve the second derivatized phenolic antioxidant and / or secondary antioxidant to form the entire liquid-stabilized composition under ambient conditions. As previously mentioned, the liquid-stabilized composition can be more readily dispersed in polyols and / or polyurethanes.

[0059] 【0062】 As outlined above, the first derivatized phenolic antioxidant does not necessarily consist of a single derivatized phenolic antioxidant, but may consist of a blend of two or more derivatized phenolic antioxidants. The two or more derivatized phenolic antioxidants may be selected to provide complementary properties, for example, with respect to melting point and low release rate.

[0060] 【0063】 In this case, it may be possible to include in the blend one or more derivatized phenolic antioxidants that do not have a melting point below approximately 100°C, but which may nevertheless be blended with one or more other compatible derivatized phenolic antioxidants to result in a blend having a melting point below approximately 100°C.

[0061] 【0064】Specific non-limiting examples of such derivatized phenolic antioxidants include tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane (ANOX® 20-CAS6683-19-8); 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate (ANOX® IC14-CAS27676-62-6); N,N'-hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide] (LOWINOX® HD98-CAS23128-74-7); 1,2-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamoyl)hydrazine (LOWINOX® MD24-CAS32687-78-8); and p-cresol and dicyclopentadiene butylation reaction Products (LOWINOX (trademark) CPL-CAS68610-51-5); 2,2'-Ethylene bis[4,6-di-t-butylphenol] (ANOX (trademark) 29-CAS35958-30-6); 1,3,5-Trimethyl-2,4,6-Tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene (ANOX (trademark) 330-CAS1709-70-2); Triethylene glycol-bis -[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate](LOWINOX® GP45-CAS36443-68-2); 2,2'-oxamidobis[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate](NAUGARD® XL-1-CAS70331-94-1); and / or mixtures of two or more thereof.

[0062] 【0065】 In a specific example, the first derivatized phenolic antioxidant may include a blend of ANOX® 1315 and ANOX® 20. In this case, ANOX® 20 (a solid with a melting range of 110-125°C) is dissolved in ANOX® 1315 to form a blend with a melting point below 100°C.

[0063] 【0066】As a further example, the first derivatized phenolic antioxidant may include a blend of ANOX® PP18 and ANOX® 20. Again, this blend has a melting point of less than 100°C.

[0064] 【0067】 Particularly preferred first derivatized phenolic antioxidants are 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, C13-15 alkyl ester (ANOX® 1315); 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, C13-15 alkyl ester (ANOX® 1315) and tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane ( Blends with ANOX® 20); octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate (ANOX® PP18); and / or blends of octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate (ANOX® PP18) and tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane (ANOX® 20).

[0065] 【0068】 The stabilizing composition preferably contains substantially no reagent phenolic compounds, i.e., phenolic compounds used in the production of the first derivatized phenolic antioxidant. In particular, the stabilizing composition preferably contains substantially no methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (CAS 6386-38-5).

[0066] 【0069】 In this context, "substantially absent" means that the reagent phenolic compound, if present, is in an amount less than 0.2% by weight of the first derivatized phenolic antioxidant.

[0067] 【0070】 By limiting the amount of reagent phenolic compounds in the stabilizing composition, the contribution to VOCs and / or FOGs is minimized. 【0071】 The first derivatized phenolic antioxidant may be present in the stabilizing composition in an amount of about 30 wt.% to about 95 wt.%, about 40 wt.% to about 95 wt.%, about 50 wt.% to about 95 wt.%, or about 60 wt.% to about 90 wt.%, based on the total weight of the stabilizing composition.

[0068] Second derivatized phenolic antioxidant 【0072】 The second derivatized phenolic antioxidant has less steric hindrance than the first derivatized phenolic antioxidant. This means that the number of ortho substituents relative to the phenol moiety in the second derivatized phenolic antioxidant is less than the number of ortho substituents relative to its or one phenol moiety in the first derivatized phenolic antioxidant, or the size of any ortho substituent relative to its or one phenol moiety in the second derivatized phenolic antioxidant is smaller than the size of any ortho substituent relative to its or one phenol moiety in the first derivatized phenolic antioxidant, or both.

[0069] 【0073】 The second derivatized phenolic antioxidant preferably has a smaller molecular weight than the first derivatized phenolic antioxidant. If this is the case and the first derivatized phenolic antioxidant contains two or more components, the second derivatized phenolic antioxidant has a smaller molecular weight than each of the components. If the second derivatized phenolic antioxidant contains two or more components, each of these components has a smaller molecular weight than the component (or each of the components) of the first derivatized phenolic antioxidant.

[0070] 【0074】The second derivatized phenolic antioxidant may have a molecular weight less than about 600 g / mol. The second derivatized phenolic antioxidant may have a molecular weight of about 550 g / mol or less, about 500 g / mol or less, about 480 g / mol or less, about 470 g / mol or less, about 460 g / mol or less, about 450 g / mol or less, about 440 g / mol or less, about 430 g / mol or less, about 420 g / mol or less, about 410 g / mol or less, or less than about 400 g / mol. In some cases, the second derivatized phenolic antioxidant may have a molecular weight of about 390 g / mol or less, about 380 g / mol or less, about 370 g / mol or less, or about 360 g / mol or less.

[0071] 【0075】 The second derivatized phenolic antioxidant is thought to increase the activity of the stabilizing composition, particularly with respect to scorch protection. Therefore, the second derivatized phenolic antioxidant may be called a “booster” antioxidant. While we do not wish to be bound by any particular theory, the second derivatized phenolic antioxidant is thought to be more reactive than the first derivatized phenolic antioxidant due to less steric hindrance around the phenol moiety and a smaller overall molecular size.

[0072] 【0076】 The second derivatized phenolic antioxidant may include a single derivatized phenolic antioxidant or a combination of two or more derivatized phenolic antioxidants.

[0073] 【0077】 The second derivatized phenolic antioxidant may include mono-hydroxybenzene and / or di-hydroxybenzene. 【0078】Mono-hydroxybenzene may include cross-linked bisphenols, such as sulfur-cross-linked bisphenol or CR2-cross-linked bisphenol. The sulfur-cross-linked bisphenol may include 4,4'-thiobis(2-t-butyl-5-methylphenol) (LOWINOX® TBM-6-CAS96-69-5); and / or 2,2'-thiobis(6-t-butyl-4-methylphenol) (LOWINOX® TBP-6-CAS90-66-4).

[0074] 【0079】 Dihydroxybenzene may also contain 4-tert-butylcatechol (4-TBC) and 2,5-di-tert-amyl-hydroquinone (LOWINOX® AH25-CAS79-74-3).

[0075] 【0080】 A second derivatized phenolic antioxidant, preferably comprising 4-tert-butylcatechol (4-TBC); 2,5-di-tert-amylhydroquinone (LOWINOX® AH25-CAS79-74-3); 4,4'-thiobis(2-t-butyl-5-methylphenol) (LOWINOX® TBM-6-CAS96-69-5); 2,2'-thiobis(6-t-butyl-4-methylphenol) (LOWINOX® TBP-6-CAS90-66-4); and / or a combination of two or more thereof.

[0076] 【0081】 A particularly preferred second derivatized phenolic antioxidant is 4-TBC. 【0082】 Another particularly preferred second derivatized phenolic antioxidant includes LOWINOX® AH25 in combination with LOWINOX® TBM-6 and / or LOWINOX® TBP-6.

[0077] 【0083】The combination of LOWINOX® AH25, LOWINOX® TBM-6 and / or LOWINOX® TBP-6, and phosfit secondary antioxidants has been found to be particularly beneficial for scorch protection and to exhibit remarkably good color stability.

[0078] 【0084】 The second derivatized phenolic antioxidant is solid under ambient conditions, i.e., atmospheric pressure (101.325 kPa) and a temperature of 25°C. 【0085】 The second derivatized phenolic antioxidant may be present in the stabilizing composition in amounts ranging from about 0.1 wt.%, about 0.5 wt.%, about 1 wt.%, or about 5 wt.%, to about 50 wt.%, about 45 wt.%, about 40 wt.%, about 35 wt.%, about 30 wt.%, about 25 wt.%, or about 20 wt.%, based on the total weight of the stabilizing composition.

[0079] 【0086】 For example, the second derivatized phenolic antioxidant may be present in the stabilizing composition in amounts of about 0.1 wt.% to about 50 wt.%, about 0.5 wt.% to about 45 wt.%, about 1 wt.% to about 40 wt.%, about 5 wt.% to about 35 wt.%, about 1 wt.% to about 20 wt.%, or about 5 wt.% to about 20 wt.%, based on the total weight of the stabilizing composition.

[0080] Secondary antioxidant 【0087】 The presence of secondary antioxidants has been found to improve the color stability of the stabilized composition. In particular, the presence of secondary antioxidants has been found to significantly reduce discoloration caused by a second derivatized phenolic antioxidant.

[0081] 【0088】For example, LOWINOX® AH25 is a good scorch inhibitor, but it is known to cause discoloration. To our surprise, the inventors of this invention found that when LOWINOX® AH25 is used in combination with a secondary antioxidant, particularly phosfit, discoloration is significantly reduced. When LOWINOX® AH25 is used in combination with LOWINOX® TBM-6 and / or LOWINOX® TBP-6, as well as the phosfit secondary antioxidant, a synergistic effect is observed, resulting in a further reduction of discoloration.

[0082] 【0089】 The secondary antioxidants include phosphates and / or thioesters. 【0090】 Preferably, the phosphites include one or more alkyl phosphites, and optionally one or more trialkyl phosphites.

[0083] 【0091】 As specific, non-limiting examples, alkyl phosphites include trilauryl phosphite (WESTON® TLP-CAS3076-63-9); triisodecyl phosphite (WESTON® TDP-CAS25448-25-3); triisodecyl phosphite, phenol-free (WESTON® TDPZP-CAS25448-25-3); and tris(dipropylene glycol) phosphite (WESTON® 430-CAS36788-39-3). ); may comprise one or more of the following: Tris(dipropylene glycol) phosphyto, phenol-free (WESTON® 430ZP-CAS36788-39-3); distearyl pentaerythritol diphosphyto (WESTON® 618-CAS3806-34-6); distearyl pentaerythritol diphosphyto, flake (WESTON® 618F-CAS3806-34-6); and / or mixtures of two or more thereof.

[0084] 【0092】 Additionally, or alternatively, the phosphyte may comprise one or more alkyl-aryl phosphytes and / or triaryl phosphytes. 【0093】 As a specific, non-limiting example, the alkyl-aryl phosphites may include butane-1,1-diylbis(2-(tert-butyl)-5-methyl-4,1-phenylene)tetratridecylbis(phosphites) (CAS 13003-12-8).

[0085] 【0094】 As a specific, non-limiting example, triaryl phosfit may include WESTON® 705-CAS939402-02-5. 【0095】 Preferably, the phosfit is substantially phenol-free.

[0086] 【0096】 In this context, "substantially absent" means that if phenol is present, it is in an amount of approximately 1% by weight or less of the phosphine. 【0097】 Certain phosphites are produced from reaction products such as triphenyl phosphites, which result in the formation of phenol byproducts. However, the presence of phenol byproducts in phosphites is undesirable due to the health and safety risks associated with phenol. Therefore, phosphites that are substantially phenol-free offer advantages from a safety standpoint.

[0087] 【0098】 The phosphine may have a melting point of less than approximately 100°C, less than approximately 90°C, less than approximately 80°C, less than approximately 70°C, less than approximately 60°C, or less than approximately 50°C. It is preferable that the phosphine is liquid under ambient conditions, i.e., at atmospheric pressure (101.325 kPa) and a temperature of 25°C.

[0088] 【0099】 In this context, "thioester" refers to a compound that contains both a thio group and an ester group. 【0100】As a specific, non-limiting example, the thioester may include one or more of the following: di(tridecyl)thiodipropionate (NAUGARD® DTDTDP-CAS10595-72-9); distearylthiodipropionate (NAUGARD® DSTDP-CAS693-36-7); dilaurylthiodipropionate (NAUGARD® DLTDP-CAS123-28-4); and / or mixtures of two or more thereof.

[0089] 【0101】 The secondary antioxidant may have a melting point of less than approximately 100°C, less than approximately 90°C, less than approximately 80°C, less than approximately 70°C, less than approximately 60°C, or less than approximately 50°C. 【0102】 The secondary antioxidant may be present in the stabilizing composition in an amount of approximately 0.01 wt.% to approximately 20 wt.%, approximately 0.05 wt.% to approximately 15 wt.%, or approximately 0.1 wt.% to approximately 10 wt.%, based on the total weight of the stabilizing composition.

[0090] Flame retardant blend 【0103】 The stabilizing composition of the present invention may be combined with a flame retardant to form a flame retardant blend.

[0091] 【0104】 Therefore, according to another aspect of the present invention, i. A stabilizing composition defined above according to any aspect of the present invention, ii. Flame retardants and A flame retardant blend containing the above is provided.

[0092] 【0105】 The flame retardant may include a halogenated flame retardant or a non-halogenated flame retardant. 【0106】 Examples of halogenated flame retardants include organic halogen compounds, such as organochlorines including chlorendic acid derivatives and chlorinated paraffins; organobromines such as decabromodiphenyl ether and decabromodiphenylethane; and chlorinated organic phosphate esters such as tris(1,3-dichloro-2-propyl) phosphate and oxydi-2,1-ethanediyl tetrakis(2-chloro-1-methylethyl) phosphate.

[0093] 【0107】 Examples of non-halogenated flame retardants include organophosphorus compounds, such as organophosphate esters including t-butylphenyl diphenyl phosphate, triphenyl phosphate (TPP), resorcinol bis(diphenyl phosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP); phosphonic acid esters such as dimethylmethyl phosphonate (DMMP); and phosphinic acid esters such as aluminum diethyl phosphinate.

[0094] 【0108】 Certain prior art stabilization compositions are known to cause discoloration in flame retardants upon exposure and thermal aging. Conversely, the inventors of the present invention have found that the stabilization compositions of the present invention, when combined with flame retardants, impart only very slight discoloration upon exposure and thermal aging. This is advantageous because it allows the stabilization compositions to be pre-mixed with flame retardants prior to their use in polyols / polyurethanes.

[0095] 【0109】 The stabilizing composition may be present in the flame retardant blend in an amount of about 0.1% to about 20%, about 0.5% to about 15%, or about 1% to about 10% by weight of the flame retardant. 【0110】 The stabilizing compositions or flame retardant blends of the present invention may be effective in stabilizing polyols and / or polyurethanes, particularly polyurethane foams. Polyols and / or polyurethanes can be stabilized against oxidation, heat, and / or radiation (e.g., light, e.g., UV light) induced degradation.

[0096] 【0111】 Accordingly, according to another aspect of the present invention, the use of the stabilizing compositions or flame retardant blends described above for stabilizing polyols and / or polyurethanes is provided.

[0097] 【0112】 According to another aspect of the present invention, Polyols and / or polyurethanes, The stabilizing composition or flame retardant blend described above and A stabilized composition containing the following is provided.

[0098] 【0113】 The polyol may include, for example, polyether polyols and / or polyester polyols. The polyol may also be a precursor of polyurethane. 【0114】 Polyurethane may also be polyurethane foam.

[0099] 【0115】 The stabilizing composition and flame retardant blend of the present invention are 15 kg / m² 3 It was found to be particularly effective in stabilizing low, medium, and high-density polyurethane foams having higher densities.

[0100] 【0116】 The stabilizing composition may be present in the stabilized composition in an amount of about 0.01% to about 10%, about 0.01% to about 5%, about 0.01% to about 3.5%, or about 0.01% to about 2% by weight of the polyol and / or polyurethane.

[0101] 【0117】 The flame retardant blend may be present in the stabilized composition in an amount of about 1% to about 30%, about 5% to about 25%, or about 10% to about 20% by weight of the polyol and / or polyurethane.

[0102] 【0118】 The present invention also provides stabilizing compositions that, when incorporated into a polyurethane foam, cause the foam to undergo a smaller color change ΩE than that of an equivalent foam incorporating an equivalent amount of an industrially available stabilizing composition, such as industrially available stabilizing compositions 1, 2, 3, or 4 specified in the following examples, when subjected to a microwave scorch test. The stabilizing compositions of the present invention are advantageously selected from stabilizing compositions according to any embodiment described above, and details of a suitable microwave scorch test are given in the following examples.

[0103] 【0119】The present invention also provides stabilizing compositions that, when incorporated into polyurethane foams, exhibit a contribution to VOC and / or FOG as measured according to the standard test method VDA278, which is smaller than the contribution shown by equivalent foams incorporating equivalent amounts of industrially available stabilizing compositions, such as industrially available stabilizing compositions 1, 2, 3, or 4 specified in the following examples. The stabilizing compositions of the present invention are advantageously selected from stabilizing compositions according to any embodiment described above.

[0104] 【0120】 The present invention will be described in more detail with reference to the following non-limiting examples, in which the first derivatized phenolic antioxidant described above is referred to as component type a), the second derivatized phenolic antioxidant described above is referred to as component type b), and the secondary antioxidant described above is referred to as component type c). [Examples]

[0105] 【0121】 The individual components of the stabilizing compositions discussed herein are briefly described in Table 1 below. Hereafter, the individual components will be referred to using the names given in the "Component" column.

[0106] [Table 1]

[0107] 【0122】 A stabilized composition was prepared by mixing the relative amounts of the components identified in Table 2.

[0108] [Table 2]

[0109] 【0123】 In addition to the stabilization compositions listed in Table 2, industrially usable stabilization compositions identified in Table 3 were also tested.

[0110] [Table 3]

[0111] Medium density (20~25kg / m 3 Preparation of polyurethane foam 【0124】 For the stabilization compositions of Examples 1-5 and 7, briefly described in Table 2, and Examples A-D, briefly described in Table 3, 0.45 g of the stabilization composition was added to 100 g of 3500 Mw polyol in a 1 liter flask. The mixture was homogenized by stirring at 1900 rpm for 1 minute. To this mixture, 1.1 g of TEGOSTAB® B8229 (Evonik), 0.27 g of a mixture of amine catalysts (3:1 DABCO® 33LV:DABCO® BL11), and 5 g of deionized water were added, and the reaction mixture was stirred for 30 seconds. 0.25 g of tin(II) ethylhexanoate (Aldrich) was immediately added, and the reaction mixture was stirred for a further 15 seconds. 62.7 g of toluene diisocyanate was added to the flask and mixed for 10 seconds. The resulting mixture was quickly poured into an 18cm x 16cm x 16cm wooden box lined with a kraft paper mold, and the internal temperature was monitored during the foaming process.

[0112] Microwave scorch testing 【0125】 For the scorching test, a BP210 / 50 research microwave oven (Microwave Research and Applications Inc.) was used. Once the foam reached its maximum internal temperature, it was immediately removed from the wooden box and placed inside the microwave cavity. The microwave was set to 20% maximum power (approximately 1300W) and operated for the desired time. After microwave irradiation, the foam was removed from the cavity and cured in a convection oven at 95°C for 30 minutes. Once cooled, the foam was cut open and the color of the maximum scorched region was measured using an X-RITE® ColorEye 7000A colorimeter.

[0113] 【0126】 The results of the microwave scorch test are shown in Table 4 below. The results are normalized to the results of Comparative Example D and are expressed as ΩE Ex / ΩE D according to the teachings of US2011 / 0230579, where ΩE is the color change.

[0114] [Table 4]

[0115] 【0127】 The results show that Examples 1-5 and 7, all according to the present invention, outperform the comparative examples in terms of scorch reduction. Gas fading test 【0128】 Regarding the stabilization compositions of Examples 1, 3, 4, 5, and 7, briefly described in Table 2, and Examples A and D, briefly described in Table 3, the term "medium density (20-25 kg / m³)" is used. 3 The foam was prepared as briefly described in the section "Preparation of Polyurethane Foam." The foam was cured at 95°C for 30 minutes and then cooled to room temperature. The foam was cut to prepare a sample with dimensions of 100 mm × 100 mm × 25 mm.

[0116] 【0129】 Samples were tested to determine their resistance to discoloration upon contact with nitrous oxide. The tests were conducted according to the standard test method AATCC164. Color was recorded after 0, 30, and 60 minutes in an oven. Color was measured using an X-RITE® Color i7 colorimeter. The results of the gas discoloration test are shown in Table 5 below.

[0117] [Table 5]

[0118] 【0130】 The results show that all embodiments according to the present invention performed at least as well as the industrially available stabilization compositions of Examples A and D with respect to the overall color change (ΔE) and individual colors, namely a* values ​​(representing color values ​​on a green-to-red scale) and b* values ​​(representing color values ​​on a blue-to-yellow scale). Examples 1, 3, 4, 5, and 7 performed better than the industrially available stabilization compositions.

[0119] High density (40kg / m 3 Preparation of polyurethane foam 【0131】 For the stabilization compositions of Examples 1-5, briefly described in Table 2, and Examples A-D, briefly described in Table 3, 0.9 g of the stabilization composition was added to 200 g of polyol in a 1 liter flask. The mixture was homogenized by stirring at 1900 rpm for 1 minute. To this mixture, 1.2 g of TEGOSTAB® B8229 (Evonik), 0.60 g of a mixture of amine catalysts (3:1 DABCO® 33LV:DABCO® BL11), and 5 g of deionized water were added, and the reaction mixture was stirred for 30 seconds. 0.45 g of tin(II) ethylhexanoate (Aldrich) was immediately added, and the reaction mixture was stirred for a further 15 seconds. 72.2 php of toluene diisocyanate was added to the flask and mixed for 10 seconds. The resulting mixture was quickly poured into an 18 cm × 16 cm × 16 cm wooden box lined with kraft paper, and the internal temperature was monitored during foaming.

[0120] 【0132】 The resulting foam was cured at 95°C for 30 minutes, and then cooled to room temperature. The foam was cut to prepare samples with dimensions of 100 mm × 100 mm × 25 mm. Emission test according to standard test method VDA278 【0133】 The foam samples were tested and emissions determined in accordance with the standard test procedure VDA278, an internationally recognized and standardized test procedure for the quantitative analysis of volatile compounds, published in October 2011 by "Verband Der Automobilindustrie". The results are shown in Table 6 below.

[0121] [Table 6]

[0122] 【0134】 The results show that Examples 1-5 according to the present invention outperform the industrially available stabilization compositions of Examples A-D. The stabilization compositions according to the present invention have a very small contribution to VOCs and a significantly lower contribution to FOG emissions compared to industrially available stabilization compositions, particularly Examples C and D.

[0123] Color stability in non-halogenated flame retardants 【0135】 The color stability of the stabilization compositions of Examples 1, 2, and 6 in flame retardants was tested and compared with the color stability of the industrially available stabilization composition represented by Example D.

[0124] 【0136】 A 3 wt% stabilizing composition was added to a sample of the flame retardant tris(1,3-dichloro-2-propyl) phosphate (TDCPP-CAS13674-87-8). The resulting blend was divided into two separate samples. One sample was stored at room temperature for 10 days, and the other was stored in an oven at 60°C for 10 days. After this, the APHA color value was measured using a LOVIBOND® PFXi-195 colorimeter.

[0125] 【0137】 The results are shown in Table 7 below.

[0126] [Table 7]

[0127] 【0138】 The results show that the stabilization compositions of Examples 1, 2, and 6 are significantly better in terms of color stability in flame retardants compared to the industrially available stabilization composition of Example D (amine-based).

[0128] Color stability of stabilized compositions containing LOWINOX® AH25 【0139】 A stabilized composition containing only LOWINOX® AH25 was prepared by mixing the relative amounts of the components identified in Table 8.

[0129] [Table 8]

[0130] 【0140】 The discoloration of each stabilization composition was examined. 【0141】Each sample of the stabilization composition was prepared under nitrogen and placed in a 40°C oven for the required duration (1 day, 1 month, and 3 months). After the allotted time, the color value was measured using a LOVIBOND® PFXi-195 colorimeter.

[0131] 【0142】 The results are shown in Table 9.

[0132] [Table 9]

[0133] 【0143】 The results show that the stabilized compositions according to the present invention (Examples 9 and 10) have better color stability compared to stabilized compositions that do not contain the phosfit secondary antioxidant. Example 10 highlights the synergistic effect of the combination of LOWINOX® AH25 with LOWINOX® TBM-6 and the phosfit antioxidant, as discoloration is further reduced. This application includes the following aspects: [Section 1] A stabilizing composition for polyols and / or polyurethanes, i. A first derivatized phenolic antioxidant having a molecular weight of at least about 400 g / mol and a melting point of less than about 100°C, ii. A second derivatized phenolic antioxidant having less steric hindrance than the first derivatized phenolic antioxidant and being solid under ambient conditions, iii. Secondary antioxidants containing phosphites and / or thioesters A stabilizing composition containing the following: [Section 2] The stabilizing composition according to claim 1, wherein diphenylamine and / or alkylated diphenylamine are absent. [Section 3] The stabilized composition according to claim 1 or 2, wherein the contribution of the first derivatized phenolic antioxidant to VOCs is less than about 10 ppm, and / or the contribution of the first derivatized phenolic antioxidant to FOGs is less than about 100 ppm. [Section 4] The first derivatized phenolic antioxidant is of formula (I) [ka] [In the formula, n is either 1 or 2. R 1 This is a linear or branched alkyl group having 1 to 30 carbon atoms, which is optionally substituted with one or more ether groups. R 2 and R3 Each of these is independently selected from linear or branched alkyl groups having 1 to 5 carbon atoms. A stabilizing composition according to any one of claims 1 to 3, comprising one or more derivatized phenolic antioxidants. [Section 5] R 2 and R 3 The stabilizing composition according to item 4, wherein both are t-butyl groups. [Section 6] The stabilized composition according to any one of claims 1 to 5, wherein the first derivatized phenolic antioxidant comprises 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, C13-15 alkyl ester; a blend of 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, C13-15 alkyl ester and tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane; octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate; and / or a blend of octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate and tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane. [Section 7] The stabilizing composition according to any one of claims 1 to 6, wherein the first derivatized phenolic antioxidant is present in the stabilizing composition in an amount of about 30 wt.% to about 95 wt.%, about 40 wt.% to about 95 wt.%, about 50 wt.% to about 95 wt.%, or about 60 wt.% to about 90 wt.%, based on the total weight of the stabilizing composition. [Section 8] The stabilizing composition according to any one of claims 1 to 7, wherein the second derivatized phenolic antioxidant has a smaller molecular weight than the first derivatized phenolic antioxidant. [Section 9] The stabilizing composition according to any one of claims 1 to 8, wherein the second derivatized phenolic antioxidant has a molecular weight less than about 400 g / mol. [Section 10] The second derivatized phenolic antioxidant is i. Monohydroxybenzene, optionally cross-linked bisphenol, and / or ii. Dihydroxybenzene A stabilizing composition according to any one of claims 1 to 9, comprising: [Section 11] The stabilizing composition according to any one of claims 1 to 10, wherein the second derivatized phenolic antioxidant is present in the stabilizing composition in an amount of about 0.1 wt.% to about 50 wt.%, about 0.5 wt.% to about 45 wt.%, about 1 wt.% to about 40 wt.%, about 5 wt.% to about 35 wt.%, about 1 wt.% to about 20 wt.%, or about 5 wt.% to about 20 wt.%, based on the total weight of the stabilizing composition. [Section 12] The stabilizing composition according to any one of claims 1 to 11, wherein the phosphi comprises one or more alkyl phosphites, and optionally one or more trialkyl phosphites. [Section 13] The stabilizing composition according to any one of claims 1 to 12, wherein the secondary antioxidant is present in the stabilizing composition in an amount of about 0.01 wt.% to about 20 wt.%, about 0.05 wt.% to about 15 wt.%, or about 0.1 wt.% to about 10 wt.%, based on the total weight of the stabilizing composition. [Section 14] A stabilizing composition according to any one of claims 1 to 13, having a melting point of less than approximately 100°C. [Section 15] The stabilizing composition according to any one of claims 1 to 14, wherein the contribution of the stabilizing composition to VOCs is less than about 20 ppm, less than about 15 ppm, less than about 10 ppm, or less than about 5 ppm. [Section 16] The stabilizing composition according to any one of claims 1 to 15, wherein the contribution of the stabilizing composition to FOG is less than about 200 ppm, less than about 150 ppm, less than about 100 ppm, or less than about 50 ppm. [Section 17] A stabilizing composition for polyols and / or polyurethanes, a) A first derivatized phenolic antioxidant having a molecular weight of at least about 400 g / mol and a melting point of less than about 100°C, which is effective in providing a contribution to VOCs of less than about 10 ppm and / or a contribution to FOG of less than about 100 ppm. b) A second derivatized phenolic antioxidant having less steric hindrance than the first derivatized phenolic antioxidant and being solid under ambient conditions, c) Secondary antioxidants comprising phosphite and / or thioesters A stabilizing composition containing the following: [Section 18] A stabilizing composition for polyols and / or polyurethanes, a) A first derivatized phenolic antioxidant having a contribution to VOCs of less than approximately 10 ppm and / or a contribution to FOG of less than approximately 100 ppm, and a melting point of less than approximately 100°C, b) A second derivatized phenolic antioxidant having less steric hindrance than the first derivatized phenolic antioxidant and being solid under ambient conditions, c) Secondary antioxidants comprising phosphite and / or thioesters A stabilizing composition containing the following: [Section 19] A stabilizing composition according to any one of claims 1 to 18, wherein, when incorporated into a polyurethane foam, the foam undergoes a smaller color change ΩE than that of an equivalent foam incorporating an equivalent amount of an industrially available stabilizing composition (optionally one of industrially available stabilizing compositions 1, 2, 3, or 4) when subjected to a microwave scorch test. [Section 20] A stabilizing composition according to any one of claims 1 to 19, which, when incorporated into a polyurethane foam, exhibits a contribution to VOC and / or FOG measured according to standard test method VDA278, which is smaller than the contribution shown by an equivalent foam incorporating an equivalent amount of an industrially available stabilizing composition (optionally, one of industrially available stabilizing compositions 1, 2, 3, or 4). [Section 21] i. A stabilizing composition according to any one of items 1 to 20, ii. Flame retardants and A flame retardant blend containing this ingredient. [Section 22] Use of a stabilizing composition according to any one of items 1 to 20, or a flame retardant blend according to item 21, for stabilizing polyols and / or polyurethanes. [Section 23] Polyols and / or polyurethanes, A stabilizing composition according to any one of items 1 to 20, or a flame retardant blend according to item 21 and A stabilized composition containing the following: [Section 24] The polyurethane is polyurethane foam, and optionally the polyurethane foam is 15 kg / m³ 3 A stabilized composition according to item 23, having a higher density. [Section 25] The stabilized composition according to claim 23 or 24, wherein the stabilizing composition is present in the stabilized composition in an amount of about 0.01% to about 10%, about 0.01% to about 5%, about 0.01% to about 3.5%, or about 0.01% to about 2% by weight of the polyol and / or polyurethane.

Claims

[Claim 1] A stabilizing composition for polyols and / or polyurethanes, i. A first derivatized phenolic antioxidant having a molecular weight of at least 400 g / mol and a melting point of less than 100°C, ii. A second derivatized phenolic antioxidant comprising sulfur-crosslinked bisphenol and / or dihydroxybenzene, wherein the second derivatized phenolic antioxidant has less steric hindrance than the first derivatized phenolic antioxidant and is solid under ambient conditions, iii. Secondary antioxidants containing phosphite and / or thioesters A stabilizing composition containing the following: [Claim 2] The stabilizing composition according to claim 1, wherein diphenylamine and / or alkylated diphenylamine are absent. [Claim 3] The stabilized composition according to claim 1 or 2, wherein the contribution of the first derivatized phenolic antioxidant to VOCs is less than 10 ppm, and / or the contribution of the first derivatized phenolic antioxidant to FOGs is less than 100 ppm. [Claim 4] The first derivatized phenolic antioxidant is of formula (I) 【Chemistry 1】 [In the formula, n is either 1 or 2, R １ This is a linear or branched alkyl group having 1 to 30 carbon atoms, which is optionally substituted with one or more ether groups. R ２ and R ３ Each of these is independently selected from linear or branched alkyl groups having 1 to 5 carbon atoms. A stabilizing composition according to any one of claims 1 to 3, comprising one or more derivatized phenolic antioxidants. [Claim 5] R ２ and R ３ The stabilizing composition according to claim 4, wherein both are t-butyl groups. [Claim 6] The stabilizing composition according to any one of claims 1 to 5, wherein the first derivatized phenolic antioxidant comprises a blend of 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, C13-15 alkyl ester; 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, C13-15 alkyl ester and tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane; octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate; and / or a blend of octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate and tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane. [Claim 7] The stabilizing composition according to any one of claims 1 to 6, wherein the first derivatized phenolic antioxidant is present in the stabilizing composition in an amount of 30 wt.% to 95 wt.% based on the total weight of the stabilizing composition. [Claim 8] The stabilizing composition according to any one of claims 1 to 7, wherein the second derivatized phenolic antioxidant has a smaller molecular weight than the first derivatized phenolic antioxidant. [Claim 9] The stabilizing composition according to any one of claims 1 to 8, wherein the second derivatized phenolic antioxidant has a molecular weight less than 400 g / mol. [Claim 10] The stabilizing composition according to any one of claims 1 to 9, wherein the second derivatized phenolic antioxidant comprises dihydroxybenzene. [Claim 11] The stabilizing composition according to any one of claims 1 to 10, wherein the second derivatized phenolic antioxidant is present in the stabilizing composition in an amount of 0.1 wt.% to 50 wt.% based on the total weight of the stabilizing composition. [Claim 12] The stabilizing composition according to any one of claims 1 to 11, wherein the phosphito comprises one or more alkyl phosphito, and optionally one or more trialkyl phosphito. [Claim 13] The stabilizing composition according to any one of claims 1 to 12, wherein the secondary antioxidant is present in the stabilizing composition in an amount of 0.01 wt.% to 20 wt.% based on the total weight of the stabilizing composition. [Claim 14] A stabilizing composition according to any one of claims 1 to 13, having a melting point of less than 100°C. [Claim 15] The stabilizing composition according to any one of claims 1 to 14, wherein the contribution of the stabilizing composition to VOCs is less than 20 ppm. [Claim 16] The stabilizing composition according to any one of claims 1 to 15, wherein the contribution of the stabilizing composition to FOG is less than 200 ppm. [Claim 17] A stabilizing composition for polyols and / or polyurethanes, a) A first derivatized phenolic antioxidant having a molecular weight of at least 400 g / mol and a melting point of less than 100°C, which is effective in providing a contribution to VOCs of less than 10 ppm and / or a contribution to FOG of less than 100 ppm. b) A second derivatized phenolic antioxidant comprising sulfur-crosslinked bisphenol and / or dihydroxybenzene, wherein the second derivatized phenolic antioxidant has less steric hindrance than the first derivatized phenolic antioxidant and is solid under ambient conditions, c) Secondary antioxidants comprising phosphite and / or thioesters A stabilizing composition containing the following: [Claim 18] A stabilizing composition for polyols and / or polyurethanes, a) A first derivatized phenolic antioxidant having a contribution to VOCs of less than 10 ppm and / or a contribution to FOG of less than 100 ppm, and a melting point of less than 100°C, b) A second derivatized phenolic antioxidant comprising sulfur-crosslinked bisphenol and / or dihydroxybenzene, wherein the second derivatized phenolic antioxidant has less steric hindrance than the first derivatized phenolic antioxidant and is solid under ambient conditions, c) Secondary antioxidants comprising phosphite and / or thioesters A stabilizing composition containing the following: [Claim 19] The stabilizing composition according to any one of claims 1 to 18, which, when incorporated into a polyurethane foam, causes a smaller color change ΔE in the polyurethane foam than that of an equivalent foam incorporating an equivalent amount of a 7:1:1 blend consisting of hindered phenol (CAS No. 125643-61-0), phosfit (CAS No. 145650-60-8), and 3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one (CAS No. 216698-07-6) when subjected to a microwave scorch test. [Claim 20] The stabilizing composition according to any one of claims 1 to 19, which, when incorporated into a polyurethane foam, exhibits a contribution to VOCs and / or FOGs, as measured according to standard test method VDA 278, that is smaller than the contribution shown by an equivalent foam incorporating an equivalent amount of a 7:1:1 blend consisting of hindered phenol (CAS No. 125643-61-0), phosfit (CAS No. 145650-60-8), and 3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one (CAS No. 216698-07-6). [Claim 21] i. A stabilizing composition according to any one of claims 1 to 20, ii. Flame retardants and A flame retardant blend containing [unspecified ingredient]. [Claim 22] Use of a stabilizing composition according to any one of claims 1 to 20, or a flame retardant blend according to claim 21, for stabilizing a polyol and / or polyurethane. [Claim 23] Polyols and / or polyurethanes, A stabilizing composition according to any one of claims 1 to 20, or a flame retardant blend according to claim 21 A stabilized composition containing the following: [Claim 24] The polyurethane is a polyurethane foam, and optionally the polyurethane foam is 15 kg / m³ ３ The stabilized composition according to claim 23, having a higher density. [Claim 25] The stabilized composition according to claim 23 or 24, wherein the stabilizing composition is present in the stabilized composition in an amount of 0.01% to 10% by weight of the polyol and / or polyurethane.

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