An anti-aging agent composition and corresponding polyol or polyurethane composition

Abstract

The present application relates to an anti-aging agent composition and the corresponding polyol or polyurethane composition, the anti-aging agent composition comprising: i) alkylated diphenylamine, and ii) hindered phenolic antioxidant of formula IV. The alkylated diphenylamine of the present application has a lower proportion of lower molecular weight components, a higher proportion of high molecular weight components, more excellent heat weight loss resistance and thermal stability and low volatility; both can improve the long-term thermal stability and reduce high-temperature degradation, and can also reduce the high-temperature volatilization of small molecular weight components to reduce the sponge FOG value.

Description

Technical Field

[0001] This application relates to the field of anti-aging polymer materials, specifically to an anti-aging agent composition suitable for polymer polyols such as polyether polyols, polyester polyols or polyurethanes, and the corresponding polyol or polyurethane compositions. Background Technology

[0002] Polyurethane is a class of polymers with urethane or urethane bonds, typically produced through the reaction of isocyanates and polyols. Polyurethane is commonly used in the manufacture of foams, coatings, fibers, molded products, elastic components, and adhesives. Downstream sectors of polyurethane are increasingly focused on environmental protection and health. Taking polyurethane foam as an example, the VOC and FOG values ​​of the foam are important parameters for evaluating and measuring environmental indicators, and the market demands lower VOC and FOG values ​​for polyurethane materials. The contribution to FOG value comes not only from small molecules generated during the aging of the foam itself and the foaming process, but also from the small molecules produced by the additives themselves or from their degradation.

[0003] During long-term storage of polyol raw materials or polyurethane, it has been found that materials with a specific amount of added antioxidant exhibit a decline in antioxidant performance over time. This reduces the antioxidant protection of the polyol raw materials, which in turn reduces the antioxidant performance in downstream polyurethane, leading to problems such as decreased physical properties of the polyurethane materials. Examples include polyurethane sponge core burning, difficulty in molding polyurethane products, yellowing and brittleness of polyurethane elastomers, and reduced tensile properties of polyurethane fibers.

[0004] There is a need in this field for anti-aging compositions of polymeric polyols such as polyether polyols, polyester polyols, or polyurethanes. Summary of the Invention

[0005] In a first aspect, this application provides an anti-aging agent composition comprising:

[0006] i) Alkylated diphenylamine, wherein the alkylated diphenylamine comprises:

[0007] 90.0~99.9% of the dialkyldiphenylamine of formula II, based on the total weight of the alkylated diphenylamine;

[0008]

[0009] R1 is independently selected from straight-chain or branched C9 alkyl groups;

[0010] ii) Hindered phenolic antioxidants of formula IV

[0011]

[0012] R2 is selected from methyl or tert-butyl, and R3 is selected from C8 to C18 alkyl or mixed alkyl.

[0013] Secondly, this application provides a polymeric polyol or polyurethane composition comprising a polymeric polyol or polyurethane and an alkylated diphenylamine, wherein the alkylated diphenylamine comprises:

[0014] 90.0~99.9% of the dialkyldiphenylamine of formula II, based on the total weight of the alkylated diphenylamine;

[0015]

[0016] R1 is independently selected from straight-chain or branched C9 alkyl groups.

[0017] Thirdly, this application also provides a polymeric polyol or polyurethane composition comprising a polymeric polyol or polyurethane and the anti-aging agent composition of the first aspect.

[0018] Fourthly, this application provides a polymeric polyol or polyurethane article formed from the polymeric polyol or polyurethane compositions of the second and third aspects of this application.

[0019] Fifthly, this application also relates to the use of alkylated diphenylamine in the preparation of polymeric polyols or polyurethane articles, wherein the alkylated diphenylamine comprises:

[0020] 90.0~99.9% of the dialkyldiphenylamine of formula II, based on the total weight of the alkylated diphenylamine;

[0021]

[0022] R1 is independently selected from straight-chain or branched C9 alkyl groups.

[0023] The alkylated diphenylamine of this application reduces the proportion of lower molecular weight components and increases the proportion of high molecular weight components, resulting in superior resistance to heat loss, thermal stability, and low volatility. It improves both its own long-term thermal stability and reduces high-temperature degradation, while also reducing the high-temperature volatilization of low molecular weight components, thereby lowering the FOG value of the sponge. When used alone or in combination with hindered phenolic antioxidants in polymer polyols, it can significantly improve the antioxidant properties, thermal stability, and long-term storage stability of the polymer polyols. It can also improve the process stability of polymer polyols during application, maintaining good processability, i.e., preserving the activity, foaming stability, and molding stability of polymer polyols such as polyether polyols or polyester polyols, and polyurethane sponges. Furthermore, it can improve the anti-burning properties and product stability of downstream applications of polymer polyols (such as polyurethane sponges) during foaming. The low volatility and thermal stability of the antioxidants help reduce the FOG value of polyurethane sponges, such as automotive and home textiles, which is more beneficial for protecting human health. Moreover, the alkylated diphenylamine and the anti-aging agent composition containing it of this application are in liquid form, adaptable to various addition methods, facilitating uniform mixing and easy processing and use. Attached Figure Description

[0024] Figure 1 Photographs of the polyurethane foam obtained by adding the anti-aging agent of Comparative Example 7 after core-sintering test.

[0025] Figure 2 Photographs of the polyurethane foam obtained by adding the anti-aging agent of Example 15 (control) after a core-sintering test;

[0026] Figure 3 Photographs of the polyurethane foam obtained by adding the anti-aging agent of Example 16 (control) after a core-sintering test;

[0027] Figure 4 Photographs of the polyurethane foam obtained by adding the anti-aging agent of Example 17 after a core-sintering test;

[0028] Figure 5 Photographs of the polyurethane foam obtained by adding the anti-aging agent of Example 18 after a core-sintering test;

[0029] Figure 6 Photographs of the polyurethane foam obtained by adding the anti-aging agent of Example 19 after a core-sintering test;

[0030] Figure 7 Photographs of the polyurethane foam obtained by adding the anti-aging agent of Example 20 after a core-burning test. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with embodiments. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of this application in any way.

[0032] In a first aspect, this application provides an anti-aging agent composition comprising:

[0033] i) Alkylated diphenylamine, wherein the alkylated diphenylamine comprises:

[0034] 90.0~99.9% of the dialkyldiphenylamine of formula II, based on the total weight of the alkylated diphenylamine;

[0035]

[0036] R1 is independently selected from straight-chain or branched C9 alkyl groups;

[0037] ii) Hindered phenolic antioxidants of formula IV

[0038]

[0039] R2 is selected from methyl or tert-butyl, and R3 is selected from C8 to C18 alkyl or mixed alkyl.

[0040] In some embodiments, the alkylated diphenylamine further includes:

[0041] 0-15% of a monoalkyl diphenylamine of formula I, based on the total weight of the alkylated diphenylamine; and / or

[0042] 0-10% of the trialkyldiphenylamine of formula III, based on the total weight of the alkylated diphenylamine;

[0043] .

[0044] In some embodiments, R1 is a straight-chain or branched C9 alkyl group. Examples of branched C9 alkyl groups include isononyl, methyl octyl, dimethyl heptyl, propyl hexyl, methyl ethyl hexyl, ethyl heptyl, trimethyl hexyl, tetramethyl pentyl, dimethyl ethyl pentyl, diethyl pentyl, butyl pentyl, etc.

[0045] In some embodiments, the alkylated diphenylamine comprises:

[0046] 0-10% of a monoalkyl diphenylamine of formula I, based on the total weight of the alkylated diphenylamine;

[0047] 92.0~99.9% of the dialkyldiphenylamine of formula II, based on the total weight of the alkylated diphenylamine;

[0048] 1-5% of the trialkyldiphenylamine of formula III, based on the total weight of the alkylated diphenylamine.

[0049] The anti-aging agent composition of this application comprises alkylated diphenylamine having a high content of bis-C9 alkyl-substituted diphenylamine (based on the total weight of the alkylated diphenylamine, the bis-C9 alkyl-substituted diphenylamine of formula II accounts for more than 90%) and a low content of mono-C9 alkyl-substituted and tri-substituted diphenylamine (based on the total weight of the alkylated diphenylamine, the mono-C9 alkyl-substituted diphenylamine of formula I and the tri-substituted diphenylamine of formula III account for less than 10%). The inventors of this application have discovered that, compared to commercially available products with conventional low-content bis-C9 alkyl-substituted diphenylamine, such alkylated diphenylamine exhibits superior resistance to heat loss, thermal stability, and low volatility. Furthermore, when used alone in polymer polyols, or in combination with hindered phenolic antioxidants, it can effectively improve the thermal stability and long-term storage stability of polyols. It is particularly suitable for protecting polyols that require long-term heating during transportation and storage, such as those undergoing prolonged sea transport or storage at high temperatures in tank trucks or storage tanks. Additionally, when used alone in polyurethanes, or in combination with hindered phenolic antioxidants, it provides good foaming stability for polyurethane foams, maintaining good resilience and storage stability, meeting conventional usage requirements. The low volatility and thermal stability of the antioxidants help reduce the FOG value of polyurethane foams, such as automotive and home textiles, further protecting human health and aligning with industry trends. Moreover, the anti-aging agent composition of this application is in liquid form, facilitating smooth delivery and uniform dispersion during use, and helping to maintain the quality stability of polymer polyols and polyurethane products.

[0050] In some embodiments, the amount of dialkyldiphenylamine of Formula II, based on the total weight of the alkylated diphenylamine, can be 90.0% to 99.9%, for example, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, etc. In some embodiments, the amount of monoalkyldiphenylamine of Formula I, based on the total weight of the alkylated diphenylamine, is 0% to 15%, for example, less than 12%, less than 10%, less than 8%, less than 6%, less than 5%, less than 4%; or more than 0.05%, or more than 0.1%, or more than 0.5%, etc. In some embodiments, the amount of trialkyldiphenylamine of Formula III, based on the total weight of the alkylated diphenylamine, is 0% to 10%, for example, 1% to 8%, 1% to 6%, 1% to 5%, 1% to 4%, etc.

[0051] The alkylated diphenylamine of this application can be obtained by reacting tripropylene (nonene) with diphenylamine. For example, tripropylene (nonene) and diphenylamine can be reacted in the presence of Lewis acids (such as metal halides such as aluminum trichloride or zinc chloride, or acidic catalysts such as sulfuric acid, phosphoric acid, or acidic clay, etc.) to obtain a reaction product containing a dialkyldiphenylamine of formula II (see JP Japanese Patent Application Publication No. 2-188555). US5449829 also discloses another method for preparing alkylated diphenylamine, which involves reacting ammonia with an alkyl-substituted phenol in the presence of a catalyst (such as a Pd / C catalyst) and an alkyl-substituted cyclohexanone, thereby obtaining a reaction product containing a dialkyldiphenylamine of formula II. CN106944142A also discloses a method for preparing nonyldiphenylamine amine antioxidants. It should be noted that the reaction products obtained by these methods, in addition to containing a dialkyldiphenylamine of formula II, also contain a certain amount of a monoalkyldiphenylamine of formula I and a trialkyldiphenylamine of formula III. Furthermore, the content of dialkyldiphenylamine in Formula II is typically low, generally not exceeding 80 wt%, while the content of monoalkyldiphenylamine in Formula I is relatively high (generally exceeding 15 wt%). As mentioned above, such products with low content of bis-C9 alkyl-substituted diphenylamine and high content of monoalkyldiphenylamine suffer from defects in thermal stability and long-term thermal stability under high-temperature conditions, and are not suitable for direct use as the alkylated diphenylamine of this application (which has a high content of bis-C9 alkyl-substituted diphenylamine (based on the total weight of the alkylated diphenylamine, bis-C9 alkyl-substituted diphenylamine of Formula II accounts for more than 90%) and a low content of mono-C9 alkyl-substituted and tri-substituted diphenylamine (based on the total weight of the alkylated diphenylamine, mono-C9 alkyl-substituted diphenylamine of Formula I and tri-substituted diphenylamine of Formula III account for less than 10%)). The resulting reaction contents need to be treated to increase the content of bis-C9 alkyl-substituted diphenylamine of Formula II and reduce the total content of mono-C9 alkyl-substituted and tri-C9 alkyl-substituted diphenylamines. For example, the reaction contents can be treated using known techniques such as distillation (e.g., thin-film evaporation, rectification, or flash evaporation), dialysis, and chromatographic separation to control the amount of dialkyldiphenylamine of Formula II, monoalkyldiphenylamine of Formula I, and trialkyldiphenylamine of Formula III to reach the ranges defined in this application, thereby obtaining the alkylated diphenylamine of this application. Preferably, the monosubstituted and trisubstituted components can be removed from the reaction contents by rectification to obtain the alkylated diphenylamine of this application, which has a high content of bis-C9 alkyl-substituted diphenylamine (based on the total weight of the alkylated diphenylamine, bis-C9 alkyl-substituted diphenylamine of Formula II accounts for more than 90%) and a low content of mono-C9 alkyl-substituted and trisubstituted diphenylamine (based on the total weight of the alkylated diphenylamine, mono-C9 alkyl-substituted diphenylamine of Formula I and trisubstituted diphenylamine of Formula III account for less than 10%). During the rectification process, the content of each component can be monitored in real time until the content of each component meets the requirements, at which point the rectification process is stopped.The content of each component in the alkylated diphenylamine of this application can be determined by methods such as UPLC and GC.

[0052] The anti-aging composition further comprises a hindered phenolic antioxidant, such as the hindered phenolic antioxidant of formula IV. In some embodiments, the hindered phenolic antioxidant is selected from one or more of the following: 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (isooctyl ester), a mixture of C7-C9 alcohols of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, a mixture of C12-C14 alcohols of 3,5-di-tert-butyl-4-hydroxyphenylpropionate, a mixture of C13-C15 alcohols of 3,5-di-tert-butyl-4-hydroxyphenylpropionate, a mixture of C14-C16 alcohols of 3,5-di-tert-butyl-4-hydroxyphenylpropionate, and octadecyl alcohol ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0053] In some embodiments, based on the total weight of the anti-aging agent composition, the amount of the alkylated diphenylamine is 10-70 wt% (e.g., 15-60 wt%, 20-50 wt%, or 25-40 wt%), and the amount of the hindered phenolic antioxidant is 30-90 wt% (e.g., 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 75 wt%, 80 wt%, or 85 wt%). The hindered phenolic antioxidant and the alkylated aniline antioxidant work synergistically, exhibiting a significant synergistic effect, which can substantially improve the antioxidant properties, thermal stability, and long-term storage stability of the polymer polyol.

[0054] In some embodiments, the anti-aging agent composition may further include phosphite antioxidants and / or free radical scavengers. Hindered phenolic antioxidants, alkyl aniline antioxidants, phosphite antioxidants, and free radical scavengers can be used synergistically to significantly improve the antioxidant properties and thermal stability of polymer polyols, as well as their long-term storage stability; effectively inhibit yellowing and reddening, and improve the storage stability of polyurethane products such as polyurethane foam under natural light and ultraviolet light, significantly enhancing their long-term storage stability.

[0055] For example, the phosphite antioxidant may be selected from one or more of tri(nonylphenyl) phosphite, diphenyl isodecyl phosphite, diphenyl diisodecyl phosphite, triphenyl phosphite, diisopropanol ether diphenyl phosphite, tris(mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl) phosphite (CAS: 939402-02-5), triisodecyl phosphite, and pentaerythritol diisodecyl diphosphite. In some embodiments, the amount of the phosphite antioxidant is 0-40 wt%, for example 10-40 wt%, for example 5-10 wt%, based on the total weight of the anti-aging agent composition. For example, the free radical scavenger may be selected from one or more of 3,4-di-tert-butyl-5-(2,4-dimethylphenyl)benzofuran-2(3H)-one and bis(octadecylhydroxylamine). In some embodiments, the amount of the free radical scavenger is 0-15 wt%, for example 2-10 wt%, or 5-8 wt%, based on the total weight of the anti-aging agent composition.

[0056] Secondly, this application provides a polymeric polyol or polyurethane composition comprising a polymeric polyol or polyurethane and an alkylated diphenylamine.

[0057] The alkylated diphenylamine includes:

[0058] 90.0~99.9% of the dialkyldiphenylamine of formula II, based on the total weight of the alkylated diphenylamine;

[0059]

[0060] R1 is independently selected from straight-chain or branched C9 alkyl groups.

[0061] As described above, the alkylated diphenylamine of this application can be used alone in polymer polyols or polyurethanes, exhibiting excellent long-term stability and minimal loss of stability within the polymer polyol or polyurethane materials. It should be noted that the embodiments of the alkylated diphenylamine described in the first aspect also apply to the second aspect of this application, and will not be repeated here.

[0062] In some embodiments, the amount of alkylated diphenylamine used is 0.5‰ to 10‰, for example 1‰ to 8‰, 2‰ to 6‰, etc., based on the total weight of the polymer polyol or polyurethane.

[0063] Furthermore, as described above, the alkylated diphenylamine of this application can be used in combination with hindered phenolic antioxidants, etc., for use in polymeric polyols or polyurethanes. A third aspect of this application relates to a polymeric polyol or polyurethane composition comprising: a polymeric polyol or polyurethane, and an anti-aging agent composition of the first aspect of this application.

[0064] In some embodiments, the amount of the anti-aging agent composition is 1‰ to 40‰, for example 1‰ to 20‰, or for example 5‰ to 10‰, based on the total weight of the polymeric polyol or polyurethane.

[0065] For the second and third aspects of this application, polymeric polyols include polyether polyols, polyester polyols, etc.; these compounds generally have a molecular weight of 300-10000 and are polyhydroxy compounds, especially compounds containing 2 to 8 hydroxyl groups, preferably polyether polyols containing 2 to 4 hydroxyl groups.

[0066] The polyurethane can be obtained from polyol precursors, such as by reacting polyether polyols or polyester polyols with terminal hydroxyl groups with aliphatic or aromatic polyisocyanates. Methods for preparing polyurethanes from polyols are well known in the art and will not be described further here.

[0067] The alkylated diphenylamine of this application reduces the proportion of lower molecular weight components and increases the proportion of high molecular weight components, resulting in superior resistance to heat loss, thermal stability, and low volatility. It improves both its own long-term thermal stability and reduces high-temperature degradation, while also reducing the high-temperature volatilization of low molecular weight components, thereby lowering the FOG value of the sponge. When used alone or in combination with hindered phenolic antioxidants in polymer polyols, it can significantly improve the antioxidant properties, thermal stability, and long-term storage stability of the polymer polyols. It can also improve the process stability of polymer polyols during application, maintaining good processability, i.e., preserving the activity, foaming stability, and molding stability of polymer polyols such as polyether polyols or polyester polyols, and polyurethane sponges. Furthermore, it can improve the anti-burning properties and product stability of downstream applications of polymer polyols (such as polyurethane sponges) during foaming. The low volatility and thermal stability of the antioxidants help reduce the FOG value of polyurethane sponges, such as automotive and home textiles, which is more beneficial for protecting human health. Moreover, the alkylated diphenylamine and the anti-aging agent composition containing it of this application are in liquid form, adaptable to various addition methods, facilitating uniform mixing and easy processing and use.

[0068] Fourthly, this application also relates to a polymeric polyol or polyurethane article formed from the polymeric polyol or polyurethane compositions of the second and third aspects of this application. The polymeric polyol article may include polyurethane foam, elastomer, coating, adhesive, and excipients, etc.

[0069] Polymer polyols are core raw materials in the polyurethane industry, primarily used to prepare flexible, semi-rigid, and high-resilience foams. For example, the polymer polyol compositions of this application can be used to form polyurethane foams, reducing their FOG value and thus better protecting human health. The polymer polyol compositions of this application can also be used to prepare elastomers, coatings, adhesives, and excipients.

[0070] Polyurethane products include rigid foams and flexible foams, and can include coatings, adhesives, sealants, elastomer formulations (e.g., thermoplastic elastomers), etc. The polyurethane products of this application can be prepared from a polymer polyol composition containing the alkylated diphenylamine or antioxidant composition of this application, or they can be prepared by adding the alkylated diphenylamine or antioxidant composition of this application after reacting the polymer polyol with a polyisocyanate to obtain polyurethane. Polyurethane products obtained through both methods are within the scope of protection of this application.

[0071] This application also relates to the use of the alkylated diphenylamine of this application in the preparation of polymeric polyols or polyurethane articles. The alkylated diphenylamine is as described in the first aspect of this application and will not be repeated here. The alkylated diphenylamine can be used alone or in combination with other components in the preparation of polymeric polyols or polyurethane articles. For example, the alkylated diphenylamine or an anti-aging agent composition containing the alkylated diphenylamine can be added to a polymeric polyol or polyurethane composition to mold it into a variety of polymeric polyol or polyurethane articles. Alternatively, the alkylated diphenylamine or an anti-aging agent composition containing the alkylated diphenylamine can be added after the preparation of the polymeric polyol or polyurethane, and then molded into a variety of polymeric polyol or polyurethane articles.

[0072] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with embodiments and accompanying drawings. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of this application in any way.

[0073] Raw materials used in the examples

[0074]

[0075] Examples 1-4 Preparation of liquid alkyl diphenylamine antioxidants

[0076] Example 1

[0077] 60.00 g of diphenylamine, 44.76 g of tripropylene, and 8 g of acidic clay catalyst were placed together in a 500 ml four-necked flask. The mixture was heated to 160 °C and refluxed. The remaining 89.52 g of tripropylene (total tripropylene 134.28 g, molar ratio of diphenylamine to tripropylene 1.0:3.0) was slowly added dropwise over a period of 4 h. The reaction temperature was controlled at 158–162 °C. After the addition was complete, the mixture was refluxed for 20–24 h. After the reaction was complete, the temperature was lowered to 90 °C and the acidic clay catalyst was removed by filtration. Activated carbon and activated clay were added for decolorization at 80 °C for 1–2 h, and the decolorizing agent was removed by filtration. A vacuum distillation apparatus was used, with the vacuum level controlled to <5 mmHg, and the temperature was raised to 180 °C. Unreacted tripropylene was collected until no fraction remained. The resulting product was labeled as sample-1. The composition of the product was determined by GC, and the weight percentage of each component, calculated as the total weight of nonyldiphenylamine, dinonyldiphenylamine, and trinonyldiphenylamine, is shown in Table 1.

[0078] Example 2

[0079] 60.00 g of diphenylamine, 44.76 g of tripropylene, and 8 g of acidic clay catalyst were placed together in a 500 ml four-necked flask. The mixture was heated to 160 °C and refluxed. The remaining 134.28 g of tripropylene (total tripropylene 179.04 g, molar ratio of diphenylamine to tripropylene 1.0:4.0) was slowly added dropwise over a period of 4 hours. The reaction temperature was controlled at 158–162 °C. After the addition was complete, the mixture was refluxed for 20–24 hours. After the reaction was complete, the temperature was lowered to 90 °C, and the acidic clay catalyst was removed by filtration. Activated carbon and activated clay were added for decolorization at 80 °C for 1–2 hours, and the decolorizing agent was removed by filtration. A vacuum distillation apparatus was used, with the vacuum level controlled to <5 mmHg, and the temperature was raised to 180 °C. Unreacted tripropylene was collected until no fraction remained. The resulting product was labeled as sample-2. The composition of the product was determined by GC, and the weight percentage of each component, calculated as the total weight of nonyldiphenylamine, dinonyldiphenylamine, and trinonyldiphenylamine, is shown in Table 1.

[0080] Example 3

[0081] 60.00 g of diphenylamine, 44.76 g of tripropylene, and 8 g of acidic clay catalyst were placed together in a 500 ml four-necked flask. The mixture was heated to 160 °C and refluxed. The remaining 179.04 g of tripropylene (total tripropylene 223.80 g, molar ratio of diphenylamine to tripropylene 1.0:5.0) was slowly added dropwise over 6 hours, with the reaction temperature controlled at 158–162 °C. After the addition was complete, the mixture was refluxed for 22–26 hours. After the reaction, the temperature was lowered to 90 °C, and the acidic clay catalyst was removed by filtration. Activated carbon and activated clay were added for decolorization, and the decolorization temperature was controlled at 80 °C for 1–2 hours. The decolorizing agent was then removed by filtration. Using a vacuum distillation apparatus, with the vacuum level controlled <5 mmHg, the mixture was heated to 180 °C, and the unreacted tripropylene was collected until no fraction remained. The resulting product was labeled sample-3. The composition of the product was determined by GC, and the weight percentage of each component, calculated as the total weight of nonyldiphenylamine, dinonyldiphenylamine, and trinonyldiphenylamine, is shown in Table 1.

[0082] Example 4

[0083] 60.00 g of diphenylamine, 44.76 g of tripropylene, and 8 g of acidic clay catalyst were placed together in a 500 ml four-necked flask. The mixture was heated to 160 °C and refluxed. The remaining 313.32 g of tripropylene (total tripropylene 358.09 g, molar ratio of diphenylamine to tripropylene 1.0:8.0) was slowly added dropwise over 8 hours at a temperature of 158–162 °C. After the addition was complete, the mixture was refluxed for 24–30 hours. After the reaction, the temperature was lowered to 90 °C, and the acidic clay catalyst was removed by filtration. Activated carbon and activated clay were added for decolorization at 80 °C for 1–2 hours, and the decolorizing agent was removed by filtration. A vacuum distillation apparatus was used, with the vacuum level controlled to <5 mmHg, and the temperature was raised to 180 °C. Unreacted tripropylene was collected until no fraction remained. The resulting product was labeled sample-4. The composition of the product was determined by GC, and the weight percentage of each component, calculated as the total weight of nonyldiphenylamine, dinonyldiphenylamine, and trinonyldiphenylamine, is shown in Table 1.

[0084] Table 1. Composition of the alkyl diphenylamine antioxidant samples in Examples 1-4

[0085]

[0086] Example 5

[0087] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0088] It consists of 33 parts of aromatic amine antioxidant sample-1 and 67 parts of hindered phenolic antioxidant 1135R.

[0089] Example 6

[0090] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0091] It consists of 33 parts of aromatic amine antioxidant sample-2 and 67 parts of hindered phenolic antioxidant 1135R.

[0092] Example 7

[0093] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0094] It consists of 33 parts of aromatic amine antioxidant sample-3 and 67 parts of hindered phenolic antioxidant 1135R.

[0095] Example 8

[0096] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0097] It consists of 33 parts of aromatic amine antioxidant sample-4 and 67 parts of hindered phenolic antioxidant 1135R.

[0098] Example 9 (Control)

[0099] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0100] By weight percentage, it consists of 65 parts hindered phenolic antioxidant 1135R, 20 parts aromatic amine antioxidant 5057, and 15 parts phosphite antioxidant DHOP.

[0101] Example 10 (Control)

[0102] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0103] By weight percentage, it consists of 65 parts hindered phenolic antioxidant 1135R, 20 parts aromatic amine antioxidant 5067, and 15 parts phosphite antioxidant DHOP.

[0104] Example 11

[0105] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0106] By weight percentage, it consists of 65 parts hindered phenolic antioxidant 1135R, 20 parts aromatic amine antioxidant sample-1, and 15 parts phosphite antioxidant DHOP.

[0107] Example 12

[0108] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0109] By weight percentage, it consists of 65 parts hindered phenolic antioxidant 1135R, 20 parts aromatic amine antioxidant sample-2, and 15 parts phosphite antioxidant DHOP.

[0110] Example 13

[0111] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0112] By weight percentage, it consists of 65 parts hindered phenolic antioxidant 1135R, 20 parts aromatic amine antioxidant sample-3, and 15 parts phosphite antioxidant DHOP.

[0113] Example 14

[0114] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0115] By weight percentage, it consists of 65 parts hindered phenolic antioxidant 1135R, 20 parts aromatic amine antioxidant sample-4, and 15 parts phosphite antioxidant DHOP.

[0116] Table 2 Composition of Examples 9-14

[0117]

[0118] Example 15 (Control)

[0119] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0120] By weight percentage, it consists of 59 parts hindered phenolic antioxidant 1135R, 29 parts aromatic amine antioxidant 5057, and 12 parts free radical scavenging antioxidant HP136.

[0121] Example 16 (Control)

[0122] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0123] By weight percentage, it consists of 59 parts hindered phenolic antioxidant 1135R, 29 parts aromatic amine antioxidant 5067, and 12 parts free radical scavenging antioxidant HP136.

[0124] Example 17

[0125] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0126] By weight percentage, it consists of 59 parts hindered phenolic antioxidant 1135R, 29 parts aromatic amine antioxidant sample-1, and 12 parts free radical scavenging antioxidant HP136.

[0127] Example 18

[0128] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0129] By weight percentage, it consists of 59 parts hindered phenolic antioxidant 1135R, 29 parts aromatic amine antioxidant sample-2, and 12 parts free radical scavenging antioxidant HP136.

[0130] Example 19

[0131] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0132] By weight percentage, it consists of 59 parts hindered phenolic antioxidant 1135R, 29 parts aromatic amine antioxidant sample-3, and 12 parts free radical scavenging antioxidant HP136.

[0133] Example 20

[0134] This embodiment provides an anti-aging agent composition for polyether polyols and polyurethanes:

[0135] By weight percentage, it consists of 59 parts hindered phenolic antioxidant 1135R, 29 parts aromatic amine antioxidant sample-4, and 12 parts free radical scavenging antioxidant HP136.

[0136] Table 3 Composition of Examples 15-20

[0137]

[0138] Comparative Example 1

[0139] This comparative example provides a blank polyether polyol without any added antioxidants as a blank control group.

[0140] Comparative Example 2

[0141] This comparative example provides an anti-aging agent for polyether polyols and polyurethanes, namely hindered phenolic antioxidant 1135R.

[0142] Comparative Example 3

[0143] This comparative example provides an anti-aging agent for polyether polyols and polyurethanes, namely aromatic amine antioxidant 5057.

[0144] Comparative Example 4

[0145] This comparative example provides an anti-aging agent for polyether polyols and polyurethanes, namely aromatic amine antioxidant 5067.

[0146] Comparative Example 5

[0147] This comparative example provides an anti-aging agent for polyether polyols and polyurethanes, namely the phosphite antioxidant DHOP.

[0148] Comparative Example 6

[0149] This comparative example provides an anti-aging agent composition for polyether polyols and polyurethanes: consisting of 33 parts of amine antioxidant 5057 and 67 parts of hindered phenolic antioxidant 1135R.

[0150] Comparative Example 7

[0151] This comparative example provides an anti-aging agent composition for polyether polyols and polyurethanes: consisting of 33 parts of amine antioxidant 5067 and 67 parts of hindered phenolic antioxidant 1135R.

[0152] Performance testing

[0153] 1. Performance Test 1 - Thermal Stability of Additives

[0154] The thermal stability and volatility resistance of the additives were determined using a thermogravimetric analyzer (TGA) under the following conditions:

[0155] The TGA test parameters were: temperature range 25℃~400℃, heating rate 10K / min, purge gas nitrogen 50mL / min, and sample mass 15±0.1mg. The test results are shown in Table 4. It can be seen that the thermogravimetric stability (i.e., thermal stability) of Examples 1-4 is more stable than that of the conventional products, namely Comparative Examples 3 and 4.

[0156] Table 4 Thermal stability test of additives

[0157]

[0158] 2. Performance Test 2 - Long-term thermal stability of the additive under continuous high temperature environment

[0159] In practical applications, many polymer polyol manufacturers have export businesses. The polymer polyols will undergo a sea transport process that takes 2-3 months, and the storage environment is complex and variable, with continuous high temperatures of 40-70°C. During this process, the polymer polyols and the antioxidants contained therein will be consumed, which may lead to a decrease in the activity of the polymer polyols in subsequent applications and unstable application effects.

[0160] To simulate this application, taking polyether polyol as an example, anti-aging agents provided in some of the above-mentioned examples and comparative examples were added to the polyether polyol (F3050) at 5‰ of its total mass. A blank group without added anti-aging agents was used as a control. After thorough mixing, the mixture was placed in a 70°C constant temperature forced-air oven for thermal aging for 30, 60, and 90 days, and the remaining antioxidant content in the polyether polyol was tested. The test results are shown in Table 5. It can be seen that Examples 1-4 are close to Comparative Examples 3 and 4 in short-term aging, with a slightly higher residual amount. However, in long-term aging, Examples 1-4 show more obvious long-term thermal stability, with a significantly higher residual amount of additives than the comparative examples, and the amount increases with the increase of the di-C9 alkyl-substituted diphenylamine component.

[0161] Table 5. Long-term thermal stability test of additives under continuous high temperature environment

[0162]

[0163] 3. Performance Test 3 - Polyurethane Sponge FOG Value Test

[0164] Test Method: Polyurethane flexible foam was prepared according to the following formulations: 100 parts by weight of high-resilience polyether 330N, 52 parts by weight of TDI, 4 parts by weight of foaming agent (water), 1.1 parts by weight of silicone foaming agent, 0.2 parts by weight of organotin catalyst, 0.15 parts by weight of amine catalyst, and 1.5‰ by weight of anti-aging agent provided in Examples 1-4 and Comparative Examples 1-5. The foamed foam sample was placed at the bottom of a fogging glass cup and secured with a sample pressing ring. The fogging cup was placed in a constant-temperature oil bath. Its upper surface was sealed with an oil-resistant and high-temperature-resistant fluororubber sealing ring. Above the sealing ring was the fogging carrier (aluminum foil), followed by filter paper and a cooling plate. At high temperatures, the volatile substances in the sample would evaporate more rapidly and condense on the fogging carrier cooled by the cooling plate above the sealing ring. The gas evaporated from the heated sponge sample in the fogging cup condensed on a low-temperature aluminum foil. The weight change of the aluminum foil before and after condensation (the aluminum foil needs to be placed in a desiccator for adjustment after fogging) was measured to determine the weight of the sample's atomized-condensate. The test results are shown in Table 6. It can be seen that compared to Comparative Example 1, Examples 1-4 effectively reduced the FOG value of the polyurethane sponge, i.e., it has lower volatility and better antioxidant properties, which increase with the increase of the di-C9 alkyl-substituted diphenylamine component. Moreover, compared to conventional antioxidants / anti-aging agents (Comparative Examples 2-4), Examples 1-4 can obtain polyurethane sponges with lower FOG values; compared to the high molecular weight polymeric phosphite antioxidant DHOP (Comparative Example 5), Examples 1-4 can obtain polyurethane sponges with comparable FOG values.

[0165] Table 6. FOG value test of polyurethane foam

[0166]

[0167] 4. Performance Test: Determination of the Initial Oxidation Temperature of 4-Polyether Polyol

[0168] The anti-aging agents provided in the above examples and comparative examples were added to the polyether polyol (F3050) at a total mass of 4.5‰. After mixing evenly, the mixture was placed in a 70°C constant temperature forced-air drying oven for 60 days. A blank group without added anti-aging agent was used as a control. The initial oxidation temperature of the polyether polyol was determined by differential scanning calorimetry (DSC) under the following conditions:

[0169] The DSC test parameters were 40℃~350℃, heating rate 20K / min, purge gas oxygen 50mL / min, protective gas nitrogen 100mL / min, and sample mass 6.5±0.5mg. The results are shown in Table 7. It can be seen that Examples 1-4 effectively protected polyether polyols from rapid oxidation, demonstrating superior thermal stability and antioxidant effects compared to conventional products (Comparative Examples 2-5). The effects were further enhanced when combined with phenolic antioxidants, phosphite antioxidants, and free radical scavengers.

[0170] Table 7. Test of initial oxidation temperature of polyether polyols

[0171]

[0172] 5. Performance Test 5 - Polyurethane Sponge Core Sintering Test

[0173] According to the total mass of polyether (F3050), the anti-aging agents provided in the above examples and comparative examples were added to the polyether at 4.5‰ of the total mass. After mixing evenly, the mixture was placed in a 70°C constant temperature forced-air drying oven for 60 days. Polyurethane flexible foam sponges were prepared according to the following formulations: 100 parts by mass of flexible foam polyether, 52 parts by mass of TDI, 4 parts by mass of foaming agent water, 1.1 parts by mass of organosilicon foaming agent, 0.2 parts by mass of organotin catalyst, 0.15 parts by mass of amine catalyst, and 4.5‰ by mass of polyether, as provided in Examples 15-20 and Comparative Example 7, for foaming. After foaming, the sponge was placed in a 700W microwave oven at P60 setting for 4 minutes for aging. The core condition of the sponge was observed. The smaller the core area, the better the anti-core burning effect. The results are as follows. Figures 1-7 As shown:

[0174] in, Figure 1 Photographs of the polyurethane foam obtained by adding the anti-aging agent of Comparative Example 7 after core-sintering test.

[0175] Figure 2 and Figure 3 Photographs of polyurethane foams obtained by adding the anti-aging agents of Example 15 (control) and Example 16 (control) after core-sintering tests;

[0176] Figures 4-7 The images show the polyurethane foam obtained by adding the anti-aging agents from Examples 17-20 after core-sintering tests.

[0177] It can be seen that the anti-aging agent compositions of Examples 17-20 can effectively improve the core burning of polyurethane sponge, and the effect is better than that of conventional products (Examples 15 / 16); the effect is even better when combined with phenolic antioxidants, phosphite antioxidants and free radical scavengers.

[0178] As can be seen from the above description, the embodiments of this application achieve the following technical effects:

[0179] The alkylated diphenylamine of this application has a high content of bis-C9 alkyl-substituted diphenylamine (based on at least 90% of the total mass of the antioxidant composition of C9 alkyl-substituted diphenylamine and 0-10% of mono-C9 alkyl-substituted and tri-substituted diphenylamine), which has superior heat loss resistance, thermal stability and low volatility compared to conventional low-C9 content products on the market.

[0180] The alkylated diphenylamine of this application, used alone or in combination with phenolic antioxidants, can effectively improve the thermal stability and long-term storage stability of polymer polyols. It is particularly suitable for protecting polymer polyols that require long-term heating during transportation and storage, such as those undergoing prolonged sea transport or storage at high temperatures in tank trucks or storage tanks. Furthermore, in downstream applications, it provides excellent foaming stability for polyurethane foams, maintaining good resilience and storage stability in foam products, meeting conventional usage requirements. The low volatility and thermal stability of the antioxidants help reduce the FOG value of polyurethane foams, such as automotive and home textile foams, thus protecting human health and aligning with industry trends. The liquid state facilitates smooth transport and uniform dispersion during use, contributing to the stability of both the polymer polyol and polyurethane product quality.

[0181] The preferred embodiments of this application have been described in detail above; however, this application is not limited thereto. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, including combining various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in this application and are all within the protection scope of this application.

Claims

1. An anti-aging agent composition comprising: i) Alkylated diphenylamine, wherein The alkylated diphenylamine comprises: 90.0~99.9% of the dialkyldiphenylamine of formula II, based on the total weight of the alkylated diphenylamine; 0-15% of a monoalkyl diphenylamine of formula I, based on the total weight of the alkylated diphenylamine; and 0-10% of the trialkyldiphenylamine of formula III, based on the total weight of the alkylated diphenylamine; R1 is independently selected from straight-chain or branched C9 alkyl groups; ii) Hindered phenolic antioxidants, wherein the hindered phenolic antioxidants are selected from one or more of the following: 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (isooctyl ester), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate C7~C9 alcohol mixture ester, 3,5-di-tert-butyl-4-hydroxyphenylpropionate C12~C14 alcohol mixture ester, 3,5-di-tert-butyl-4-hydroxyphenylpropionate C13~C15 alcohol mixture ester, 3,5-di-tert-butyl-4-hydroxyphenylpropionate C14~C16 alcohol mixture ester, and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol ester.

2. The anti-aging agent composition according to claim 1, wherein, The alkylated diphenylamine comprises: Based on the total weight of the alkylated diphenylamine, 0-10% of a monoalkyl diphenylamine of formula I; Based on the total weight of the alkylated diphenylamine, 92.0% to 99.9% of the dialkyl diphenylamine of formula II; Based on the total weight of the alkylated diphenylamine, 1 to 5% of the trialkyldiphenylamine of formula III.

3. The anti-aging agent composition according to claim 1, wherein, Based on the total weight of the anti-aging agent composition, the amount of the alkylated diphenylamine is 10-70%, and the amount of the hindered phenolic antioxidant is 30-90%.

4. The anti-aging agent composition according to any one of claims 1-3, wherein, The anti-aging agent composition further includes phosphite antioxidants and / or free radical scavengers; Wherein, based on the total weight of the anti-aging agent composition, the amount of the phosphite antioxidant is 10-40%, and the amount of the free radical scavenger is 0-15%.

5. The anti-aging agent composition according to claim 4, wherein, The phosphite antioxidant is selected from one or more of the following: tri(nonylphenyl) phosphite, diphenyl isodecyl phosphite, diphenyl diisodecyl phosphite, triphenyl phosphite, diisopropanol ether diphenyl phosphite, tris(mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl) phosphite, triisodecyl phosphite, and pentaerythritol diisodecyl diphosphite; and / or The free radical scavenger is selected from one or more of 3,4-di-tert-butyl-5-(2,4-dimethylphenyl)benzofuran-2(3H)-one and dioctadecylhydroxylamine.

6. A polymeric polyol or polyurethane composition comprising: Polymer polyols or polyurethanes, and Alkylated diphenylamine, wherein, The alkylated diphenylamine comprises: 90.0~99.9% of the dialkyldiphenylamine of formula II, based on the total weight of the alkylated diphenylamine; 0-15% of a monoalkyl diphenylamine of formula I, based on the total weight of the alkylated diphenylamine; and 0-10% of the trialkyldiphenylamine of formula III, based on the total weight of the alkylated diphenylamine; R1 is independently selected from straight-chain or branched C9 alkyl groups.

7. The polymeric polyol or polyurethane composition according to claim 6, wherein, The alkylated diphenylamine comprises: Based on the total weight of the alkylated diphenylamine, 0-10% of a monoalkyl diphenylamine of formula I; Based on the total weight of the alkylated diphenylamine, 92.0% to 99.9% of the dialkyldiphenylamine of formula II; and Based on the total weight of the alkylated diphenylamine, 1 to 5% of the trialkyldiphenylamine of formula III.

8. The polymer polyol or polyurethane composition according to claim 6, wherein, The amount of alkylated diphenylamine used is 0.5‰ to 20‰, based on the total weight of the polymer polyol or polyurethane.

9. A polymeric polyol or polyurethane composition comprising: Polymer polyols or polyurethanes, and The anti-aging composition according to any one of claims 1-5.

10. The polymeric polyol or polyurethane composition according to claim 9, wherein, The amount of the anti-aging agent composition is 1‰ to 40‰ based on the total weight of the polymer polyol or polyurethane.

11. A polymeric polyol or polyurethane article formed from any one of the polymeric polyol or polyurethane compositions of claims 6-10.

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