Anti-aging agent composition and corresponding polyol or polyurethane composition

Abstract

The invention relates to an anti-aging agent composition and a corresponding polyol or polyurethane composition. The anti-aging agent composition comprises: i) alkylated diphenylamine, and ii) a hindered phenol antioxidant of formula IV. According to the alkylated diphenylamine, the proportion of low-molecular-weight components is reduced, the proportion of high-molecular-weight components is increased, and the alkylated diphenylamine has more excellent heat weight loss resistance, heat stability and low volatility; the long-term thermal stability of the sponge can be improved, high-temperature degradation is reduced, and high-temperature volatilization of small-molecular-weight components can be reduced, so that the FOG value of the sponge is reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polymer material anti-aging, in particular to an anti-aging agent composition suitable for polymer polyol, such as polyether polyol, polyester polyol or polyurethane, and a corresponding polyol or polyurethane composition. BACKGROUND

[0002] Polyurethane is a kind of polymer with urethane or urea bond, which is generally prepared by the reaction of isocyanate and polyol. Polyurethane is generally used to manufacture foams, coatings, fibers, molded products, elastic components, adhesives, etc. The downstream field of polyurethane pays more and more attention to environmental protection and health. For example, the VOC and FOG values of polyurethane sponge are important parameters for evaluating and measuring environmental protection indicators, and the market demands polyurethane materials with lower VOC values and lower FOG values. Among them, the contribution of FOG value comes from small molecule substances generated by aging of the sponge itself, small molecule substances generated in the foaming process, and small molecule substances generated by degradation of the additives added in the sponge.

[0003] During the long-term storage of polyol raw materials or polyurethane, it is found that the antioxidant performance of the material with a specific amount of antioxidant will decrease over time, the antioxidant protection performance of the polyol raw material will also decrease, and then the antioxidant performance in the downstream polyurethane will decrease, resulting in problems such as decrease of physical properties of polyurethane material, etc. For example, polyurethane sponge burning core, polyurethane product not easy to shape, polyurethane elastomer yellowing and brittle, decrease of tensile properties of polyurethane fiber, etc.

[0004] There is a need in the art for an anti-aging agent composition suitable for polymer polyol, such as polyether polyol, polyester polyol or polyurethane. SUMMARY

[0005] In a first aspect, the present application provides an anti-aging agent composition comprising: i) an alkylated diphenylamine, wherein the alkylated diphenylamine comprises: 90.0-99.9% of a dialkyl diphenylamine of formula II, based on the total weight of the alkylated diphenylamine; each R1is independently selected from linear or branched C9alkyl; ii) a hindered phenolic antioxidant of formula IV R2is selected from methyl or tert-butyl, and R3is selected from C8-C18alkyl or mixed alkyl.

[0006] In a second aspect, the present application provides a polyol or polyurethane composition comprising a polyol or polyurethane, and an alkylated diphenylamine, wherein the alkylated diphenylamine comprises: 90.0-99.9% of a dialkyl diphenylamine of Formula II, based on the total weight of the alkylated diphenylamine; each R1is independently selected from linear or branched C9alkyl.

[0007] In a third aspect, the present application also provides a polyol or polyurethane composition comprising a polyol or polyurethane, and the anti-aging agent composition of the first aspect.

[0008] In a fourth aspect, the present application provides a polyol or polyurethane article formed from the polyol or polyurethane composition of the second and third aspects of the present application.

[0009] In a fifth aspect, the present application also relates to the use of an alkylated diphenylamine in the preparation of a polyol or polyurethane article, wherein the alkylated diphenylamine comprises: 90.0-99.9% of a dialkyl diphenylamine of Formula II, based on the total weight of the alkylated diphenylamine; each R1is independently selected from linear or branched C9alkyl.

[0010] The alkylated diphenylamine of the present application has a reduced proportion of lower molecular weight components and an increased proportion of high molecular weight components, and has more excellent heat weight loss resistance and thermal stability and low volatility; it can not only improve its own long-term thermal stability and reduce high-temperature degradation, but also reduce the high-temperature volatilization of small molecular weight components and thus reduce the FOG value of the sponge. When it is used alone or in combination with a hindered phenolic antioxidant in a polyol, it can significantly improve the antioxidation and thermal stability of the polyol, as well as the long-term storage stability; it can also improve the process stability of the polyol when it is applied, and maintain good processability, i.e., maintain the activity, foaming stability of the polyol such as a polyether polyol or a polyester polyol, the forming stability of a polyurethane sponge, etc.; it can also improve the anti-core burning property and product stability of the polyol downstream application product (such as a polyurethane sponge) when it is foamed, and the low volatility and thermal stability of the antioxidant are conducive to reducing the FOG value of the polyurethane sponge such as a car sponge or a home sponge, and are more conducive to protecting human health. Moreover, the alkylated diphenylamine of the present application and the anti-aging agent composition comprising the same are in a liquid state, can be adapted to various addition modes, are conducive to uniform mixing, and are convenient to process and use. BRIEF DESCRIPTION OF DRAWINGS

[0011] Figure 1Post core burn test photograph of polyurethane sponge obtained by adding the anti-aging agent of Comparative Example 7; Figure 2 Post core burn test photograph of polyurethane sponge obtained by adding the anti-aging agent of Example 15 (control); Figure 3 Post core burn test photograph of polyurethane sponge obtained by adding the anti-aging agent of Example 16 (control); Figure 4 Post core burn test photograph of polyurethane sponge obtained by adding the anti-aging agent of Example 17; Figure 5 Post core burn test photograph of polyurethane sponge obtained by adding the anti-aging agent of Example 18; Figure 6 Post core burn test photograph of polyurethane sponge obtained by adding the anti-aging agent of Example 19; Figure 7 Post core burn test photograph of polyurethane sponge obtained by adding the anti-aging agent of Example 20. DETAILED DESCRIPTION

[0012] In order to make the purposes, technical solutions, and advantages of the present application clearer, the present application is further described in detail below with reference to the embodiments. The specific embodiments described herein are only used to explain the present application and do not constitute any limitation on the present application.

[0013] In a first aspect, the present application provides an anti-aging agent composition comprising: i) an alkylated diphenylamine, wherein the alkylated diphenylamine comprises: 90.0-99.9% of a dialkyl diphenylamine of Formula II, based on the total weight of the alkylated diphenylamine; each R1is independently selected from linear or branched C9alkyl; ii) a hindered phenolic antioxidant of Formula IV R2is selected from methyl or tert-butyl, and R3is selected from C8-C18alkyl or mixed alkyl.

[0014] In some embodiments, the alkylated diphenylamine further comprises: 0-15% of a monoalkyl diphenylamine of Formula I, based on the total weight of the alkylated diphenylamine; and / or 0-10% of a trialkyl diphenylamine of Formula III, based on the total weight of the alkylated diphenylamine; .

[0015] In some embodiments, R1is a linear or branched C9alkyl group. Examples of branched C9alkyl groups include isononyl, methyloctyl, dimethylheptyl, propylhexyl, methylethylhexyl, ethylheptyl, trimethylhexyl, tetramethylpentyl, dimethylethylpentyl, diethylpentyl, butylpentyl, and the like.

[0016] In some embodiments, the alkylated diphenylamine comprises: 0-10% monoalkyldiphenylamine of Formula I, based on the total weight of the alkylated diphenylamine; 92.0-99.9% dialkyldiphenylamine of Formula II, based on the total weight of the alkylated diphenylamine; 1-5% trialkyldiphenylamine of Formula III, based on the total weight of the alkylated diphenylamine.

[0017] The anti-aging agent composition of the present application comprises an alkylated diphenylamine having a high content of bis-C9alkyl-substituted diphenylamine (bis-C9alkyl-substituted diphenylamine of Formula II accounts for more than 90% based on the total weight of the alkylated diphenylamine) and a low content of mono-C9alkyl-substituted and tri-substituted diphenylamine (mono-C9alkyl-substituted diphenylamine of Formula I and tri-substituted diphenylamine of Formula III accounts for less than 10% based on the total weight of the alkylated diphenylamine). The inventors of the present application have found that, compared with conventional products on the market having a low content of bis-C9alkyl-substituted diphenylamine, such alkylated diphenylamine has more excellent heat weight loss resistance, thermal stability and low volatility. When used alone in a polyol or in combination with a hindered phenolic antioxidant in a polyol, it can effectively improve the thermal stability and long-term storage stability of the polyol, and is particularly suitable for protecting polyols that need to be heated for a long time during transportation and storage, such as conditions that need to undergo sea transportation for a long time, or environments that need to undergo high tank or storage temperature for a long time. In addition, when used alone in a polyurethane or in combination with a hindered phenolic antioxidant in a polyurethane, it can provide good foaming stability for polyurethane sponge, the sponge product maintains good resilience and storage stability, can meet conventional use requirements, and the low volatility and thermal stability of the antioxidant are conducive to reducing the FOG value of polyurethane sponge such as automotive sponge and home sponge, are more conducive to protecting human health, and are more in line with the development trend of the industry. At the same time, the anti-aging agent composition of the present application is in a liquid state, which is conducive to smooth transportation and uniform dispersion during use, and is conducive to maintaining the quality stability of the polyol and polyurethane products.

[0018] In some embodiments, the amount of dialkyl diphenylamine of Formula II can be 90.0 to 99.9%, e.g., 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, etc., based on the total weight of the alkylated diphenylamine. In some embodiments, the amount of monoalkyl diphenylamine of Formula I is 0 to 15%, e.g., 12% or less, 10% or less, 8% or less, 6% or less, 5% or less, 4% or less; or 0.05% or more, or 0.1% or more, or 0.5% or more, etc., based on the total weight of the alkylated diphenylamine. In some embodiments, the amount of trialkyl diphenylamine of Formula III is 0 to 10%, e.g., 1 to 8%, 1 to 6%, 1 to 5%, 1 to 4%, etc., based on the total weight of the alkylated diphenylamine.

[0019] The alkylated diphenylamine of the present application can be obtained by reacting tripropylene (nonene) and diphenylamine. For example, tripropylene (nonene) and diphenylamine can be reacted in the presence of a Lewis acid (e.g. metal halide such as aluminum trichloride or zinc chloride or an acidic catalyst such as sulfuric acid, phosphoric acid or an acidic clay, etc.) to obtain a reaction content comprising dialkyl diphenylamine of formula II (see JP Kokai Hei 2-188555). US5449829 also discloses another method for preparing alkylated diphenylamine, which comprises reacting ammonia with alkyl-substituted phenol in the presence of a catalyst (e.g. Pd / C catalyst) and alkyl-substituted cyclohexanone, i.e. a reaction content comprising dialkyl diphenylamine of formula II can be obtained. CN106944142A also discloses a method for preparing nonyl diphenylamine amine antioxidant. It is to be noted that the reaction content obtained by these methods contains dialkyl diphenylamine of formula II, monoalkyl diphenylamine of formula I and trialkyl diphenylamine of formula III. Moreover, the content of dialkyl diphenylamine of formula II is usually not high, generally not more than 80 wt%, and the content of monoalkyl diphenylamine of formula I is relatively high (generally more than 15 wt%). As mentioned above, such a product of low content of double C9 alkyl-substituted diphenylamine and high content of monoalkyl diphenylamine has defects in thermal stability and long-term thermal stability at high temperature, and is not suitable for direct use as the alkylated diphenylamine of the present application (which has a high content of double C9 alkyl-substituted diphenylamine (more than 90% of the double C9 alkyl-substituted diphenylamine of formula II based on the total weight of the alkylated diphenylamine) and a low content of mono- and tri-substituted diphenylamine (less than 10% of the mono-substituted diphenylamine of formula I and the tri-substituted diphenylamine of formula III based on the total weight of the alkylated diphenylamine)). The obtained reaction content needs to be treated to increase the content of double C9 alkyl-substituted diphenylamine of formula II and reduce the total content of mono- and tri-substituted diphenylamine. For example, the reaction content can be treated by known techniques such as distillation (e.g. thin film evaporation, rectification or flash evaporation, etc.), dialysis, chromatographic separation, etc. to control the amount of dialkyl diphenylamine of formula II and the amount of monoalkyl diphenylamine of formula I and trialkyl diphenylamine of formula III within the above ranges defined in the present application, i.e. to obtain the alkylated diphenylamine of the present application. Preferably, the reaction content can be treated by rectification to remove the mono- and tri-substituted components therein, thereby obtaining the alkylated diphenylamine of the present application, which has a high content of double C9 alkyl-substituted diphenylamine (more than 90% of the double C9 alkyl-substituted diphenylamine of formula II based on the total weight of the alkylated diphenylamine) and a low content of mono- and tri-substituted diphenylamine (less than 10% of the mono-substituted diphenylamine of formula I and the tri-substituted diphenylamine of formula III based on the total weight of the alkylated diphenylamine). During the rectification process, the content of each component can be detected in real time, and the rectification process is stopped until the content of each component meets the requirements.The content of each component in the alkylated diphenylamine of the present application can be determined by methods such as UPLC and GC.

[0020] The anti-aging agent composition also comprises a hindered phenolic antioxidant, such as a hindered phenolic antioxidant of Formula IV. In some embodiments, the hindered phenolic antioxidant is selected from one or more of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid (iso)octyl ester, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid C7-C9 alcohol mixed ester, 3,5-di-tert-butyl-4-hydroxybenzylpropionic acid C12-C14 alcohol mixed ester, 3,5-di-tert-butyl-4-hydroxybenzylpropionic acid C13-C15 alcohol mixed ester, 3,5-di-tert-butyl-4-hydroxybenzylpropionic acid C14-C16 alcohol mixed ester, and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid stearyl ester.

[0021] In some embodiments, the amount of alkylated diphenylamine is 10-70 wt% (e.g., 15-60 wt%, 20-50 wt%, or 25-40 wt%, etc.) and the amount of 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%, etc.), based on the total weight of the anti-aging agent composition. The combination of the hindered phenolic antioxidant and the alkylated aniline antioxidant has a significant synergistic effect, which can significantly improve the antioxidant properties and thermal stability of the polymer polyol, as well as long-term storage stability.

[0022] In some embodiments, the anti-aging agent composition can also include a phosphite antioxidant and / or a radical scavenger. The combination of the hindered phenolic antioxidant, the alkylated aniline antioxidant, the phosphite antioxidant, and the radical scavenger has a significant synergistic effect, which can significantly improve the antioxidant properties and thermal stability of the polymer polyol, as well as long-term storage stability; effectively inhibits yellowing and reddening, improves the storage stability of polyurethane products such as polyurethane sponges under natural light and ultraviolet light, and significantly improves their long-term storage stability.

[0023] For example, the phosphite antioxidant can be selected from one or more of tris(nonylphenyl) phosphite, diphenyl monoisodecyl phosphite, monophenyl diisodecyl phosphite, triphenyl phosphite, diisopropyl 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 pentaerythrityl 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 radical scavenger can be selected from one or more of 3,4-di-tert-butyl-5-(2,4-dimethylphenyl)benzofuran-2(3H)-one and dioctadecyl hydroxylamine. In some embodiments, the amount of the radical scavenger is 0-15 wt%, for example 2-10 wt%, 5-8 wt%, based on the total weight of the anti-aging agent composition.

[0024] In a second aspect, the present application provides a polymeric polyol or polyurethane composition comprising a polymeric polyol or polyurethane, and an alkylated diphenylamine, wherein the alkylated diphenylamine comprises: 90.0~99.9% of the dialkyl diphenylamine of Formula II, based on the total weight of the alkylated diphenylamine; each R1is independently selected from linear or branched C9alkyl.

[0025] As mentioned above, the alkylated diphenylamine of the present application can be used alone in the polymeric polyol or polyurethane, with the advantage of good long-term stability and less loss in the polymeric polyol or polyurethane material. It is to be noted that the embodiments of the alkylated diphenylamine in the first aspect are also applicable to the second aspect of the present application, which will not be repeated here.

[0026] In some embodiments, the amount of the alkylated diphenylamine is 0.5‰~10‰, for example 1‰~8‰, 2‰~6‰, etc., based on the total weight of the polymeric polyol or polyurethane.

[0027] Moreover, as mentioned above, the alkylated diphenylamine of the present application can be used in combination with a hindered phenolic antioxidant, etc., in the polymeric polyol or polyurethane. The third aspect of the present application relates to a polymeric polyol or polyurethane composition comprising: a polymeric polyol or polyurethane, and the anti-aging agent composition of the first aspect of the present application.

[0028] In some embodiments, the anti-aging agent composition is used in an amount of 1 ‰ to 40 ‰, for example 1 ‰ to 20 ‰, for example 5 ‰ to 10 ‰, based on the total weight of the polymeric polyol or polyurethane.

[0029] For the second and third aspects of the present application, the polymeric polyol includes polyether polyols, polyester polyols, etc.; such compounds generally have a molecular weight of 300 to 10,000 and are polyhydric compounds, especially compounds containing 2 to 8 hydroxyl groups, preferably polyether polyols containing 2 to 4 hydroxyl groups.

[0030] The polyurethane can be obtained from a polyol precursor, for example by reacting a polyether polyol or polyester polyol containing a hydroxyl group at the end thereof with an aliphatic or aromatic polyisocyanate, i.e. the corresponding polyurethane can be obtained. The method for preparing polyurethane from a polyol is well known in the art and will not be described here.

[0031] The alkylated diphenylamine of the present application has a reduced proportion of lower molecular weight components and an increased proportion of high molecular weight components, and has more excellent thermal weight loss resistance and thermal stability and low volatility; it can not only improve its own long-term thermal stability and reduce high-temperature degradation, but also reduce the high-temperature volatilization of small molecular weight components to reduce the FOG value of the sponge. When it is used alone or in combination with a hindered phenolic antioxidant in a polymeric polyol, it can significantly improve the antioxidation and thermal stability of the polymeric polyol, as well as the long-term storage stability; it can also improve the process stability of the polymeric polyol when it is applied, maintaining good processability, i.e. maintaining the activity, foaming stability of the polymeric polyol such as a polyether polyol or a polyester polyol, the forming stability of the polyurethane sponge, etc.; it can also improve the anti-core burning property and product stability of the polymeric polyol downstream application product (such as a polyurethane sponge) when it is foamed, and the low volatility and thermal stability of the antioxidant are conducive to reducing the FOG value of the polyurethane sponge such as a car sponge and a home sponge, and are more conducive to protecting human health. Moreover, the alkylated diphenylamine of the present application and the anti-aging agent composition containing the same are in a liquid state, can be adapted to various adding modes, are conducive to uniform mixing, and are convenient to process and use.

[0032] In a fourth aspect, the present application also relates to a polymeric polyol or polyurethane product formed from the polymeric polyol or polyurethane composition of the second and third aspects of the present application. The polymeric polyol product can include a polyurethane foam, an elastomer, a coating, an adhesive, an excipient, etc.

[0033] The polymeric polyol is a core raw material in the polyurethane industry, and is mainly used for preparing soft, semi-rigid and high-resilience foams. For example, the polymeric polyol composition of the present application can be used to form a polyurethane foam, which can reduce its FOG value and is more conducive to protecting human health. The polymeric polyol composition of the present application can also be used to prepare an elastomer, a coating, an adhesive, an excipient, etc.

[0034] Polyurethane articles include rigid foams as well as flexible foams, and can include coatings, adhesives, sealants, elastomeric formulations (e.g., thermoplastic elastomers), and the like. The polyurethane articles of the present application can be prepared from a polymeric polyol composition containing the alkylated diphenylamine or antioxidant composition of the present application, or the alkylated diphenylamine or antioxidant composition of the present application can be added after the polymeric polyol has been reacted with a polyisocyanate to form the polyurethane. Both of these methods of preparing polyurethane articles are within the scope of the present application.

[0035] The present application also relates to the use of the alkylated diphenylamine of the present application in the preparation of a polymeric polyol or polyurethane article. The alkylated diphenylamine is as described in the first aspect of the present application, and will not be repeated here. The alkylated diphenylamine can be used alone or in combination with other components in the preparation of a polymeric polyol or polyurethane article. For example, the alkylated diphenylamine or an antioxidant composition containing the alkylated diphenylamine can be added to a polymeric polyol or polyurethane composition, and formed into a variety of polymeric polyol or polyurethane articles. Alternatively, the alkylated diphenylamine or an antioxidant composition containing the alkylated diphenylamine can be added after the polymeric polyol or polyurethane has been prepared, and then formed into a variety of polymeric polyol or polyurethane articles.

[0036] For the purpose of clarity, technical solutions and advantages of the present application, the present application is further described in detail below in combination with the embodiments and drawings. The specific embodiments described herein are only used to explain the present application, and are not used to constitute any limitation on the present application.

[0037] Raw materials used in the examples

[0038] Example 1-4 Preparation of liquid alkylated diphenylamine antioxidant Example 1 Diphenylamine 60.00 g, 44.76 g of tripropylene and 8 g of acidic clay catalyst were placed in a 500 ml four-necked flask, and the temperature was raised to 160°C and refluxed. The remaining tripropylene 89.52 g (total tripropylene 134.28 g, the molar ratio of diphenylamine and tripropylene was 1.0:3.0) was slowly added dropwise, the dropwise time was controlled for 4 h, and the reaction temperature was controlled at 158~162°C. After the dropwise addition was completed, the reaction was refluxed for 20~24 h. After the reaction was completed, the temperature was lowered to 90°C, the acidic clay catalyst was removed by filtration, and the appropriate amount of activated carbon and activated clay were added for decolorization, the decolorization temperature was controlled at 80°C, the decolorization was carried out for 1~2 h, and the decolorization agent was removed by filtration. The unreacted tripropylene was distilled out at a temperature of 180°C using a vacuum distillation device, and the vacuum degree was controlled to be less than 5 mmHg. The product was obtained and marked as sample-1. The composition of the product was determined by GC, and the results of the weight percentage of each component based on the total weight of monononyl diphenylamine, dinonyl diphenylamine and trinonyl diphenylamine are shown in Table 1.

[0039] Example 2 Diphenylamine 60.00 g, 44.76 g of tripropylene and 8 g of acidic clay catalyst were placed in a 500 ml four-necked flask, and the temperature was raised to 160°C and refluxed. The remaining tripropylene 89.52 g (total tripropylene 134.28 g, the molar ratio of diphenylamine and tripropylene was 1.0:3.0) was slowly added dropwise, the dropwise time was controlled for 4 h, and the reaction temperature was controlled at 158~162°C. After the dropwise addition was completed, the reaction was refluxed for 20~24 h. After the reaction was completed, the temperature was lowered to 90°C, the acidic clay catalyst was removed by filtration, and the appropriate amount of activated carbon and activated clay were added for decolorization, the decolorization temperature was controlled at 80°C, the decolorization was carried out for 1~2 h, and the decolorization agent was removed by filtration. The unreacted tripropylene was distilled out at a temperature of 180°C using a vacuum distillation device, and the vacuum degree was controlled to be less than 5 mmHg. The product was obtained and marked as sample-1. The composition of the product was determined by GC, and the results of the weight percentage of each component based on the total weight of monononyl diphenylamine, dinonyl diphenylamine and trinonyl diphenylamine are shown in Table 1.

[0040] Example 3 Diphenylamine 60.00 g, 44.76 g of tripropylene and 8 g of acidic clay catalyst were placed in a 500 ml four-necked flask, heated to 160 °C and refluxed. The remaining tripropylene 179.04 g (total tripropylene 223.80 g, the molar ratio of diphenylamine and tripropylene was 1.0:5.0) was slowly added dropwise, the dropwise time was controlled for 6 h, and the reaction temperature was controlled at 158-162 °C. After the dropwise addition was completed, the reaction was refluxed for 22-26 h. After the reaction was completed, the acidic clay catalyst was removed by filtering at 90 °C, and a proper amount of activated carbon and activated clay were added for decolorization, the decolorization temperature was controlled at 80 °C, and the decolorization was carried out for 1-2 h. The decolorizing agent was removed by filtering. A vacuum distillation device was used, the vacuum degree was controlled to be less than 5 mmHg, and the temperature was raised to 180 °C. The unreacted tripropylene was collected until no fraction was collected. The finished product was marked as sample-3. The composition of the product was determined by GC, and the results of the weight percentage of each component based on the total weight of monononyl diphenylamine, dinonyl diphenylamine and trinonyl diphenylamine are shown in Table 1.

[0041] Example 4 Diphenylamine 60.00 g, 44.76 g of tripropylene and 8 g of acidic clay catalyst were placed in a 500 ml four-necked flask, heated to 160 °C and refluxed. The remaining tripropylene 179.04 g (total tripropylene 223.80 g, the molar ratio of diphenylamine and tripropylene was 1.0:5.0) was slowly added dropwise, the dropwise time was controlled for 6 h, and the reaction temperature was controlled at 158-162 °C. After the dropwise addition was completed, the reaction was refluxed for 22-26 h. After the reaction was completed, the acidic clay catalyst was removed by filtering at 90 °C, and a proper amount of activated carbon and activated clay were added for decolorization, the decolorization temperature was controlled at 80 °C, and the decolorization was carried out for 1-2 h. The decolorizing agent was removed by filtering. A vacuum distillation device was used, the vacuum degree was controlled to be less than 5 mmHg, and the temperature was raised to 180 °C. The unreacted tripropylene was collected until no fraction was collected. The finished product was marked as sample-3. The composition of the product was determined by GC, and the results of the weight percentage of each component based on the total weight of monononyl diphenylamine, dinonyl diphenylamine and trinonyl diphenylamine are shown in Table 1.

[0042] Table 1 Composition of alkyl diphenylamine antioxidant samples of examples 1-4

[0043] Example 5 The present example provides an anti-aging agent composition for polyether polyols and polyurethanes: consisting of 33 parts of aromatic amine antioxidant sample-1 and 67 parts of hindered phenolic antioxidant 1135R.

[0044] Example 6 The present example provides an anti-aging agent composition for polyether polyols and polyurethanes: consisting of 33 parts of aromatic amine antioxidant sample-2, 67 parts of hindered phenolic antioxidant 1135R.

[0045] Example 7 This example provides an anti-aging agent composition for polyether polyols and polyurethanes: consisting of 33 parts of aromatic amine antioxidant sample-3, 67 parts of hindered phenolic antioxidant 1135R.

[0046] Example 8 This example provides an anti-aging agent composition for polyether polyols and polyurethanes: consisting of 33 parts of aromatic amine antioxidant sample-4, 67 parts of hindered phenolic antioxidant 1135R.

[0047] Example 9 (control) This example provides an anti-aging agent composition for polyether polyols and polyurethanes: consisting of 65 parts of hindered phenolic antioxidant 1135R and 20 parts of aromatic amine antioxidant 5057 and 15 parts of phosphite antioxidant DHOP by mass percent.

[0048] Example 10 (control) This example provides an anti-aging agent composition for polyether polyols and polyurethanes: consisting of 65 parts of hindered phenolic antioxidant 1135R and 20 parts of aromatic amine antioxidant 5067 and 15 parts of phosphite antioxidant DHOP by mass percent.

[0049] Example 11 This example provides an anti-aging agent composition for polyether polyols and polyurethanes: consisting of 65 parts of hindered phenolic antioxidant 1135R and 20 parts of aromatic amine antioxidant sample-1 and 15 parts of phosphite antioxidant DHOP by mass percent.

[0050] Example 12 This example provides an anti-aging agent composition for polyether polyols and polyurethanes: consisting of 65 parts of hindered phenolic antioxidant 1135R and 20 parts of aromatic amine antioxidant sample-2 and 15 parts of phosphite antioxidant DHOP by mass percent.

[0051] Example 13 This example provides an anti-aging agent composition for polyether polyols and polyurethanes: By mass percent, consisting of 65 parts of hindered phenolic antioxidant 1135R and 20 parts of aromatic amine antioxidant sample-3 and 15 parts of phosphite antioxidant DHOP.

[0052] Example 14 This example provides an anti-aging agent composition for polyether polyols and polyurethanes: By mass percent, consisting of 65 parts of hindered phenolic antioxidant 1135R and 20 parts of aromatic amine antioxidant sample-4 and 15 parts of phosphite antioxidant DHOP.

[0053] Table 2 Compositions of Examples 9-14

[0054] Example 15 (control) This example provides an anti-aging agent composition for polyether polyols and polyurethanes: By mass percent, consisting of 59 parts of hindered phenolic antioxidant 1135R and 29 parts of aromatic amine antioxidant 5057 and 12 parts of radical scavenger antioxidant HP136.

[0055] Example 16 (control) This example provides an anti-aging agent composition for polyether polyols and polyurethanes: By mass percent, consisting of 59 parts of hindered phenolic antioxidant 1135R and 29 parts of aromatic amine antioxidant 5067 and 12 parts of radical scavenger antioxidant HP136.

[0056] Example 17 This example provides an anti-aging agent composition for polyether polyols and polyurethanes: By mass percent, consisting of 59 parts of hindered phenolic antioxidant 1135R and 29 parts of aromatic amine antioxidant sample -1 and 12 parts of radical scavenger antioxidant HP136.

[0057] Example 18 This example provides an anti-aging agent composition for polyether polyols and polyurethanes: By mass percent, consisting of 59 parts of hindered phenolic antioxidant 1135R and 29 parts of aromatic amine antioxidant sample-2 and 12 parts of radical scavenger antioxidant HP136.

[0058] Example 19 This example provides an anti-aging agent composition for polyether polyols and polyurethanes: consists of 59 parts of hindered phenolic antioxidant 1135R and 29 parts of aromatic amine antioxidant sample-3 and 12 parts of radical scavenger antioxidant HP136 by mass percentage.

[0059] Example 20 The present example provides an anti-aging agent composition for polyether polyol and polyurethane: consists of 59 parts of hindered phenolic antioxidant 1135R and 29 parts of aromatic amine antioxidant sample-4 and 12 parts of radical scavenger antioxidant HP136 by mass percentage.

[0060] Table 3 Composition of Examples 15-20

[0061] Comparative Example 1 The present comparative example provides a blank polyether polyol without addition of any antioxidant as a blank control group.

[0062] Comparative Example 2 The present comparative example provides an anti-aging agent for polyether polyol and polyurethane, i.e. hindered phenolic antioxidant 1135R.

[0063] Comparative Example 3 The present comparative example provides an anti-aging agent for polyether polyol and polyurethane, i.e. aromatic amine antioxidant 5057.

[0064] Comparative Example 4 The present comparative example provides an anti-aging agent for polyether polyol and polyurethane, i.e. aromatic amine antioxidant 5067.

[0065] Comparative Example 5 The present comparative example provides an anti-aging agent for polyether polyol and polyurethane, i.e. phosphite antioxidant DHOP.

[0066] Comparative Example 6 The present comparative example provides an anti-aging agent composition for polyether polyol and polyurethane: consisting of 33 parts of amine antioxidant 5057 and 67 parts of hindered phenolic antioxidant 1135R.

[0067] Comparative Example 7 The present comparative example provides an anti-aging agent composition for polyether polyol and polyurethane: consisting of 33 parts of amine antioxidant 5067 and 67 parts of hindered phenolic antioxidant 1135R.

[0068] Performance Test 1. Performance Test 1 - Additive thermal stability The thermal stability and volatility resistance of the auxiliary agent were determined by a thermal gravimetric analyzer (TGA), and the determination conditions were as follows: The TGA test parameters were as follows: temperature range 25-400°C, heating rate 10 K / min, purging gas nitrogen 50 mL / min, sample mass 15±0.1 mg. The determination results are shown in Table 4. It can be seen that the heat resistance, i.e., thermal stability, of Examples 1-4 is more stable than that of the conventional product, i.e., Comparative Examples 3 and 4.

[0069] Table 4 Thermal stability test of auxiliary agent

[0070] 2. Performance test 2 - long-term thermal stability of auxiliary agent in a continuous high-temperature environment In actual applications, many polymer polyol manufacturers have export businesses, and the polymer polyol will undergo a 2-3 month sea transportation process, and the storage environment is complex and variable, and there is a continuous high temperature of 40-70°C. The polymer polyol and the antioxidant therein will be consumed during this process, which may cause the activity of the polymer polyol to decrease in subsequent applications, and the application effect is unstable.

[0071] To simulate this application situation, taking polyether polyol as an example, 5‰ of the total mass of polyether polyol (F3050) was added to the polyether polyol according to the anti-aging agents provided in the above examples and comparative examples, and the blank group without adding anti-aging agent was used as a control. After mixing uniformly, it was placed in a 70°C constant temperature air oven, and the residual content of the antioxidant in the polyether polyol was tested after heat aging for 30 days, 60 days and 90 days. 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, and the residual amount is slightly higher. However, in long-term aging, Examples 1-4 show more obvious long-term thermal stability, and the residual amount of the auxiliary agent is significantly higher than that of the comparative examples, and increases with the increase of the component of the double C9 alkyl-substituted diphenylamine.

[0072] Table 5 Long-term thermal stability test of auxiliary agent in a continuous high-temperature environment

[0073] 3. Performance test 3 - polyurethane sponge FOG value test Test method: polyurethane soft foam sponges were prepared according to the following formulations: 100 parts of high resilience polyether 330N, 52 parts of TDI, 4 parts of foaming agent water, 1.1 parts of silicone foam stabilizer, 0.2 parts of organotin catalyst, 0.15 parts of amine catalyst, and 1.5% of the weight of polyether of the anti-aging agents provided in Examples 1-4 and Comparative Examples 1-5 were foamed. The sponge sample after foaming was taken to the bottom of a fogging glass cup and was pressed with a sample pressing ring. The fogging cup was placed in a constant temperature oil bath, the upper opening plane of which was an oil-resistant and high-temperature-resistant fluororubber sealing ring, and the upper surface of the sealing ring was the fogging carrier (aluminum foil paper). The filter paper and cooling plate were sequentially placed on the aluminum foil paper. The volatile substances in the sponge sample were accelerated to volatilize at high temperature, and then condensed on the fogging carrier cooled by the cooling plate. The gas evaporated from the sponge sample in the fogging cup was condensed on the low-temperature aluminum foil, and the weight change of the aluminum foil before and after condensation was measured (the aluminum foil sheet after fogging needed to be placed in a desiccator for conditioning). The weight of the sample fogging-condensed substance was obtained. The test results are shown in Table 6. It can be seen that compared with Comparative Example 1, Examples 1-4 effectively reduce the FOG value of the polyurethane sponge, i.e., have lower volatility and better oxidation resistance, and increase with the increase of the component of the di-C9 alkyl-substituted diphenylamine. Moreover, compared with conventional antioxidants / anti-aging agents (Comparative Examples 2-4), Examples 1-4 can obtain polyurethane sponges with lower FOG values; compared with the macromolecular polymeric phosphite antioxidant DHOP (Comparative Example 5), Examples 1-4 can obtain polyurethane sponges with equivalent FOG values.

[0074] Table 6 FOG value test of polyurethane sponge

[0075] 4. Performance Test 4 - Determination of the Initial Oxidation Temperature of Polyether Polyol The anti-aging agents provided in the above examples and comparative examples were added to the polyether polyol according to 4.5% of the total mass of the polyether polyol, and after mixing uniformly, the mixture was placed in a 70°C constant temperature air oven for 60 days, and a blank group without the addition of the anti-aging agent was used as a control. The initial oxidation temperature of the polyether polyol was determined by differential scanning calorimetry (DSC), and the determination conditions were as follows: The DSC test parameters were 40°C-350°C, the temperature rise rate was 20K / min, the purge gas was oxygen at 50mL / min, the protective gas was nitrogen at 100 mL / min, and the sample mass was 6.5±0.5mg. The determination results are shown in Table 7. It can be seen that Examples 1-4 effectively protect the polyether polyol from rapid oxidation, and the thermal stability protection effect and the antioxidant effect on the polyether polyol are better than those of conventional products (Comparative Examples 2-5); after compounding with phenolic antioxidants, phosphite antioxidants and free radical scavengers, the effect is better.

[0076] Table 7 Polyether polyol starting oxidation temperature test

[0077] 5. Performance test 5 - polyurethane sponge burning core test According to 4.5 ‰ of the total mass of polyether (F3050), the anti-aging agents provided in the above examples and comparative examples were added to the polyether, and after uniform mixing, they were placed in a 70°C constant temperature air oven for 60 days. According to the following formulation, polyurethane soft foam sponge was prepared: according to the mass fraction, 100 parts of soft foam polyether, 52 parts of TDI, 4 parts of foaming agent water, 1.1 parts of silicone foam stabilizer, 0.2 parts of organotin catalyst, 0.15 parts of amine catalyst, and 4.5 ‰ of the weight of the polyether Anti-aging agents provided in Examples 15-20 and Comparative Example 7 were foamed. After foaming, the sponge was placed in a 700W microwave oven and aged for 4min at P60, the core of the sponge was observed, the smaller the burning core area, the better the anti-burning core effect, and the results are shown in Table 7. Figures 1-7 Figure 1 Figure 2 Figure 3 Figures 4-7

[0078] It can be seen that the anti-aging agent composition added in Examples 17-20 can effectively improve the burning core condition of the polyurethane sponge, and the effect is better than that of the conventional product (Examples 15 / 16); after compounding with phenolic antioxidant, phosphite antioxidant and free radical scavenger, the effect is better.

[0079] From the above description, it can be seen that the above-mentioned examples of the present application achieve the following technical effects: The alkylated diphenylamine of the present application has a high content of double C9 alkyl-substituted diphenylamine (at least 90% C9 alkyl-substituted diphenylamine and 0-10% single C9 alkyl-substituted and triple-substituted diphenylamine based on the total mass of the antioxidant composition), which has more excellent heat weight loss resistance, thermal stability and low volatility compared to conventional low-content C9 products on the market.

[0080] ​​​​​​The alkylated diphenylamine of the present application can be used alone or in combination with phenolic antioxidants and the like to effectively improve the thermal stability and long-term storage stability of polymer polyols, and is particularly suitable for protecting polymer polyols that need to be heated for a long time during transportation and storage, such as conditions that need to undergo sea transportation for a long time, or conditions that need to undergo high tank truck or storage tank storage temperature for a long time. In addition, in downstream applications, the alkylated diphenylamine can provide good foaming stability for polyurethane sponge, the sponge product maintains good resilience and storage stability, can meet the requirements of conventional use, and the low volatility and thermal stability of the antioxidant are conducive to reducing the FOG value of polyurethane sponge such as automotive sponge and home sponge, are more conducive to protecting human health, and are more in line with the development trend of the industry. The liquid state is conducive to smooth transportation and uniform dispersion during use, and is conducive to maintaining the quality stability of polymer polyol and polyurethane products.

[0081] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. An anti-aging agent composition comprising: i) alkylated diphenylamines, wherein, the alkylated diphenylamine includes 90.0 to 99.9% of the dialkyl diphenylamine of Formula II, based on the total weight of the alkylated diphenylamine; each R1is independently selected from linear or branched C9alkyl; ii) a hindered phenolic antioxidant of Formula IV R2is selected from methyl or tert-butyl, and R3is selected from C8to C18alkyl or mixed alkyl.

2. The anti-aging agent composition according to claim 1, wherein, the alkylated diphenylamine further includes: 0 to 15% of the monoalkyl diphenylamine of Formula I, based on the total weight of the alkylated diphenylamine; and / or 0 to 10% of the trialkyl diphenylamine of Formula III, based on the total weight of the alkylated diphenylamine; 。 3. The anti-aging agent composition according to claim 2, wherein, the alkylated diphenylamine includes: 0 to 10% of the 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 trialkyl diphenylamine of Formula III, based on the total weight of the alkylated diphenylamine.

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

5. The anti-aging agent composition according to claim 1, wherein the hindered phenolic antioxidant is selected from one or more of 3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionic acid (iso)octyl ester, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid C7to C9alcohol mixed ester, 3,5-di-tert-butyl-4-hydroxybenzylpropionic acid C12to C14alcohol mixed ester, 3,5-di-tert-butyl-4-hydroxybenzylpropionic acid C13to C15alcohol mixed ester, 3,5-di-tert-butyl-4-hydroxybenzylpropionic acid C14to C16alcohol mixed ester, and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid stearyl ester.

6. The anti-aging agent composition according to any one of claims 1-5, wherein, the anti-aging agent composition further includes a phosphite antioxidant and / or a radical scavenger; wherein the amount of the phosphite antioxidant is 10 to 40%, and the amount of the radical scavenger is 0 to 15%, based on the total weight of the anti-aging agent composition.

7. The anti-aging agent composition of claim 6, wherein, the phosphite antioxidant is selected from one or more of tris(nonylphenyl) phosphite, diphenyl monoisodecyl phosphite, monophenyl diisodecyl phosphite, triphenyl phosphite, diphenyl ether diphosphite, tris(mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl) phosphite, triisodecyl phosphite, and dipentaerythritol diisodecyl phosphite; and / or the radical scavenger is selected from one or more of 3,4-di-tert-butyl-5-(2,4-dimethylphenyl)benzofuran-2(3H)-one and distearyl hydroxylamine.

8. A polymeric polyol or polyurethane composition comprising: a polymeric polyol or polyurethane, and alkylated diphenylamines, wherein, the alkylated diphenylamine includes 90.0 to 99.9% of the dialkyl diphenylamine of Formula II, based on the total weight of the alkylated diphenylamine; each R1is independently selected from linear or branched C9alkyl.

9. The polymeric polyol or polyurethane composition of claim 8, wherein, the alkylated diphenylamine further includes: 0 to 15% monoalkyldiphenylamine of Formula I, based on the total weight of the alkylated diphenylamine; and / or 0 to 10% trialkyldiphenylamine of Formula III, based on the total weight of the alkylated diphenylamine; 。 10. The polymeric polyol or polyurethane composition of claim 9, wherein, the alkylated diphenylamine includes: 0 to 10% monoalkyldiphenylamine of Formula I, based on the total weight of the alkylated diphenylamine; 92.0 to 99.9% dialkyldiphenylamine of Formula II, based on the total weight of the alkylated diphenylamine; and 1 to 5% trialkyldiphenylamine of Formula III, based on the total weight of the alkylated diphenylamine.

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

12. A polyol or polyurethane composition comprising: a polyol or polyurethane, and the anti-aging agent composition of any one of claims 1-7.

13. The polymeric polyol or polyurethane composition of claim 12, wherein, the anti-aging agent composition is used in an amount of 1 ‰ to 40 ‰, based on the total weight of the polyol or polyurethane.

14. A polyol or polyurethane article formed from the polyol or polyurethane composition of any one of claims 8-13.

15. Use of an alkylated diphenylamine in the manufacture of a polymeric polyol or polyurethane article, wherein, the alkylated diphenylamine includes 90.0 to 99.9% dialkyldiphenylamine of Formula II, based on the total weight of the alkylated diphenylamine; each R1is independently selected from linear or branched C9alkyl.

16. The use according to claim 15, wherein, the alkylated diphenylamine includes: 0 to 5% monoalkyldiphenylamine of Formula I, based on the total weight of the alkylated diphenylamine; 92.0 to 99.9% dialkyldiphenylamine of Formula II, based on the total weight of the alkylated diphenylamine; and 1 to 5% trialkyldiphenylamine of Formula III, based on the total weight of the alkylated diphenylamine; 。

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