Antioxidant Composition, Its Application and Antioxidant Polymer Material

Abstract

The present invention provides an anti-aging agent composition, its application and an anti-aging polymer material. The anti-aging agent composition includes gallate and / or p-hydroxybenzoate antioxidant, phosphite antioxidant, hindered phenol antioxidant and / or free radical scavenger. The anti-aging agent composition provided in this application does not contain aromatic amine antioxidants. Through the mutual synergy among several components, it can not only effectively inhibit the core burning and the fire caused by core burning during the production of polymer sponges, and has good sponge core burning resistance ability, but also can improve the antioxidant property and thermal stability of the polymer sponge, effectively inhibit yellowing and redness, improve the storage stability of the polymer sponge under natural light and ultraviolet light, and significantly improve its long-term storage stability.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-aging agents, and in particular, to an anti-aging agent composition, its application, and an anti-aging polymer material. Background Art

[0002] During the production, use, and storage of polyurethane flexible foam sponges, thermo-oxidative aging inevitably occurs, resulting in the appearance of the product turning yellow or even red, and the mechanical strength of the material also decreases. This is also an important problem that has long troubled polyurethane manufacturers. Currently, the commonly used method in the market is to add antioxidants and light stabilizers to slow down the yellowing of the sponge. However, it is worth mentioning that common hindered phenol antioxidants may cause phenol yellowing under high-temperature conditions, further affecting the appearance of the sponge.

[0003] Secondly, at present, there are mainly two types of polyurethane sponge foaming equipment, namely mechanical continuous foaming and discontinuous box foaming. The above methods both have the problem of sponge core burning, that is, due to the exothermic reaction of foaming, the internal and external temperatures rise during the foaming process, especially the internal temperature. The heat at the core is difficult to disperse, resulting in high-temperature oxidation of the polymer molecular chains at the center, and the color of the foam center turns yellow or even black. The heat release problem is a key common problem, which severely restricts the further optimization of product quality. Conventionally, aromatic amine catalysts are added to improve the thermal stability of polyethers to solve the problem of sponge core burning.

[0004] Aromatic amine antioxidants have very good high-temperature antioxidant ability and can inhibit the aging degradation of polymers at high temperatures during sponge foaming. However, the residual amine antioxidants will promote the yellowing of the sponge when contacting nitrogen oxides in the air and under light, and will promote the phenol redness of the sponge when used together with hindered phenol antioxidants.

[0005] Therefore, developing an anti-aging agent formulation that can endow polyurethane with excellent thermal stability and improve its weather resistance and long-term storage stability is one of the important methods to solve the existing technical problems. Summary of the Invention

[0006] The main object of the present invention is to provide an anti-aging agent composition, its application, and an anti-aging polymer material to solve the problems that common hindered phenol antioxidants used in existing polyurethane sponges may cause phenol yellowing under high-temperature conditions, affecting the appearance of the sponge; and although common aromatic amine oxidants can improve sponge core burning, the residual amine antioxidants will promote the yellowing of the sponge, and will also promote the phenol redness of the sponge when used together with hindered phenol antioxidants.

[0007] To achieve the above object, according to one aspect of the present invention, an anti-aging agent composition is provided, which includes gallate and / or p-hydroxybenzoate antioxidant, hindered phenol antioxidant, phosphite antioxidant and / or free radical scavenger.

[0008] Further, the anti-aging agent composition includes gallate and / or p-hydroxybenzoate antioxidant, hindered phenol antioxidant, phosphite antioxidant and free radical scavenger.

[0009] Further, by mass, the anti-aging agent composition includes: 2 to 10 parts of the gallate and / or p-hydroxybenzoate antioxidant, 5 to 20 parts of the phosphite antioxidant, 50 to 75 parts of the hindered phenol antioxidant, and 5 to 20 parts of the free radical scavenger;

[0010] Further, in the above anti-aging agent composition, the gallate and / or p-hydroxybenzoate antioxidant is 3 to 8 parts, the phosphite antioxidant is 8 to 18 parts, the hindered phenol antioxidant is 60 to 75 parts, and the free radical scavenger is 5 to 13 parts.

[0011] Further, the gallate antioxidant has the structure shown in formula (Ⅰ-1), and the p-hydroxybenzoate antioxidant has the structure shown in formula (I-2):

[0012]

[0013] Wherein, R 1 is selected from any one of H, a linear or branched alkyl group with 1 to 12 carbon atoms, an alkylated aryl group with 6 to 18 carbon atoms, an esterified aryl group with 6 to 18 carbon atoms, a thioetherified aryl group with 6 to 18 carbon atoms, and an etherified aryl group with 6 to 18 carbon atoms;

[0014] Further, the gallate antioxidant is selected from at least one of methyl gallate, propyl gallate, octyl gallate or epigallocatechin gallate; the p-hydroxybenzoate antioxidant is selected from at least one of methyl paraben and butyl paraben.

[0015] Further, the phosphite antioxidant has the structure shown in formula (Ⅱ) or formula (Ⅲ):

[0016]

[0017] Wherein, R 2 , R 3 , R 4 , R 5Each independently selected from any one of linear or branched C1-C30 alkyl groups, linear or branched C1-C30 alkyl groups containing an ether bond, and substituted or unsubstituted C6-C20 aryl groups; n is an integer between 1 and 5, preferably an integer between 1 and 3.

[0018] Further, the phosphite antioxidant is selected from at least one of triisodecyl phosphite, tris(tridecyl) phosphite, dipentaerythritol diisodecyl diphosphite, dipentaerythritol ditridecyl diphosphite, tetraphenyldipropylene glycol diphosphite, poly(dipropylene glycol) phenyl phosphite, triphenyl phosphite, diphenylisodecyl phosphite, isodecyl diphenyl phosphite, tris(nonylphenyl) phosphite.

[0019] Further, the hindered phenol antioxidant has the structure shown in formula (IV):

[0020]

[0021] Wherein, R 6 is a linear or branched C6-C20 alkyl group, preferably any one or a mixture of n-octyl, isooctyl, n-heptyl, isoheptyl, n-nonyl, isononyl, C12-C18;

[0022] Further, the hindered phenol antioxidant is selected from at least one of isooctyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate and its derivatives, isotridecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 13-15 carbon alcohol ester of 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 14-16 carbon alcohol ester of 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, isooctadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate.

[0023] Further, the radical scavenger has the structure shown in the following formula (V-1) or (V-2):

[0024]

[0025] Wherein, R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 Each independently selected from H or linear or branched C1-C30 alkyl groups;

[0026] Further, R 7 , R 8 Each independently selected from isopropyl or isobutyl, tert-butyl, R 9 , R10 each independently selected from methyl, ethyl or tert-butyl; R 11 、R 12 、R 13 、R 14 、R 15 each independently selected from methyl, tert-butyl, tert-amyl;

[0027] Furthermore, the radical scavenger is at least one of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, 2-[1-(2-hydroxy-3,5-di-tert-amylphenyl)ethyl]-4,6-di-tert-amylphenyl acrylate or 2-acrylate-2-(1,1-dimethylethyl)-6-[[3-(1,1-dimethylethyl)-2-hydroxy-5-methylphenyl]methyl]-4-tolyl ester.

[0028] Further, the anti-aging agent composition is liquid; furthermore, the gallate and / or p-hydroxybenzoate antioxidant, the phosphite antioxidant, the hindered phenol antioxidant and the radical scavenger are each independently liquid;

[0029] Further, the gallate and / or p-hydroxybenzoate antioxidant is dispersed in a solvent to form a gallate and / or p-hydroxybenzoate antioxidant solution, and the solvent is a fat-soluble solvent;

[0030] Further, the fat-soluble solvent is selected from at least one of white oil, ethanol, propanol, ether, glycerol, propylene glycol or polyether.

[0031] Further, the anti-aging agent composition includes a gallate antioxidant, dipentaerythritol diisotridecyl diphosphite, octyl 3,5-di-tert-butyl-4-hydroxycinnamate and 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and the mass ratio of the four is (3-8):(8-18):(60-75):(5-20);

[0032] Further, by mass percentage, the anti-aging agent composition includes 4 parts of propyl gallate, 15 parts of dipentaerythritol diisotridecyl diphosphite, 10 parts of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one and 65 parts of isooctyl 3,5-di-tert-butyl-4-hydroxycinnamate;

[0033] Further, the anti-aging agent composition comprises 6 parts of propyl gallate, 10 parts of dipentaerythritol diisotridecyl diphosphite, 10 parts of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 65 parts of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate;

[0034] Further, the anti-aging agent composition comprises 6 parts of propyl gallate, 15 parts of dipentaerythritol diisodecyl diphosphite, 10 parts of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 60 parts of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0035] According to another aspect of the present application, the present application provides the use of any of the anti-aging agent compositions provided in the first aspect above in anti-aging of polymer materials.

[0036] According to the third aspect of the present application, the present application provides an anti-aging polymer material, which comprises a polymer and any of the anti-aging agent compositions provided in the first aspect above.

[0037] Further, the polymer comprises at least one of polyether or polyurethane.

[0038] Further, the mass ratio of the anti-aging agent composition to the polymer is 0.1-5:100.

[0039] Applying the technical solution of the present application, the anti-aging agent composition provided by the present application comprises gallate and / or p-hydroxybenzoate antioxidant, phosphite antioxidant, hindered phenol antioxidant and / or free radical scavenger. These components are used in combination with each other, having a remarkable synergistic effect, which can significantly improve the initial oxidation temperature, antioxidant property and thermal stability of polyether, as well as the long-term storage stability; effectively inhibit yellowing and red change, improve the storage stability of the sponge under natural light and ultraviolet light, and significantly improve its long-term storage stability. The anti-aging agent composition provided by the present application can also be added during the foaming of polyether, so as to effectively inhibit or avoid the phenomenon of core burning and fire caused by core burning during the production of polyurethane flexible foam.

[0040] In addition, the anti-aging agent composition provided by the present application has a good effect of inhibiting yellowing on ordinary soft foam polyurethane sponges. During the production of polyurethane sponge, adding this composition can significantly improve the processing stability of soft foam polyether for preparing polyurethane sponge, and the obtained polyurethane sponge has good weather resistance. Compared with the polyurethane sponge containing aromatic amine antioxidant, its resistance to sunlight yellowing, gas fume red change and weather resistance have been significantly improved. Specific embodiments

[0041] It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments may be combined with each other. The present invention will be described in detail below with reference to the embodiments.

[0042] As analyzed in the background art of the present application, in the existing polyurethane sponge, antioxidants and light stabilizers are added to improve stability and slow down yellowing. The commonly used hindered phenol antioxidants may cause phenolic yellowing under high-temperature conditions, further affecting the appearance of the sponge. Although the commonly used amine oxidants can improve the core burning of the sponge, the residual amine antioxidants will promote the yellowing of the sponge, and when used together with the hindered phenol antioxidants, it will also promote the phenolic red change of the sponge. To solve this problem, the present application provides an anti-aging agent composition, its application, and an anti-aging polymer material.

[0043] In a typical embodiment of the present application, an anti-aging agent composition is provided, which includes gallate and / or p-hydroxybenzoate antioxidants, hindered phenol antioxidants, phosphite antioxidants, and / or radical scavengers.

[0044] The composition of the present application does not contain aromatic amine antioxidants. The anti-aging agent composition provided by the present application includes gallate and / or p-hydroxybenzoate antioxidants, phosphite antioxidants, hindered phenol antioxidants, and / or radical scavengers. These components are used in combination with each other, having a significant synergistic effect, which can significantly increase the initial oxidation temperature, antioxidant property, and thermal stability of the polyether, as well as the long-term storage stability; effectively inhibit yellowing and red change, improve the storage stability of the sponge under natural light and ultraviolet light, and significantly improve its long-term storage stability. The anti-aging agent composition provided by the present application can also be added during the polyether foaming process to effectively inhibit or avoid core burning and the fire caused by core burning during the production process of flexible polyurethane foam.

[0045] In addition, the anti-aging agent composition provided by the present application has a good effect of inhibiting yellowing on ordinary flexible polyurethane sponges. During the production process of polyurethane sponges, adding this composition can significantly improve the processing stability of flexible polyether foaming to prepare polyurethane sponges, and the obtained polyurethane sponges have good weather resistance. Compared with the polyurethane sponges containing aromatic amine antioxidants, their resistance to sunlight yellowing, gas fume red change, and weather resistance have been significantly improved.

[0046] To further improve the stability and weather resistance of the above anti-aging agent composition, calculated by mass fraction, the anti-aging agent composition includes: 2 - 10 parts of the gallate and / or p-hydroxybenzoate antioxidants, 5 - 20 parts of the phosphite antioxidants, 50 - 75 parts of the hindered phenol antioxidants, and 5 - 20 parts of the radical scavengers;

[0047] Especially when in the anti-aging agent composition, the gallate and / or p-hydroxybenzoate antioxidant is 3 to 8 parts, the phosphite antioxidant is 8 to 18 parts, the hindered phenol antioxidant is 60 to 75 parts, and the free radical scavenger is 5 to 13 parts, when added to polyether or polyurethane and their sponge products, the sponge has more excellent thermal stability, light stability and weather resistance.

[0048] Typical but non-limiting, in the anti-aging agent composition provided in the present application, the mass fraction of the gallate and / or p-hydroxybenzoate antioxidant is, for example, 5, 8, 10, 12, 15, 20 or a range value composed of any two numerical values; the mass fraction of the phosphite antioxidant is, for example, 5, 8, 10, 12, 15, 20 or a range value composed of any two numerical values; the mass fraction of the hindered phenol antioxidant is, for example, 50, 55, 58, 60, 62, 65, 68, 70, 72, 75 or a range value composed of any two numerical values; the mass fraction of the free radical scavenger is, for example, 5, 8, 10, 12, 15, 20 or a range value composed of any two numerical values.

[0049] In order to further improve the antioxidant property, thermal stability and the performance of inhibiting yellowing and redness of the above anti-aging agent composition, it is preferred that the mass ratio of the gallate and / or p-hydroxybenzoate antioxidant, the phosphite antioxidant, the hindered phenol antioxidant and the free radical scavenger is (2 - 10):(5 - 20):(50 - 75):(5 - 20).

[0050] The above gallate antioxidant has the structure shown in formula (Ⅰ-1), and the p-hydroxybenzoate antioxidant has the structure shown in formula (I-2):

[0051]

[0052] In the above formula (Ⅰ), R 1 is selected from any one of H, a straight-chain or branched-chain alkyl group with 1 to 12 carbon atoms, an alkylated aryl group with 6 to 18 carbon atoms, an ester-substituted aryl group with 6 to 18 carbon atoms, a thioether-substituted aryl group with 6 to 18 carbon atoms, and an ether-substituted aryl group with 6 to 18 carbon atoms. Especially when the gallate antioxidant is selected from methyl gallate, propyl gallate, octyl gallate, epigallocatechin gallate; and the p-hydroxybenzoate antioxidant is selected from any one or a mixture of antioxidants formed by methyl paraben and butyl paraben, when the anti-aging agent is added to materials such as polyether polyurethane, it is more beneficial to improve the quality stability during production, storage and transportation.

[0053] In a preferred embodiment of the present application, the phosphite antioxidant has the structure shown in formula (Ⅱ) or formula (Ⅲ):

[0054]

[0055] Among them, R 2 and R 3 and R 4 and R 5 are each independently selected from any one of linear or branched C1-C30 alkyl groups, linear or branched C1-C30 alkyl groups containing an ether bond, and substituted or unsubstituted C6-C20 aryl groups; n is selected from integers between 1 and 5. If R 2 is a linear or branched C1-30 alkyl group or a linear or branched C1-30 alkyl group containing an ether bond, then n is selected from any integer between 1 and 4, preferably any integer between 1 and 3; if R 3 is a substituted or unsubstituted C6-20 aryl group, then n is selected from any integer between 1 and 5, preferably any integer between 1 and 3.

[0056] In order to further improve the weather resistance of the antioxidant composition, it is preferred that the phosphite antioxidant is selected from any one or a mixture of antioxidants formed by tris(isodecyl) phosphite, tris(tridecyl) phosphite, dipentaerythritol diisodecyl diphosphite, dipentaerythritol ditridecyl diphosphite, tetraphenyldipropylene glycol diphosphite, poly(dipropylene glycol) phenyl phosphite, or triphenyl phosphite, diphenylisodecyl phosphite, monophenyl diisodecyl phosphite, tris(nonylphenyl) phosphite.

[0057] In a preferred embodiment of the present application, the above-mentioned hindered phenol antioxidant has the structure shown in formula (IV):

[0058]

[0059] In formula (IV), R 6 is a linear or branched C6-C20 alkyl group, preferably any one or a mixture of n-octyl, isooctyl, n-heptyl, isoheptyl, n-nonyl, isononyl, C12-C18.

[0060] In order to further improve the anti-aging performance of the antioxidant composition, it is preferred that the hindered phenol antioxidant is at least one of isooctyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate and its derivatives, isotridecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 13-15 carbon alcohol ester of 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 14-16 carbon alcohol ester of 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, isooctadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate.

[0061] In a preferred embodiment of the present application, the radical scavenger has the structure shown in the following formula (V-1) or (V-2):

[0062]

[0063] Among them, R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 are each independently selected from H or a linear or branched alkyl group having 1 to 30 carbon atoms; preferably, R 7 , R 8 are each independently selected from isopropyl, isobutyl, or tert-butyl, and R 9 , R 10 are each independently selected from methyl, ethyl, or tert-butyl; when R 11 , R 12 , R 13 , R 14 , R 15 are each independently selected from methyl, tert-butyl, or tert-amyl, the radical scavenger and other antioxidants synergistically exhibit more excellent anti-aging performance.

[0064] In particular, when the radical scavenger is 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, 2-[1-(2-hydroxy-3,5-di-tert-amylphenyl)ethyl]-4,6-di-tert-amylphenyl acrylate, or 2-acrylate-2-(1,1-dimethylethyl)-6-[[3-(1,1-dimethylethyl)-2-hydroxy-5-methylphenyl]methyl]-4-tolyl ester, it synergistically with other antioxidants can further improve the light stability and yellowing resistance of the anti-aging agent composition.

[0065] To further improve the dispersion uniformity of the above anti-aging agent composition in the polymer, it is preferred that the anti-aging agent composition is in a liquid form. The gallic acid antioxidant, phosphite antioxidant, hindered phenol antioxidant, and radical scavenger can each independently be in a liquid state.

[0066] To further improve the dispersion uniformity of the above anti-aging agent composition in the polymer sponge, it is preferred that the gallate or p-hydroxybenzoate antioxidant is dispersed in a solvent to form a gallate or p-hydroxybenzoate antioxidant solution. The solvent is a fat-soluble solvent, and the mass concentration of the gallic acid or p-hydroxybenzoate is controlled to be 20 - 90%; preferably 40% - 70%, to further facilitate the dispersion of the aging agent when added to high molecular materials such as polyether polyurethane.

[0067] The specific type of the above-mentioned fat-soluble solvent is not limited, and any fat-soluble solvent that can dissolve and disperse gallate antioxidants or p-hydroxybenzoate antioxidants can be used, including but not limited to any one or more of white oil, ethanol, propanol, ether, glycerol, propylene glycol or polyether to form a mixed fat-soluble solvent. The models of the white oil and polyether are not particularly limited and are known in the art, as long as they can dissolve gallate antioxidants or p-hydroxybenzoate antioxidants.

[0068] In some embodiments of the present application, the anti-aging agent composition includes gallate antioxidants, pentaerythritol diisotridecyl diphosphite, octyl 3,5-di-tert-butyl-4-hydroxycinnamate and 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one. When the mass ratio of the four is (3-8):(8-18):(60-75):(5-20), when the anti-aging agent composition is added to the polymer sponge, the polymer sponge has more excellent light stability, yellowing resistance and storage stability.

[0069] In one embodiment of the present application, the anti-aging agent composition includes 4 parts of propyl gallate, 15 parts of pentaerythritol diisotridecyl diphosphite as a phosphite antioxidant, 10 parts of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one and 65 parts of isooctyl 3,5-di-tert-butyl-4-hydroxycinnamate;

[0070] Preferably, the gallate is a polyether solution with a mass concentration of 40%.

[0071] In another embodiment of the present application, the anti-aging agent composition includes 6 parts of propyl gallate, 10 parts of pentaerythritol diisotridecyl diphosphite, 10 parts of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one and 65 parts of isooctyl 3,5-di-tert-butyl-4-hydroxycinnamate.

[0072] Further, by mass percentage, the anti-aging agent composition includes 6 parts of propyl gallate, 15 parts of pentaerythritol diisodecyl diphosphite, 10 parts of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one and 60 parts of isooctyl 3,5-di-tert-butyl-4-hydroxycinnamate.

[0073] The composition further includes commonly used polymer material additives in the art, such as ultraviolet absorbers, hindered amine light stabilizers, flame retardants, light-shielding agents, etc.

[0074] In the second typical embodiment of the present application, an application of the above anti-aging agent composition in a polymer material is further provided, thereby improving the weather resistance and storage stability of the polymer material.

[0075] The specific type of the above polymer material is not specifically limited, including but not limited to polyethers or polyurethanes and their sponge products, etc.

[0076] In the third typical embodiment of the present application, an anti-aging polymer material is further provided. The anti-aging polymer material includes a polymer and any one of the anti-aging agent compositions provided in the first typical embodiment above.

[0077] The anti-aging polymer material provided by the present application not only can inhibit the core burning and the fire caused by core burning during the production process by adding a liquid anti-aging agent composition to the polymer, especially adding it to polyethers and / or polyurethanes, but also has excellent antioxidant and thermal stability and storage stability under natural light and ultraviolet light, and thus has excellent long-term storage stability.

[0078] The specific type of the above polymer is not specifically limited, including but not limited to polyethers or polyurethanes, etc.

[0079] In order to further improve the weather resistance and storage stability of the above anti-aging polymer material, the mass ratio of the anti-aging agent to the polymer is preferably 0.1 - 5:100.

[0080] Typical but non-limiting, the mass ratio of the liquid anti-aging agent to the polymer is such as 0.1:100, 0.2:100, 0.3:100, 0.5:100, 0.8:100, 1:100, 2:100, 3:100, 4:100, 5:100 or a range value composed of any two numerical values.

[0081] Next, the beneficial effects of the present application will be described in conjunction with examples and comparative examples.

[0082] All substances used in the following examples are commercially available products and can be obtained through commercial purchase; all gallate antioxidants used are in the form of solutions dissolved in fat-soluble solvents.

[0083] Example 1

[0084] This example provides a liquid anti-aging agent composition, by mass percentage, including 4 g of propyl gallate, 10 g of phosphite antioxidant tris(tridecyl) phosphite, 5 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 75 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate; wherein, the 4 g of propyl gallate is dispersed in 6 g of polyether F3050 to form a 40% mass fraction solution of propyl gallate.

[0085] Example 2

[0086] This example provides a liquid anti-aging agent composition, by mass percentage, including 4 g of propyl gallate, 10 g of tris(tridecyl) phosphite, 10 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 70 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0087] Example 3

[0088] This example provides a liquid anti-aging agent composition, by mass percentage, including 4 g of propyl gallate, 10 g of dipentaerythritol diisotridecyl diphosphite, 10 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 70 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0089] Example 4

[0090] This example provides a liquid anti-aging agent composition, by mass percentage, including 4 g of propyl gallate, 10 g of dipentaerythritol diisotridecyl diphosphite, 15 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 65 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0091] Example 5

[0092] This example provides a liquid anti-aging agent composition, by mass percentage, including 4 g of propyl gallate, 15 g of dipentaerythritol diisotridecyl diphosphite, 10 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 65 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0093] Example 6

[0094] This example provides a liquid anti-aging agent composition, by mass percentage, including 6 g of propyl gallate, 10 g of dipentaerythritol diisotridecyl diphosphite, 10 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 65 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0095] Example 7

[0096] This example provides a liquid anti-aging agent composition, which, by mass percentage, includes 6 g of propyl gallate, 15 g of dipentaerythritol diisodecyl diphosphite, 10 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 60 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0097] Example 8

[0098] This example provides a liquid anti-aging agent composition, which, by mass percentage, includes 6 g of propyl gallate, 10 g of dipentaerythritol diisodecyl diphosphite, 15 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 60 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0099] Example 9

[0100] This example provides a liquid anti-aging agent composition, which, by mass percentage, includes 8 g of propyl gallate, 10 g of dipentaerythritol diisodecyl diphosphite, 10 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 60 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0101] Example 10

[0102] This example provides a liquid anti-aging agent composition, which, by mass percentage, includes 8 g of propyl gallate, 15 g of dipentaerythritol diisodecyl diphosphite, 10 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 55 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0103] Example 11

[0104] This example provides a liquid anti-aging agent composition, which, by mass percentage, includes 8 g of propyl gallate, 10 g of dipentaerythritol diisodecyl diphosphite, 15 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 55 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0105] Example 12

[0106] This example provides a liquid anti-aging agent composition, which, by mass percentage, includes 2 g of propyl gallate, 20 g of dipentaerythritol diisodecyl diphosphite, 5 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 70 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0107] Example 13

[0108] This example provides a liquid anti-aging agent composition, which, by mass percentage, includes 8 g of propyl gallate, 10 g of dipentaerythritol diisodecyl diphosphite, 20 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 50 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0109] Example 14

[0110] This example provides a liquid anti-aging agent composition, which, by mass percentage, includes 6 g of propyl gallate, 5 g of dipentaerythritol diisodecyl diphosphite, 10 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 70 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0111] Example 15

[0112] This example provides a liquid anti-aging agent composition, which, by mass percentage, includes 3.2 g of propyl gallate, 18 g of dipentaerythritol diisodecyl diphosphite, 14 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 60 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0113] Example 16

[0114] This example provides a liquid anti-aging agent composition, which, by mass percentage, includes 3.2 g of propyl gallate antioxidant, 9 g of dipentaerythritol diisodecyl diphosphite, 8 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 75 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0115] Example 17

[0116] This embodiment provides a liquid anti-aging agent composition, which includes 6.4 g of propyl gallate, 8 g of dipentaerythritol diisodecyl diphosphite, 16 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 60 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate by mass percentage. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0117] Example 18

[0118] The difference between this embodiment and Example 6 is that a polyether solution of octyl gallate is used to replace the propyl gallate solution, and the mass concentrations and solvents of the two solutions are the same.

[0119] Example 19

[0120] The difference between this embodiment and Example 6 is that a butyl paraben solution is used to replace the propyl gallate solution, and the mass concentrations and solvents of the two solutions are the same.

[0121] Example 20

[0122] The difference between this embodiment and Example 6 is that isotridecyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate is used to replace isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate.

[0123] Example 21

[0124] The difference between this embodiment and Example 6 is that octadecyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is used to replace isooctyl 3,5-di-tert-butyl-4-hydroxybenzenepropionate.

[0125] Example 22

[0126] The difference between this embodiment and Example 6 is that 2-[1-(2-hydroxy-3,5-di-tert-amylphenyl)ethyl]-4,6-di-tert-amylphenyl acrylate is used to replace 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one.

[0127] Example 23

[0128] The difference between this embodiment and Example 6 is that 2-(1,1-dimethylethyl)-6-[[3-(1,1-dimethylethyl)-2-hydroxy-5-methylphenyl]methyl]-4-methylphenyl 2-propenoate is used to replace 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one.

[0129] Example 24

[0130] The difference between this embodiment and Embodiment 6 lies in that triisodecyl phosphite is used to replace pentaerythritol diisotridecyl diphosphite.

[0131] Example 25

[0132] This comparative example provides an antioxidant which, by mass percentage, includes 0.8 g of propyl gallate, 10 g of tris(tridecyl) phosphite, 10 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 78 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0133] Example 26

[0134] This comparative example provides an antioxidant which, by mass percentage, includes 6 g of propyl gallate, 25 g of tris(tridecyl) phosphite, 20 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 40 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate. Among them, the solution preparation and concentration of propyl gallate are the same as those in Example 1.

[0135] Example 27

[0136] This comparative example provides an antioxidant which, by mass percentage, includes 10 g of propyl gallate antioxidant, 10 g of tris(tridecyl) phosphite, and 80 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate. Among them, propyl gallate is the same as that in Example 1.

[0137] Example 28

[0138] This comparative example provides an antioxidant which, by mass percentage, includes 10 g of propyl gallate, 10 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 80% of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate. Among them, propyl gallate is the same as that in Example 1.

[0139] Example 29

[0140] This comparative example provides an antioxidant which, by mass percentage, includes 10 g of tris(tridecyl) phosphite, 10 g of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and 80 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0141] Comparative Example 1

[0142] This comparative example provides an antioxidant, and the antioxidant is 100 g of isooctyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0143] Comparative Example 2

[0144] This comparative example provides an antioxidant, which is 100 g of tris(tridecyl) phosphite.

[0145] Comparative Example 3

[0146] This comparative example provides an antioxidant, which is 100 g of 5,7 - di - tert - butyl - 3-(3,4 - dimethylphenyl)-3H - benzofuran - 2 - one.

[0147] Comparative Example 4

[0148] This comparative example provides an antioxidant, which is a propyl gallate solution, the same as the 40% mass fraction of propyl gallate antioxidant solution provided in Example 1, 100 g.

[0149] Comparative Example 5

[0150] This comparative example provides an antioxidant, that is, 100 g of arylamine antioxidant 5057.

[0151] Comparative Example 6

[0152] This comparative example provides an antioxidant, by mass percentage, comprising 20 g of arylamine antioxidant 5057 and 80 g of isooctyl 3,5 - di - tert - butyl - 4 - hydroxybenzenepropionate.

[0153] Comparative Example 7

[0154] This comparative example provides an antioxidant, by mass percentage, comprising 30 g of arylamine antioxidant 5057 and 70 g of isooctyl 3,5 - di - tert - butyl - 4 - hydroxybenzenepropionate.

[0155] Comparative Example 8

[0156] This comparative example provides an antioxidant, by mass percentage, comprising 20 g of tris(tridecyl) phosphite and 80 g of isooctyl 3,5 - di - tert - butyl - 4 - hydroxybenzenepropionate.

[0157] Test Example 1 Determination of the initial oxidation temperature

[0158] Add the antioxidants provided in the above examples and comparative examples to the polyether according to 4.5‰ of the total mass of the polyether (F3050), and use the blank group without adding antioxidants as a control. The initial oxidation temperature of the polyether was measured by differential scanning calorimetry (DSC), and the measurement conditions are as follows:

[0159] The DSC test parameters were 40 °C to 350 °C, heating rate 20 K / min, purge gas oxygen 50 mL / min, protective gas nitrogen 100 mL / min, and sample mass 6.7 ± 0.2 mg. The measurement results are shown in Table 1.

[0160] Table 1

[0161]

[0162] Test Example 2 Gas fumigation experiment and ultraviolet aging test

[0163] Prepare polyurethane flexible foam sponge according to the following formula respectively: By mass fraction, 100 parts of flexible polyether F5030, 45 parts of TDI, 3.5 parts of blowing agent water, 0.8 part of silicone foam stabilizer, 0.25 part of organotin catalyst, 0.19 part of amine catalyst, and anti-aging agents provided in Examples 5-8, 18-24 and Comparative Examples 5-7 at 4.5‰ of the polyether weight were used for foaming. After foaming, gas fumigation discoloration and ultraviolet anti-aging tests were carried out. The specific test conditions were as follows:

[0164] (1) Discoloration under different gas fumigation times: Use the Ci7600 spectrophotometer colorimeter of X-Rite. The light source and angle were C light source at 10 degrees. The instrument method was set to the reflection test mode. Measure the color of the sponge after aging and calculate the color difference. The test results are shown in Table 2.

[0165] (2) Anti-aging of ultraviolet rays: The sponge was aged under a UVA-340 ultraviolet lamp at 340 nm irradiance of 0.76 W / m 2 ·nm and 50 °C for 8 hours. Use the Ci7600 spectrophotometer colorimeter of X-Rite. The light source and angle were C light source at 10 degrees. The instrument method was set to the reflection test mode. Measure the color of the sponge after aging and calculate the color difference. The test results are shown in Table 3.

[0166] Table 2

[0167]

[0168] Table 3

[0169]

[0170]

[0171] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0172] The anti-aging agent composition provided by the present application does not contain aromatic amine antioxidants. When used in combination with gallate antioxidants, phosphite antioxidants, hindered phenol antioxidants, and / or free radical scavengers, they have mutual synergy, can not only effectively inhibit the core burning and fire caused by core burning during the production of polyurethane sponges, and have good sponge core burning resistance, but also can improve the antioxidant and thermal stability of polyurethane sponges, effectively inhibit yellowing and red discoloration, improve the storage stability of polyurethane sponges under natural light and ultraviolet light, and significantly improve their long-term storage stability.

[0173] After adding aromatic amine antioxidants to the anti-aging composition, although the initial oxidation temperature increases, it will accelerate the yellowing and red discoloration of polyurethane sponges. The anti-aging agent composition provided by the present application significantly improves the anti-yellowing and anti-red discoloration properties of polyurethane sponges, and can improve the weather resistance and long-term storage stability of polyethers and polyurethanes under natural light and ultraviolet light.

[0174] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An anti-aging agent composition, characterized in that, by mass, the anti-aging agent composition comprises: 2-10 parts of gallate and / or p-hydroxybenzoate antioxidant, 5-20 parts of phosphite antioxidant, 50-80 parts of hindered phenol antioxidant and 5-20 parts of free radical scavenger; The gallate antioxidant is selected from at least one of methyl gallate, propyl gallate, octyl gallate or epigallocatechin gallate; the p-hydroxybenzoate antioxidant is selected from at least one of methyl paraben and butyl paraben; The free radical scavenger is 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, 2-[1-(2-hydroxy-3,5-di-tert-amylphenyl)ethyl]-4,6-di-tert-amylphenyl acrylate or 2-acrylate-2-(1,1-dimethylethyl)-6-[[3-(1,1-dimethylethyl)-2-hydroxy-5-methylphenyl]methyl]-4-tolyl ester.

2. The anti-aging agent composition according to claim 1, characterized in that, in the anti-aging agent composition, the mass content of the gallate and / or p-hydroxybenzoate antioxidant is 3-8 parts, the mass content of the phosphite antioxidant is 8-18 parts, the mass content of the hindered phenol antioxidant is 60-75 parts, and the mass content of the free radical scavenger is 5-13 parts.

3. The anti-aging agent composition according to claim 1, characterized in that, the phosphite antioxidant has the structure shown in formula (Ⅱ) or formula (Ⅲ): Formula (II); Formula (III); Among them, R 2 , R 3 , R 4 , R 5 are each independently selected from any one of straight-chain or branched alkyl groups having 1 to 30 carbon atoms, straight-chain or branched alkyl groups having 1 to 30 carbon atoms containing an ether bond, and substituted or unsubstituted aryl groups having 6 to 20 carbon atoms; n is selected from integers between 1 and 5.

4. The anti-aging agent composition according to claim 3, characterized in that, n is an integer between 1 and 3.

5. The anti-aging agent composition according to claim 1, characterized in that, the phosphite antioxidant is selected from at least one of tris(isodecyl) phosphite, tris(tridecyl) phosphite, dipentaerythritol diisodecyl diphosphite, dipentaerythritol ditridecyl diphosphite, tetraphenyldipropylene glycol diphosphite, poly(dipropylene glycol) phenyl phosphite, triphenyl phosphite, diphenylisodecyl phosphite, isodecyldiphenyl phosphite, tris(nonylphenyl) phosphite.

6. The anti-aging agent composition according to claim 1, characterized in that, the hindered phenol antioxidant has the structure shown in formula (Ⅳ): Formula (IV); Among them, R 6 is a straight-chain or branched-chain alkyl group having 6 to 20 carbon atoms.

7. The anti-aging agent composition according to claim 6, characterized in that, R 6 is any one or a mixture of more than one of n-octyl, isooctyl, n-heptyl, isoheptyl, n-nonyl, isononyl, C12-C18.

8. The anti-aging agent composition according to claim 1, characterized in that, the hindered phenol antioxidant is selected from at least one of isooctyl 3,5-di-tert-butyl-4-hydroxycinnamate and its derivatives, isotridecyl 3,5-di-tert-butyl-4-hydroxycinnamate, 13-15 carbon alcohol ester of 3,5-di-tert-butyl-4-hydroxycinnamate, 14-16 carbon alcohol ester of 3,5-di-tert-butyl-4-hydroxycinnamate, isooctadecyl 3,5-di-tert-butyl-4-hydroxycinnamate.

9. The anti-aging agent composition according to any one of claims 1 to 8, characterized in that, The anti-aging agent composition is in liquid form.

10. The anti-aging agent composition according to claim 9, wherein, the gallate and / or p-hydroxybenzoate antioxidant, the phosphite antioxidant, the hindered phenol antioxidant and the radical scavenger are each independently in liquid form.

11. The anti-aging agent composition according to claim 9, wherein, the gallate and / or p-hydroxybenzoate antioxidant is dispersed in a solvent to form a gallate and / or p-hydroxybenzoate antioxidant solution, and the solvent is a fat-soluble solvent.

12. The anti-aging agent composition according to claim 11, wherein, the fat-soluble solvent is selected from at least one of white oil, ethanol, propanol, ether, glycerol, propylene glycol or polyether.

13. The anti-aging agent composition according to claim 9, wherein, the anti-aging agent composition comprises gallate, dipentaerythritol diisotridecyl diphosphite, octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate and 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and the mass ratio of the four is (3 - 8):(8 - 18):(60 - 75):(5 - 20).

14. The anti-aging agent according to claim 9, wherein, by mass parts, the anti-aging agent composition comprises 4 parts of propyl gallate, 15 parts of dipentaerythritol diisotridecyl diphosphite, 10 parts of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one and 65 parts of isooctyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate.

15. The anti-aging agent according to claim 9, wherein, by mass parts, the anti-aging agent composition comprises 6 parts of propyl gallate, 10 parts of dipentaerythritol diisotridecyl diphosphite, 10 parts of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one and 65 parts of isooctyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate.

16. The anti-aging agent according to claim 9, wherein, by mass parts, the anti-aging agent composition comprises 6 parts of propyl gallate, 15 parts of dipentaerythritol diisodecyl diphosphite, 10 parts of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one and 60 parts of isooctyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate.

17. Use of the anti-aging agent composition according to any one of claims 1 to 16 in anti-aging of polymer materials.

18. An anti-aging polymer material, wherein, the anti-aging polymer material comprises a polymer and the anti-aging agent composition according to any one of claims 1 to 16.

19. The anti-aging polymer material according to claim 18, wherein, the polymer comprises at least one of polyether or polyurethane.

20. The anti-aging polymer material according to claim 18, wherein, The mass ratio of the anti-aging agent composition to the polymer is 0.1 to 5:100.

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