Migration-resistant anti-aging master batch as well as preparation method and application thereof

Abstract

The invention provides a migration-resistant anti-aging master batch as well as a preparation method and application thereof. The migration-resistant anti-aging master batch is prepared from the following raw materials: an anti-aging auxiliary agent, metal salt and resin, the number-average molecular weight of the anti-aging additive is greater than or equal to 1000. The migration-resistant anti-aging master batch is prepared by blending the anti-aging aid, the metal salt and the resin in a melt state, the problem that a traditional anti-aging aid is easy to migrate in a polymer matrix is solved, the migration-resistant anti-aging master batch is good in anti-aging effect, the service life of a polymer material can be further prolonged when the migration-resistant anti-aging master batch is applied to the polymer material, the process is simple, and the cost is low. And the application field is wide.

Description

Technical Field

[0001] The invention belongs to the technical field of anti-aging materials, and in particular relates to a migration-resistant anti-aging masterbatch and a preparation method and application thereof. Background Art

[0002] During use, polymer materials are easily affected by light, heat and oxygen, resulting in aging and degradation. In order to inhibit the aging of polymer materials, anti-aging agents such as antioxidants, ultraviolet light absorbers and light stabilizers are usually added. However, traditional anti-aging agents have poor thermal stability during processing and use, and are easily volatilized or migrated from the polymer matrix, making it difficult to exert long-term anti-aging effects. In order to solve this problem, people have developed high molecular weight anti-aging agents, which can improve the long-term anti-aging effect to a certain extent, and can currently reach a lifespan of 3-5 years. However, with the development of emerging industries, higher requirements are placed on the service life of polymer products. The use conditions of these products are more stringent, and the influence of factors such as water, light, oxygen and microorganisms on the materials is aggravated, making the existing anti-aging agents have the risk of migration during longer-term use, making it difficult to meet the expected use requirements.

[0003] In the prior art, the method for improving the migration resistance of anti-aging agents mainly adopts the inorganic loading method. Inorganic loading is to load the organic anti-aging agents onto the surface of inorganic materials by physical adsorption to achieve the purpose of limiting the migration of the anti-aging agents. However, the anti-aging agents loaded by the physical adsorption method and the inorganic materials are only interacted with by weak bonds such as hydrogen bonds or van der Waals forces, resulting in the problem that the agents are still easy to precipitate, making it difficult to achieve a lasting anti-aging function.

[0004] Therefore, developing an anti-aging auxiliary agent that is resistant to migration, has good anti-aging effect, and can extend the service life of polymer materials is an urgent problem to be solved in the field. Summary of the invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a migration-resistant anti-aging masterbatch and its preparation method and application. The migration-resistant anti-aging masterbatch solves the problem that traditional anti-aging additives are easy to migrate in polymer matrices, and has good anti-aging effects. Application to polymer materials can further improve the service life of polymer materials, has simple processes, strong versatility, does not require harsh reaction conditions, and is environmentally friendly.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a migration-resistant anti-aging masterbatch, wherein the raw materials for preparing the migration-resistant anti-aging masterbatch include an anti-aging aid, a metal salt and a resin; and the number average molecular weight of the anti-aging aid is ≥1000.

[0008] In the present invention, the migration-resistant anti-aging masterbatch adopts an anti-aging agent with a number average molecular weight of ≥1000, which can reduce the migration and precipitation of the anti-aging agent in the polymer material; at the same time, the anti-aging agent coordinates with the metal ions in the metal salt, further improves the molecular weight of the anti-aging agent and forms a cross-linked network structure, improves the extraction ability of the anti-aging agent to resist the external environment (that is, reduces the solubility of the anti-aging agent in the external environment), thereby further reducing the precipitation and migration of the anti-aging agent in the polymer material, and the metal ions can also capture and remove free radicals, terminate the chain reaction, which is beneficial to improve the anti-aging performance of the agent; when used in polymer materials, it can effectively improve the anti-aging performance of the polymer material and extend the service life of the polymer material.

[0009] In the present invention, the number average molecular weight of the anti-aging agent is ≥1000, for example, it can be 1000, 1100, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, 3400, 3600, 3800, 4000, 4200, 4600, 4800, 5000, 5200, 5400, 5600, 5800, 6000, etc.; more preferably, it is 1000-4000.

[0010] Preferably, the migration-resistant anti-aging masterbatch comprises a masterbatch prepared by blending an anti-aging aid, a metal salt and a resin in a molten state.

[0011] In the present invention, by blending the components in a molten state, the coordination reaction between the anti-aging agent and the metal salt is more conducive, the reaction efficiency is improved, and an anti-aging agent with a higher molecular weight and a denser cross-linked network structure is obtained, thereby further improving the anti-aging performance and migration resistance of the masterbatch.

[0012] Preferably, the anti-aging aid comprises an antioxidant and / or a light stabilizer.

[0013] Preferably, the antioxidant comprises a hindered phenol antioxidant and / or a hindered amine antioxidant.

[0014] Preferably, the antioxidant includes at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1010), tris[2.4-di-tert-butylphenyl]phosphite (antioxidant 168), pentaerythritol tetrakis(3-laurylthiopropionate) (antioxidant 412S), 4,4'-para-isopropyl diphenyl C12-15-ol phosphite (antioxidant 1500), 4,4'-butylene bis-(3-methyl-6-tert-butylphenyl)-tetrakis(tridecyl) diphosphite (antioxidant 4500), and poly(dipropylene glycol) phenyl phosphite (antioxidant DHOP).

[0015] Preferably, the light stabilizer comprises a hindered amine light stabilizer and / or a benzoate light stabilizer.

[0016] Preferably, the light stabilizer comprises poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-bis[(2,2,6,6-tetramethyl-piperidinyl)imino]-1,6-hexanediamine[(2,2,6,6-tetramethyl-4-piperidinyl)imino]} (light stabilizer UV-944), the reaction product of 1,6-hexanediamine N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) and 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine (light stabilizer UV-2020), polysuccinic acid (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyl) The invention can be selected from the group consisting of at least one of poly(6-morpholinyl-5-triazine-2,4-diyl)(2,2,6,6-tetramethylpiperidinyl)iminohexamethylene[(2,2,6,6-tetramethylpiperidinyl)-imino](light stabilizer UV3346), methylated polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine with morpholine-2,4,6-trichloro-1,3,5-triazine (light stabilizer UV3529, molecular weight 1700), light stabilizer 783, light stabilizer 362, light stabilizer 119, light stabilizer 625, light stabilizer T68, light stabilizer T69 or light stabilizer 356.

[0017] Preferably, the metal salt comprises a metal organic salt and / or a metal inorganic salt.

[0018] Preferably, the metal organic salt comprises a fatty acid salt and / or an aromatic acid salt.

[0019] Preferably, the number of carbon atoms in the fatty acid salt is ≥1, for example, it can be 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, etc.

[0020] Preferably, the fatty acid salt comprises at least one of formates, acetates, lactates, tartrates or citrates, palmitates and stearates.

[0021] Preferably, the aromatic acid salt comprises at least one of benzoate and salicylate.

[0022] Preferably, the metal inorganic salt includes at least one of chloride, nitrate, nitrite, sulfate, sulfite, carbonate, bicarbonate, phosphate, hydrogen phosphate, dihydrogen phosphate or borate.

[0023] Preferably, the metal salt comprises a rare earth metal salt and / or a non-rare earth metal salt.

[0024] Preferably, the rare earth metal ions in the rare earth metal salt include La 3+ 、Ce 3+ 、Eu 3+ , Yb 3+ , Gd 3+ , Tb 3+ 、Sm 3+ 、Dy 3+ 、Nd 3+ 、Ho 3+ , Er 3+ 、Tm 3+ , Pr 3+ At least one of .

[0025] Preferably, the non-rare earth metal salt comprises at least one of ferric salt, ferrous salt, zinc salt, cuprous salt, copper salt, sodium salt, potassium salt, calcium salt, barium salt or magnesium salt.

[0026] Preferably, the metal salt includes a rare earth metal salt and a non-rare earth metal salt, and the molar ratio of the metal ion in the rare earth metal salt to the metal ion in the non-rare earth metal salt is 1:(0.05-5), wherein the specific value in (0.05-5) can be, for example, 0.05, 0.06, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, 4.2, 4.5, 4.8, 5, etc.; more preferably 1:(0.2-0.8).

[0027] Preferably, the ratio of the total molar amount of the coordinating functional groups in the anti-aging aid to the molar amount of the metal salt is (0.1-30):1, wherein the specific value in (0.1-30) can be, for example, 0.1, 0.2, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24, 26, 28, 30, etc.; more preferably (0.5-12):1.

[0028] In the present invention, the metal salt includes a metal salt containing water of crystallization or a metal salt not containing water of crystallization. When water of crystallization is contained, the ratio of the total molar amount of the coordinating functional groups in the anti-aging agent to the molar amount of the metal salt refers to the ratio of the total molar amount of the metal salt including water of crystallization to the total molar amount of the coordinating functional groups in the anti-aging agent.

[0029] Preferably, the migration and anti-aging masterbatch comprises 50-99.9% resin in terms of mass percentage, for example, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96%, 98%, 99%, etc.

[0030] Preferably, the resin includes at least one of polyethylene (PE), ethylene-vinyl acetate copolymer (EVA), thermoplastic elastomer, polyvinyl chloride (PVC), polystyrene (PS), polypropylene (PP), polyvinylidene chloride (PVDC), polyamide (PA), polyester (PET), polyurethane (PU), polyvinyl alcohol (PVA), polyvinyl acetate (PVAC), polyacrylonitrile (PAN), polycarbonate (PC), and polytetrafluoroethylene (PTFE).

[0031] In a second aspect, the present invention provides a method for preparing the migration-resistant and anti-aging masterbatch according to the first aspect, the preparation method comprising the following steps:

[0032] The anti-aging auxiliary agent, metal salt and resin are mixed and melted, and extruded into granules to obtain the migration-resistant anti-aging masterbatch.

[0033] Preferably, the temperature of the mixed melting is 80-400°C, for example, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, 320°C, 340°C, 360°C, 380°C, 400°C, etc.

[0034] Preferably, the mixing and melting time is 0.1 to 200 min, for example, it can be 1 min, 2 min, 4 min, 6 min, 8 min, 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 120 min, 140 min, 160 min, 180 min, 200 min, etc.; more preferably, it is 0.1 to 30 min.

[0035] In the present invention, when the temperature and time of the mixed melting are within the above ranges, the coordination reaction efficiency of the anti-aging additive and the metal salt is higher, and the obtained masterbatch has better anti-aging performance and migration resistance.

[0036] Preferably, the rotation speed of the mixed melting is 10 to 200 rpm, for example, it can be 10 rpm, 20 rpm, 40 rpm, 60 rpm, 80 rpm, 100 rpm, 120 rpm, 140 rpm, 160 rpm, 180 rpm, 200 rpm, etc.

[0037] In the present invention, the mixing and melting equipment includes but is not limited to an open mixer, an internal mixer, and the like.

[0038] In the present invention, the extrusion equipment includes but is not limited to an internal mixer, a twin-screw extruder, a single-screw extruder, a flat vulcanizer, a vacuum film press, and the like.

[0039] In the present invention, a master batch containing a metal salt and a coordinating polymer auxiliary agent is prepared by blending in a melt state. The preparation method has simple process and operation and is suitable for large-scale industrial production.

[0040] In a third aspect, the present invention provides an anti-aging product, wherein the material of the anti-aging product comprises a base resin and the migration-resistant anti-aging masterbatch described in the first aspect.

[0041] Preferably, the mass ratio of the migration resistant and anti-aging masterbatch to the matrix resin is (1-30):(40-99), wherein the specific values ​​in (1-30) can be, for example, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, etc., and the specific values ​​in (40-99) can be, for example, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, etc.

[0042] In the present invention, the matrix resin is the same as or different from the resin in the migration-resistant and anti-aging masterbatch, and the matrix resin includes at least one of polyethylene, ethylene-vinyl acetate copolymer, thermoplastic elastomer, polyvinyl chloride, polystyrene, polypropylene, polyvinylidene chloride, polyamide, polyester, polyurethane, polyvinyl alcohol, polyvinyl acetate, polyacrylonitrile, polycarbonate or polytetrafluoroethylene.

[0043] In the present invention, the anti-aging product may also be added with other additives according to actual needs, including but not limited to flame retardants, lubricants, antistatic agents, colorants, plasticizers, foaming agents, fillers, vulcanizers, inhibitors, compatibilizers, toughening agents, etc.; fillers may also be added according to actual needs.

[0044] In the present invention, the preparation method of the anti-aging product comprises: mixing a base resin and a migration-resistant anti-aging masterbatch, and molding to obtain the anti-aging product.

[0045] In the present invention, after the base resin and the migration-resistant and anti-aging masterbatch are mixed, the molding temperature is 80-400°C, for example, it can be 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, 320°C, 340°C, 360°C, 380°C, 400°C, etc.

[0046] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] The migration-resistant anti-aging masterbatch provided by the present invention is compounded with an anti-aging auxiliary agent and a metal salt, which can inhibit the migration and precipitation of the anti-aging masterbatch in the polymer material, and at the same time can also improve the anti-aging effect of the anti-aging masterbatch, extend the service life of the polymer material, and meet the higher requirements for material aging performance of new energy, high-speed rail, polymer materials for microalgae cultivation, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 This is a process flow chart of preparing anti-aging products using the migration-resistant anti-aging masterbatch prepared in Example 1 of the present invention.

[0050] Figure 2 This is the infrared spectrum of the migration-resistant and anti-aging masterbatch and polyethylene provided in Example 1. DETAILED DESCRIPTION

[0051] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0052] Example 1

[0053] The present embodiment provides a migration-resistant and anti-aging masterbatch, which includes, by weight percentage, 70% polyethylene (Daqing Petrochemical, DFDA-7042) and 30% antioxidant 1010 and zinc stearate in total weight; the molar ratio of the antioxidant 1010 to the zinc stearate is 0.5:1, wherein the ratio of the total molar amount of the coordinating functional groups in the antioxidant 1010 to the molar amount of zinc stearate is 2:1.

[0054] This embodiment provides a method for preparing the migration-resistant and anti-aging masterbatch, and its process flow chart is as follows: Figure 1 As shown, metal salt, anti-aging additive and resin are mixed, melted and extruded to obtain migration-resistant anti-aging masterbatch; specifically, the following steps are included:

[0055] According to the formula, polyethylene, antioxidant 1010 and zinc stearate are melt-blended at a temperature of 170°C and a rotation speed of 50 rpm for 30 minutes, and then extruded, cooled and granulated to obtain the migration-resistant and anti-aging masterbatch; wherein the melt-blending is carried out in an internal mixer, and the extrusion is carried out in a twin-screw extruder, and the extrusion temperature is 170°C.

[0056] The infrared spectra of polyethylene (i.e. blank PE) and the migration and anti-aging masterbatch (i.e. PE masterbatch) provided in Example 1 were tested by Fourier infrared spectrometer. The results are as follows: Figure 2 As shown, by comparing the infrared spectra of the two, it can be seen that the metal salt coordinates with the antioxidant 1010 to form a complex.

[0057] Example 2

[0058] The present embodiment provides a migration-resistant and anti-aging masterbatch, which includes, by weight percentage, 50% polyethylene (Daqing Petrochemical, DFDA-7042) and 50% of a light stabilizer UV2020 (number average molecular weight of 2800) and sodium benzoate; the ratio of the total molar amount of the coordinated functional groups in the light stabilizer UV2020 to the molar amount of sodium benzoate is 2:1.

[0059] This embodiment provides a method for preparing the migration-resistant and anti-aging masterbatch, and the specific steps include the following steps:

[0060] According to the formula, polyethylene, light stabilizer UV2020 and sodium benzoate are melt-blended at a temperature of 150°C and a rotation speed of 20 rpm for 20 minutes, and then extruded, cooled and granulated to obtain the migration-resistant and anti-aging masterbatch; wherein the melt-blending is carried out in an internal mixer, and the extrusion is carried out in a twin-screw extruder, and the extrusion temperature is 150°C.

[0061] Example 3

[0062] The present embodiment provides a migration-resistant and anti-aging masterbatch, which includes, by weight percentage, 85% of ethylene-vinyl acetate copolymer (EVAV5110J, Yangzi Petrochemical) and 15% of light stabilizer UV3529 and zinc chloride in total weight; the ratio of the total molar amount of the coordinating functional groups in the light stabilizer UV3529 to the molar amount of zinc chloride is 2:1.

[0063] This embodiment provides a method for preparing the migration-resistant and anti-aging masterbatch, which specifically comprises the following steps:

[0064] According to the formula, ethylene-vinyl acetate copolymer, light stabilizer UV3529 and zinc chloride are melt-blended at a temperature of 120°C and a rotation speed of 100 rpm for 10 minutes, and then extruded, cooled and granulated to obtain the migration-resistant and anti-aging masterbatch; wherein the melt-blending is carried out in an internal mixer, and the extrusion is carried out in a twin-screw extruder, and the extrusion temperature is 120°C.

[0065] Example 4

[0066] This embodiment provides a migration-resistant and anti-aging auxiliary agent, which includes, by weight percentage, 85% polyurethane (BASF 1195A) and 15% of a light stabilizer UV3529 and cerium nitrate; the ratio of the total molar amount of the coordinating functional groups in the light stabilizer UV3529 to the molar amount of cerium nitrate is 3:1.

[0067] This embodiment provides a method for preparing the migration-resistant anti-aging additive, which specifically comprises the following steps:

[0068] According to the formula, polyurethane, light stabilizer UV3529 and cerium nitrate are melt-blended at a temperature of 220°C and a rotation speed of 150rpm for 15 minutes, and then extruded, cooled and granulated to obtain the migration-resistant and anti-aging masterbatch; wherein the melt-blending is carried out in an internal mixer, and the extrusion is carried out in a twin-screw extruder, and the extrusion temperature is 220°C.

[0069] Example 5

[0070] This embodiment provides a migration-resistant and anti-aging masterbatch, which differs from Embodiment 1 only in that the ratio of the total molar amount of the coordinating functional groups of the antioxidant 1010 to the molar amount of zinc stearate is 0.2:1, and the other components, amounts and preparation methods are the same as those in Embodiment 1.

[0071] Example 6

[0072] This embodiment provides a migration-resistant and anti-aging masterbatch, which differs from Embodiment 1 only in that the ratio of the total molar amount of the coordinating functional groups of the antioxidant 1010 to the molar amount of zinc stearate is 20:1, and the other components, amounts and preparation methods are the same as those in Embodiment 1.

[0073] Example 7

[0074] This embodiment provides a migration-resistant and anti-aging masterbatch, which differs from Embodiment 1 only in that the zinc stearate is replaced by a mixture of cerium nitrate and zinc stearate with equal molar amounts of metal ions, and the molar ratio of the metal ions in the cerium nitrate to the metal ions in the zinc stearate is 1:0.2. The other components, amounts and preparation methods are the same as those in Embodiment 1.

[0075] Example 8

[0076] This embodiment provides a migration-resistant and anti-aging masterbatch, which differs from Embodiment 1 only in that the zinc stearate is replaced by a mixture of cerium nitrate and zinc stearate with equal molar amounts of metal ions, and the molar ratio of the metal ions in the cerium nitrate to the metal ions in the zinc stearate is 1:0.8. The other components, amounts and preparation methods are the same as those in Embodiment 1.

[0077] Example 9

[0078] This embodiment provides a migration-resistant and anti-aging masterbatch, which differs from Embodiment 1 only in that the zinc stearate is replaced by a mixture of cerium nitrate and zinc stearate with equal molar amounts of metal ions, and the molar ratio of the metal ions in the cerium nitrate to the metal ions in the zinc stearate is 1:0.1. The other components, amounts and preparation methods are the same as those in Embodiment 1.

[0079] Example 10

[0080] This embodiment provides a migration-resistant and anti-aging masterbatch, which differs from Embodiment 1 only in that the zinc stearate is replaced by a mixture of cerium nitrate and zinc stearate with equal molar amounts of metal ions, the molar ratio of the metal ions in the cerium nitrate to the metal ions in the zinc stearate is 1:3, and the other components, amounts and preparation methods are the same as those in Embodiment 1.

[0081] Embodiment 11

[0082] This embodiment provides a migration-resistant and anti-aging masterbatch, which differs from Embodiment 2 only in that the light stabilizer UV2020 is replaced by a light stabilizer UV622 having an equal molar amount of coordinating functional groups, and the other components, amounts and preparation methods are the same as those in Embodiment 2.

[0083] Example 12

[0084] This embodiment provides a migration-resistant and anti-aging masterbatch, which is different from Embodiment 1 only in that the melting temperature in the preparation method is 100° C. and the time is 50 min. Other components, dosages and preparation methods are the same as those in Embodiment 1.

[0085] Embodiment 13

[0086] This embodiment provides a migration-resistant and anti-aging masterbatch, which is different from Embodiment 1 only in that the melting temperature in the preparation method is 500° C. and the time is 2 min. Other components, dosages and preparation methods are the same as those in Embodiment 1.

[0087] Embodiment 14

[0088] The present embodiment provides a precipitation-resistant and anti-aging masterbatch, which differs from the embodiment 1 only in that the preparation method comprises: dissolving the antioxidant 1010 in ethanol, adding the solution into a conical flask, slowly dropping an anhydrous ethanol solution of zinc stearate, adjusting the pH to 8 with a sodium hydroxide solution, stirring and reacting at 60° C. for 24 hours to obtain a complex; then mixing the complex with polyethylene at 80° C. for 30 minutes using a high-speed mixer, and adding the mixture to a twin-screw extruder after uniform mixing, and performing melting, mixing, extrusion, cooling, and granulation. The process parameters of the twin-screw extruder are the same as those in the embodiment 1, and the other components and amounts are also the same as those in the embodiment 1.

[0089] Comparative Example 1

[0090] This comparative example provides a migration-resistant anti-aging masterbatch, which differs from Example 1 only in that the migration-resistant anti-aging masterbatch does not contain zinc stearate, the mass percentage of antioxidant 1010 is 30%, and the other components, dosages and preparation methods are the same as those in Example 1.

[0091] Comparative Example 2

[0092] This comparative example provides a migration-resistant and anti-aging masterbatch, which differs from Example 2 only in that the light stabilizer UV2020 is replaced by a light stabilizer UV770 (bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate) with an equal molar amount of coordinating functional groups, and the other components, amounts and preparation methods are the same as those in Example 2.

[0093] Application Examples

[0094] This application example provides an anti-aging product, which includes a base resin (polyethylene, 7042) and an anti-aging masterbatch in a mass ratio of 90:10; the anti-aging masterbatch is the migration-resistant anti-aging masterbatch provided in Examples 1 to 14 and Comparative Examples 1 and 2.

[0095] The flow chart of the preparation method of the anti-aging product is as follows Figure 1 As shown, the method comprises mixing the migration-resistant anti-aging masterbatch with the matrix resin, molding, and obtaining the anti-aging product; specifically comprising the following steps: uniformly mixing the matrix resin and the anti-aging masterbatch at room temperature according to the formula amount, and then molding by extrusion blow molding using a single screw extruder. The barrel temperature of the single screw extruder is set to 175°C, and the head temperature is set to 200°C. After being melted and extruded by the extruder, the film enters the die head to form a film for extrusion. Compressed air is blown into the cooling air duct at the center of the die head to inflate the film into a cylindrical film. After being cooled by internal and external air, the herringbone splint exhausts the air in the film bubble, and then the film is pulled and rolled up to obtain the anti-aging product.

[0096] Performance Testing

[0097] (1) Migration resistance: 1 g of the anti-aging product was cut into pieces of 0.75 cm × 2.5 cm in size and placed in a non-woven bag. The non-woven bag was placed in a flat-bottomed flask and the Soxhlet extraction reaction equipment was assembled. Then 200 mL of dichloromethane was added to the flat-bottomed flask and the extraction was performed at 50°C for 24 h. 1 mL of the extract was taken and the content of the anti-aging agent therein was detected by high performance liquid chromatography, and the retention rate of the anti-aging agent was calculated.

[0098] (2) Anti-aging performance: Cut the anti-aging products into 6×10 cm and put them into the mold, and then put them into the UV aging box. Set the aging program according to GB / T 14522-2008 (8h drying (0.76W / (m 2 ·nm), 50℃; 0.25h spray; 3.75h condensation, 50℃). After the aging time reaches 30 days, the anti-aging products are taken out and cut into 1×5cm, with three parallel samples for each sample. The mechanical properties of the film before and after aging are tested, and the mechanical property retention rate of the film after 30 days of ultraviolet light acceleration is used to characterize the anti-aging performance of the product; among them, the mechanical property test refers to GB / T1040.1-2018, and the tensile strength retention rate of the test product is tested.

[0099] The specific test results are shown in Table 1.

[0100] Table 1

[0101] Migration resistance (additive retention rate, %) Anti-aging performance (tensile strength retention rate %) Example 1 87 81 Example 2 88 83 Example 3 83 78 Example 4 87 81 Example 5 85 79 Example 6 81 76 Example 7 91 86 Example 8 91 87 Example 9 88 82 Example 10 89 83 Embodiment 11 77 60 Example 12 61 48 Embodiment 13 64 49 Embodiment 14 71 61 Comparative Example 1 51 36 Comparative Example 2 45 32

[0102] As can be seen from Table 1, the migration-resistant anti-aging masterbatch provided by the present invention is compounded with an anti-aging additive having a number average molecular weight greater than or equal to 1000 and a metal salt, so that the migration and precipitation of the additive on the surface of the polymer material are reduced, and the anti-aging performance is good, the anti-aging performance is stable, and the long-term anti-aging effect is good.

[0103] Comparison of Examples 1 and 2 with Comparative Examples 1 and 2 shows that the migration-resistant anti-aging masterbatch contains no metal salt or the molecular weight of the anti-aging additive is low, and the additive in the polymer material is easy to migrate and has poor anti-aging performance.

[0104] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A migration-resistant and anti-aging masterbatch, characterized in that: The raw materials for preparing the migration-resistant and anti-aging masterbatch include anti-aging additives, metal salts and resins; The number average molecular weight of the anti-aging agent is ≥1000.

2. The migration-resistant and anti-aging masterbatch according to claim 1, characterized in that: The migration-resistant anti-aging masterbatch comprises a masterbatch prepared by blending an anti-aging aid, a metal salt and a resin in a molten state; Preferably, the number average molecular weight of the anti-aging agent is 1000 to 4000; Preferably, the anti-aging aid comprises an antioxidant and / or a light stabilizer; Preferably, the antioxidant comprises a hindered phenol antioxidant and / or a hindered amine antioxidant; Preferably, the antioxidant includes at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris[2.4-di-tert-butylphenyl]phosphite, pentaerythritol tetrakis(3-laurylthiopropionate), 4,4'-isopropyl diphenyl C12-15-ol phosphite, 4,4'-butylene bis-(3-methyl-6-tert-butylphenyl)-tetrakis(tridecyl)diphosphite, and poly(dipropylene glycol)phenyl phosphite.

3. The migration-resistant and anti-aging masterbatch according to claim 2, characterized in that: The light stabilizer includes a hindered amine light stabilizer and / or a benzoate light stabilizer; Preferably, the light stabilizer comprises a reaction product of poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-bis[(2,2,6,6-tetramethyl-piperidinyl)imino]-1,6-hexanediamine[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}, 1,6-hexanediamine N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) and 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, poly(succinic acid (4-hydroxy-2 ,2,6,6-tetramethyl-1-piperidinylethanol) ester, poly(6-morpholinyl-5-triazine-2,4-diyl)(2,2,6,6-tetramethylpiperidinyl)iminohexamethylene[(2,2,6,6-tetramethylpiperidinyl)-imino], methylated polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine with morpholinyl-2,4,6-trichloro-1,3,5-triazine, light stabilizer 783, light stabilizer 362, light stabilizer 119, light stabilizer 625, light stabilizer T68, light stabilizer T69 or light stabilizer 356.

4. The migration-resistant and anti-aging masterbatch according to any one of claims 1 to 3, characterized in that: The metal salt includes metal organic salt and / or metal inorganic salt; Preferably, the metal organic salt comprises a fatty acid salt and / or an aromatic acid salt; Preferably, the number of carbon atoms in the fatty acid salt is ≥1; Preferably, the fatty acid salt comprises at least one of formate, acetate, lactate, tartrate, citrate, palmitate, and stearate; Preferably, the aromatic acid salt comprises at least one of benzoate and salicylate; Preferably, the metal inorganic salt comprises at least one of chloride, nitrate, nitrite, sulfate, sulfite, carbonate, bicarbonate, phosphate, hydrogen phosphate, dihydrogen phosphate or borate; Preferably, the metal salt comprises a rare earth metal salt and / or a non-rare earth metal salt; Preferably, the rare earth metal ions in the rare earth metal salt include La 3+ 、Ce 3+ 、Eu 3+ , Yb 3+ , Gd 3+ , Tb 3+ 、Sm 3+ 、Dy 3+ 、Nd 3+ 、Ho 3+ , Er 3+ 、Tm 3+ , Pr 3+ At least one of; Preferably, the non-rare earth metal salt comprises at least one of ferric salt, ferrous salt, zinc salt, cuprous salt, copper salt, sodium salt, potassium salt, calcium salt, barium salt or magnesium salt.

5. The migration-resistant and anti-aging masterbatch according to any one of claims 1 to 4, characterized in that: The metal salt includes a rare earth metal salt and a non-rare earth metal salt, and the molar ratio of the metal ions in the rare earth metal salt to the metal ions in the non-rare earth metal salt is 1:(0.05-5), and more preferably 1:(0.2-0.8).

6. The migration-resistant and anti-aging masterbatch according to any one of claims 1 to 5, characterized in that: The ratio of the total molar amount of the coordinating functional groups in the anti-aging agent to the molar amount of the metal salt is (0.1-30):1, more preferably (0.5-12):1; Preferably, the migration-resistant and anti-aging masterbatch comprises 50 to 99.9% of resin in terms of mass percentage; Preferably, the resin includes at least one of polyethylene, ethylene-vinyl acetate copolymer, thermoplastic elastomer, polyvinyl chloride, polystyrene, polypropylene, polyvinylidene chloride, polyamide, polyester, polyurethane, polyvinyl alcohol, polyvinyl acetate, polyacrylonitrile, polycarbonate or polytetrafluoroethylene.

7. A method for preparing the migration-resistant and anti-aging masterbatch according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: The anti-aging auxiliary agent, metal salt and resin are mixed and melted, and extruded into granules to obtain the migration-resistant anti-aging masterbatch.

8. The preparation method according to claim 7, characterized in that: The temperature of the mixed melting is 80 to 400° C. Preferably, the mixing and melting time is 0.1 to 200 min, more preferably 0.1 to 30 min; Preferably, the rotation speed of the mixed melting is 10 to 200 rpm.

9. An anti-aging product, characterized in that: The material of the anti-aging product comprises a base resin and the migration-resistant anti-aging masterbatch according to any one of claims 1 to 6.

10. The anti-aging product according to claim 9, characterized in that: The mass ratio of the migration-resistant and anti-aging masterbatch to the matrix resin is (1-30):(40-99).

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