Thiamine compound and application thereof

Abstract

The invention provides a thiamine compound as shown in a formula (I) and application thereof. The thiamine compound can be used for preparing a polyolefin antioxidant. According to the thiamine compound disclosed by the invention, thioether bonds are introduced into a primary antioxidant such as aryl secondary amine, so that the antioxidant contains naphthylamine groups of the primary antioxidant and thioether groups of an auxiliary antioxidant, free radicals can be terminated by providing hydrogen protons, and the thiamine compound can react with hydroperoxide to achieve dual effects of the primary antioxidant and the auxiliary antioxidant; therefore, the anti-oxidation effect is obviously enhanced. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of chemical materials, and in particular to a thiamine compound and application thereof. Background Art

[0002] Polyolefin materials are widely used in various fields of production and life due to their excellent mechanical properties and chemical inertness. In recent years, the polymer materials industry has developed rapidly, especially the gap in high-end products has continued to increase, such as high-end polyethylene pipe materials, highly transparent medical resin poly-4-methyl-1-pentene and high-end polybutene-1 pipe materials. However, during its processing and use, it is inevitably affected by light, heat, oxygen, mechanical shear and heavy metal ions, which causes it to age and degrade, until it loses its commercial value and use value. For most polyolefin materials, adding antioxidants to improve their antioxidant properties is a simple and effective way. According to the different mechanisms of action of antioxidants, antioxidants mainly include two categories: primary antioxidants and auxiliary antioxidants. The primary antioxidants terminate free radical chain reactions by providing hydrogen protons or capturing free radicals to generate inert products, thereby inhibiting chain growth reactions. Commonly used primary antioxidants are hindered phenols and aromatic secondary amines. Auxiliary antioxidants terminate oxidation reactions by decomposing the hydroperoxides produced by chain growth reactions. Commonly used auxiliary antioxidants are phosphites and thioethers. Since the primary antioxidants and auxiliary antioxidants have different mechanisms of action, they are usually mixed and added to polyolefin materials to produce antioxidant synergistic effects, thereby having better antioxidant effects.

[0003] Since single-function antioxidants cannot meet the multi-faceted performance requirements of high-end polyolefin materials, composite antioxidants have low cost, good comprehensive performance, short development cycle, and multiple additives that fully exert synergistic effects, which can meet the multi-faceted performance requirements of high-end polyolefin materials, multifunctional, compound antioxidants have become one of the main trends in the current development of antioxidants. Intermolecular composite antioxidants are made by mixing the main antioxidant and the auxiliary antioxidant in a certain proportion. This type of composite antioxidant has a highly efficient antioxidant effect, allowing various antioxidants to complement each other and synergistically exert antioxidant properties.

[0004] More and more studies have shown that high molecular weight antioxidants have the advantages of low volatility, resistance to extraction, and high temperature resistance, which can reduce their losses during high-temperature processing and application of polymers. Therefore, research on high molecular weight antioxidants with superior performance has become a trend in the field of antioxidant research. Summary of the invention

[0005] In order to solve the problems that high-end polyolefin antioxidants have a single antioxidant mechanism and limited antioxidant effect, resulting in poor antioxidant effect, antioxidants are easily decomposed at high temperatures during processing and application, have poor stability, and have poor resistance to migration and extraction between antioxidants and materials, and are easy to precipitate, resulting in poor antioxidant performance of materials, they are applied to polyolefin materials such as poly-4-methyl-1-pentene, which has a very excellent antioxidant effect.

[0006] One object of the present invention is to provide a thiamine compound;

[0007] Another object of the present invention is to provide a method for preparing the thiamine compound;

[0008] Another object of the present invention is to provide the use of the thiamine compound in the preparation of antioxidants;

[0009] Another object of the present invention is to provide a polyolefin antioxidant composite auxiliary agent;

[0010] Another object of the present invention is to provide a polyolefin material;

[0011] Another object of the present invention is to provide a method for preparing the polyolefin material.

[0012] To achieve the above object, in one aspect, the present invention provides a thiamine compound represented by formula (I):

[0013]

[0014] Where R1 is C2-C 20 of alkylene;

[0015] R2, R3, R4 and R5 are each independently selected from the following general formula:

[0016]

[0017] Wherein R6 is an alkylene group;

[0018] R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 Each is independently selected from hydrogen or C1-C6 alkyl;

[0019] R 15 Selected from C6-C 20 Aryl or C1-C 10 A branched or straight chain alkyl group.

[0020] The thiamine compound of the present invention contains both the naphthylamine group of the main antioxidant and the thioether group of the auxiliary antioxidant, which can achieve the synergistic effect of the main and auxiliary antioxidants in the molecule, that is, can quickly terminate the free radical chain reaction and decompose the hydroperoxides produced by the chain reaction, and has a very excellent antioxidant effect.

[0021] The thiamine compound of the present invention has a large molecular weight, is not easy to precipitate during processing and use, has good extraction resistance, has multiple rigid benzene ring structures and non-hydrolyzable connecting groups in the molecular structure, is not easy to hydrolyze and thermally decompose into small molecules during processing and use, and has better stability. The thiamine compound of the present invention is applied to high-end polyolefin materials, especially poly-4-methyl-1-pentene resin, to effectively improve the antioxidant performance of the material.

[0022] According to some specific embodiments of the present invention, wherein R1 is C2-C 14 of alkylene.

[0023] According to some specific embodiments of the present invention, R6 is a straight-chain alkylene group.

[0024] According to some specific embodiments of the present invention, R6 is a C2-C5 straight chain alkylene group.

[0025] According to some specific embodiments of the present invention, R6 is a C2-C3 straight chain alkylene group.

[0026] According to some specific embodiments of the present invention, R6 is a C2 straight chain alkylene group.

[0027] According to some specific embodiments of the present invention, R2, R3, R4 and R5 have the same structure.

[0028] According to some specific embodiments of the present invention, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 Each is independently selected from hydrogen or C1-C4 alkyl.

[0029] According to some specific embodiments of the present invention, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 Each is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.

[0030] According to some specific embodiments of the present invention, R7, R8, R9, R 10 , R11 , R 12 , R 13 , R 14 For hydrogen.

[0031] According to some specific embodiments of the present invention, wherein R 15 Selected from C6-C 16 or a C1-C6 branched or straight chain alkyl group.

[0032] According to some specific embodiments of the present invention, wherein R 15 Selected from C6-C 14 or a C1-C6 branched or straight chain alkyl group.

[0033] According to some specific embodiments of the present invention, wherein R 15 Selected from C6-C 12 or a C1-C6 branched or straight chain alkyl group.

[0034] According to some specific embodiments of the present invention,

[0035] R1 is C2-C 14 of alkylene;

[0036] R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 is hydrogen;

[0037] R 15 is selected from phenyl, naphthyl, isopropyl or isobutyl.

[0038] According to some specific embodiments of the present invention, the compound is a compound represented by the following formula (II):

[0039]

[0040] According to some specific embodiments of the present invention,

[0041] R1 is C2-C 14 of alkylene;

[0042] R 15 is selected from phenyl, naphthyl, isopropyl, isobutyl or isopentyl.

[0043] According to some specific embodiments of the present invention, wherein R1 is C8-C 14 of alkylene.

[0044] According to some specific embodiments of the present invention, wherein R 15is selected from phenyl, naphthyl, isopropyl or isobutyl. According to some specific embodiments of the present invention, wherein R 15 Selected from naphthyl or isobutyl.

[0045] According to some specific embodiments of the present invention, the compound is selected from the following compounds:

[0046]

[0047]

[0048]

[0049]

[0050] On the other hand, the present invention also provides a method for preparing the thiamine compound of the present invention, the method comprising: 15 X is a raw material for preparing a thiamine compound represented by formula (I), wherein X is selected from F, Cl, Br or I,

[0051]

[0052] According to some specific embodiments of the present invention, the compound of formula (III) and R 15 Formula X undergoes a substitution reaction in the presence of a catalyst to prepare a thiamine compound represented by formula (I).

[0053] According to some specific embodiments of the present invention, the compound of formula (III) and R 15 Formula X undergoes a substitution reaction in the presence of a catalyst and a promoter to prepare a thiamine compound represented by formula (I).

[0054] According to some specific embodiments of the present invention, the catalyst is bistriphenylphosphine palladium dichloride and / or palladium acetate.

[0055] According to some specific embodiments of the present invention, the accelerator is N,N-diisopropylethylamine.

[0056] According to some specific embodiments of the present invention, the molar amount of the promoter is 0.01-0.07 times the molar amount of the compound of formula (III).

[0057] According to some specific embodiments of the present invention, the molar amount of the promoter is 0.03-0.05 times the molar amount of the compound of formula (III).

[0058] According to some specific embodiments of the present invention, the molar amount of the catalyst is 0.05-0.12 times the molar amount of the compound of formula (III).

[0059] According to some specific embodiments of the present invention, the molar amount of the catalyst is 0.08-0.10 times the molar amount of the compound of formula (III).

[0060] According to some specific embodiments of the present invention, wherein R 15 The molar amount of X is 5-10 times the molar amount of the compound of formula (III).

[0061] According to some specific embodiments of the present invention, wherein R 15 The molar amount of X is 6-7 times the molar amount of the compound of formula (III).

[0062] According to some specific embodiments of the present invention, wherein the compound of formula (III) and R 15 The step of preparing the thiamine compound represented by formula (I) wherein X is a raw material comprises: 15 The X solution is dropped into the reaction system to react.

[0063] According to some specific embodiments of the present invention, wherein R 15 The dripping rate of X solution is 5-10 ml / min.

[0064] According to some specific embodiments of the present invention, wherein the compound of formula (III) and R 15 In the step of preparing the thiamine compound represented by formula (I) using X as a raw material, the reaction temperature is 50-100°C.

[0065] According to some specific embodiments of the present invention, wherein the compound of formula (III) and R 15 In the step of preparing the thiamine compound represented by formula (I) using X as a raw material, the reaction temperature is 70-80°C.

[0066] According to some specific embodiments of the present invention, wherein the compound of formula (III) and R 15 In the step of preparing the thiamine compound represented by formula (I) using X as a raw material, the reaction time is 2-6 hours.

[0067] According to some specific embodiments of the present invention, wherein the compound of formula (III) and R 15 In the step of preparing the thiamine compound represented by formula (I) using X as a raw material, the reaction time is 4-5 hours.

[0068] According to some specific embodiments of the present invention, the method further comprises preparing a compound of formula (III) using a compound of formula (IV) and a compound of formula (V) as raw materials:

[0069]

[0070] According to some specific embodiments of the present invention, the compound of formula (IV) and the compound of formula (V) are prepared under alkaline conditions to obtain the compound of formula (III).

[0071] According to some specific embodiments of the present invention, the compound of formula (IV) and the compound of formula (V) are prepared under an inert gas atmosphere to obtain the compound of formula (III).

[0072] According to some specific embodiments of the present invention, the compound of formula (IV) and the compound of formula (V) are prepared in the presence of a basic catalyst to obtain the compound of formula (III).

[0073] According to some specific embodiments of the present invention, the compound of formula (IV) and the compound of formula (V) are prepared in a non-polar solvent in the presence of a basic catalyst to obtain the compound of formula (III).

[0074] According to some specific embodiments of the present invention, the alkaline catalyst is pyridine.

[0075] According to some specific embodiments of the present invention, the molar amount of the compound of formula (V) is 5-10 times the molar amount of the compound of formula (IV).

[0076] According to some specific embodiments of the present invention, the molar amount of the compound of formula (V) is 5-7 times the molar amount of the compound of formula (IV).

[0077] According to some specific embodiments of the present invention, the molar amount of the alkaline catalyst is 0.02-0.4 times the molar amount of the compound of formula (IV).

[0078] According to some specific embodiments of the present invention, the molar amount of the alkaline catalyst is 0.15-0.2 times the molar amount of the compound of formula (IV).

[0079] According to some specific embodiments of the present invention, the mass amount of the non-polar solvent is 5-9 times the total mass of the compound of formula (V) and the compound of formula (IV).

[0080] According to some specific embodiments of the present invention, the non-polar solvent is one or a mixture of benzene, toluene and ethylbenzene.

[0081] According to some specific embodiments of the present invention, in the step of preparing the compound represented by formula (III) using the compound represented by formula (IV) and the compound represented by formula (V) as raw materials, the reaction temperature is 80-140°C.

[0082] According to some specific embodiments of the present invention, in the step of preparing the compound represented by formula (III) using the compound represented by formula (IV) and the compound represented by formula (V) as raw materials, the reaction temperature is 90-100°C.

[0083] According to some specific embodiments of the present invention, in the step of preparing the compound represented by formula (III) using the compound represented by formula (IV) and the compound represented by formula (V) as raw materials, the reaction time is 4-12 hours.

[0084] According to some specific embodiments of the present invention, in the step of preparing the compound represented by formula (III) using the compound represented by formula (IV) and the compound represented by formula (V) as raw materials, the reaction time is 6-8 hours.

[0085] According to some specific embodiments of the present invention, the method further comprises preparing a compound represented by formula (IV) using a compound represented by formula (VI) and a compound represented by formula (VII) as raw materials:

[0086]

[0087] R 16 It is a bond or an alkylene group having 2 carbon atoms less than R6.

[0088] According to some specific embodiments of the present invention, the compound of formula (VI) and the compound of formula (VII) undergo Michael addition reaction to obtain the compound of formula (IV).

[0089] According to some specific embodiments of the present invention, the compound of formula (VI) and the compound of formula (VII) are reacted under an inert gas atmosphere to obtain the compound represented by formula (IV).

[0090] According to some specific embodiments of the present invention, the compound of formula (VI) and the compound of formula (VII) are reacted in the presence of a catalyst to obtain the compound of formula (IV).

[0091] According to some specific embodiments of the present invention, the compound of formula (VI) and the compound of formula (VII) are reacted in a non-polar solvent in the presence of a catalyst to obtain the compound represented by formula (IV).

[0092] According to some specific embodiments of the present invention, the catalyst used in the step of preparing the compound represented by formula (IV) from the compound represented by formula (VI) and the compound represented by formula (VII) is diazabicycle or hexahydropyridine.

[0093] According to some specific embodiments of the present invention, the molar amount of the catalyst used in the step of preparing the compound represented by formula (IV) from the compound represented by formula (VI) and the compound represented by formula (VII) is 0.05-0.2 times the molar amount of the compound represented by formula (VI).

[0094] According to some specific embodiments of the present invention, the molar amount of the catalyst used in the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is 0.1-0.15 times the molar amount of the compound represented by formula (VI).

[0095] According to some specific embodiments of the present invention, the mass amount of the non-polar solvent used in the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is 7-12 times the total mass of the compound represented by formula (VI) and the compound represented by formula (VII).

[0096] According to some specific embodiments of the present invention, the non-polar solvent used in the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is a mixture of one or more of benzene, toluene and ethylbenzene.

[0097] According to some specific embodiments of the present invention, the molar amount of the compound of formula (VII) is 2-4 times the molar amount of the compound of formula (VI).

[0098] According to some specific embodiments of the present invention, the molar amount of the compound of formula (VII) is 3-4 times the molar amount of the compound of formula (VI).

[0099] According to some specific embodiments of the present invention, the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials comprises dropping the compound represented by formula (VII) into the reaction system and then reacting.

[0100] According to some specific embodiments of the present invention, the dripping rate of the compound of formula (VII) is 5-10 ml / min.

[0101] According to some specific embodiments of the present invention, the reaction temperature of the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is room temperature to 50°C.

[0102] According to some specific embodiments of the present invention, the reaction temperature of the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is room temperature to 30°C.

[0103] According to some specific embodiments of the present invention, the reaction time of the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is 6-14 hours.

[0104] According to some specific embodiments of the present invention, the reaction time of the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is 6-8 hours.

[0105] According to some specific embodiments of the present invention, the preparation method of the compound of formula (I) is as follows:

[0106]

[0107] In another aspect, the present invention also provides use of the thiamine compound of the present invention in the preparation of an antioxidant.

[0108] According to some specific embodiments of the present invention, the antioxidant is an antioxidant for polyolefins.

[0109] On the other hand, the present invention also provides a polyolefin antioxidant composite additive, wherein the composite additive comprises the thiamine compound, heat stabilizer and rheological agent described in any one of the present invention; the mass ratio of the thiamine compound, heat stabilizer and rheological agent is 1: (0.25-0.75): (0.05-0.15).

[0110] In another aspect, the present invention further provides a polyolefin material, wherein the polyolefin material comprises: 100 parts by mass of a polyolefin resin and 0.1-0.26 parts by mass of the polyolefin antioxidant composite auxiliary agent described in the present invention.

[0111] According to some specific embodiments of the present invention, the heat stabilizer is selected from one or a combination of at least two of calcium stearate, magnesium stearate, zinc stearate and aluminum stearate; and the rheological agent is a fluorine rheological agent.

[0112] According to some specific embodiments of the present invention, the polyolefin is poly-4-methyl-1-pentene or polybutene-1.

[0113] On the other hand, the present invention also provides a method for preparing the polyolefin material, wherein the method comprises fully mixing the polyolefin resin with the polyolefin antioxidant composite auxiliary agent of the present invention and then extruding and granulating to obtain the polyolefin material, wherein the extrusion granulation temperature is 250-270°C and the extrusion rate is 5-15r / min.

[0114] According to some specific embodiments of the present invention, the mixing time for fully mixing the polyolefin resin and the polyolefin antioxidant composite auxiliary agent of the present invention is 5-20 minutes.

[0115] According to some specific embodiments of the present invention, the method comprises adding a polyolefin resin and the polyolefin antioxidant composite auxiliary agent of the present invention into a high-speed mixer and mixing them thoroughly, and then transferring them to a twin-screw extruder for extrusion granulation to obtain the polyolefin material, wherein the mixing time is 5-20 min, the extrusion granulation temperature is 250-270°C, and the extrusion rate is 5-15 r / min.

[0116] It can be understood that, under the premise of no contradiction, the specific embodiments of the present invention can be arbitrarily combined with each other.

[0117] In summary, the present invention provides a thiamine compound and its application. The thiamine compound of the present invention has the following advantages:

[0118] (1) The thiamine compound of the present invention has a relatively large molecular weight, which can be as high as 1641, and has excellent extraction resistance. At the same time, the molecular structure has a flexible long chain, and there are multiple rigid benzene ring structures and non-hydrolyzable linking groups. It is not easy to hydrolyze and thermally decompose into small molecules during processing and use, and enhances compatibility with polymer materials. Therefore, the antioxidant is not easy to precipitate during material processing and use, and the migration loss is small;

[0119] (2) The thiamine compound of the present invention introduces a thioether bond into a primary antioxidant such as an aromatic secondary amine, so that the antioxidant contains the naphthylamine group of the primary antioxidant and the thioether group of the auxiliary antioxidant. It can not only terminate free radicals by providing hydrogen protons, but also react with hydroperoxides to achieve the dual role of primary and auxiliary antioxidants. In addition, the thioether bond introduced is located at the para position of the aromatic secondary amine. Due to the electron-withdrawing effect, the electron cloud density at the position where the para position of the benzene ring is connected to the secondary amine group is reduced, thereby making it easier for the hydrogen on the secondary amine group to leave and causing a free radical termination reaction. This can quickly terminate the free radical chain reaction and decompose the hydroperoxides produced by the chain reaction, thereby significantly enhancing the antioxidant effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0120] Figure 1 This is the H NMR spectrum of the thiamine composite antioxidant prepared in Example 1;

[0121] Figure 2 The mass spectrum of the thiamine composite antioxidant prepared in Example 1;

[0122] Figure 3 This is the H-NMR spectrum of the thiamine composite antioxidant prepared in Example 11;

[0123] Figure 4 is the mass spectrum of the thiamine composite antioxidant prepared in Example 11;

[0124] Figure 5 This is the H-NMR spectrum of the thiamine composite antioxidant prepared in Example 12;

[0125] Figure 6 This is the mass spectrum of the thiamine composite antioxidant prepared in Example 12;

[0126] Figure 7 This is the H NMR spectrum of the thiamine composite antioxidant prepared in Example 13;

[0127] Figure 8 This is the mass spectrum of the thiamine complex antioxidant prepared in Example 13. DETAILED DESCRIPTION

[0128] The implementation process of the present invention and the beneficial effects produced are described in detail below through specific embodiments, which is intended to help readers better understand the essence and characteristics of the present invention, and is not intended to limit the scope of implementation of the present invention.

[0129] Example 1

[0130] The preparation process of the antioxidant intermediate and the thiamine composite antioxidant (A1) of this embodiment is as follows:

[0131] The preparation route is as follows:

[0132]

[0133] a. Synthesis of antioxidant intermediate (I): Accurately weigh 100 mL of 0.1 mol / L 4-mercaptostyrene methanol solution, add 0.0003 mol of the catalyst hexahydropyridine under nitrogen protection, slowly add 30 mL of 0.1 mol / L 1,14-tetradecanediamine methanol solution dropwise while stirring at room temperature, and react for 8 hours under constant room temperature conditions. Remove methanol by reduced pressure distillation, then wash three times with ethyl acetate: ether = 1:10, and vacuum dry at 30°C for 24 hours to obtain antioxidant intermediate (I), with a yield of 91.2%.

[0134] b. Synthesis of antioxidant intermediate (II): Accurately weigh 30 mL of 0.1 mol / L antioxidant intermediate (I) toluene solution, add 0.0003 mol of catalyst pyridine, slowly add 200 mL of 0.1 mol / L p-phenylenediamine toluene solution at 60°C, heat to 100°C after the addition is complete, react for 8 hours, remove toluene by distillation under reduced pressure to obtain a crude product, and purify the crude product by silica gel column chromatography. The volume ratio of petroleum ether:ethyl acetate used as the eluent is 10:1 to obtain antioxidant intermediate (II) with a yield of 84.8%.

[0135] c. Synthesis of thiamine composite antioxidant (A1): Accurately weigh 100 mL of 0.1 mol / L toluene solution of antioxidant intermediate (II), add 0.001 mol of catalyst bistriphenylphosphine palladium dichloride and 0.0005 mol of promoter N,N-diisopropylethylamine under nitrogen protection, slowly add 120 mL of 0.5 mol / L toluene solution of 2-iodonaphthalene at 0°C while stirring, heat to 80°C and react for 5 hours, concentrate the reaction mixture under vacuum, dissolve the crude product in a mixed solvent of ethyl acetate and tetrahydrofuran, wash with the solution, and chromatograph the obtained organic phase to obtain thiamine composite antioxidant (A1) with a yield of 83.4%.

[0136] The thiamine composite antioxidant (thiamine compound, A1) synthesized in this example was analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry. The results are as follows: Figure 1 ,and Figure 2 As shown. Figure 1 It can be seen that the characterization data of thiamine antioxidant is: 1 HNMR(CD3Cl,400MHz): δ(ppm)1.29-1.36(m,24H,-CH2-CH2-),3.01(t,4H,N-CH2-),2.67-2.69(m ,16H,N-CH2-CH2-Ar),4.0(s,4H,NH-Ar),6.43-7.54(m,32H,Ar-H),7.36-7.88(m,28h,naph-H). Depend on Figure 2 It can be seen that m / z=1641.8 is the molecular ion peak of thiamine complex antioxidant.

[0137] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% (based on the total mass of the poly 4-methyl-1-pentene as 100%, the same below) of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0138] Embodiment 2:

[0139] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheology body (model FX5920A) were put into a high-speed mixer according to a mass ratio of 1:0.15:0.15:0.05, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to a powder extruder for extrusion to obtain a composite additive package.

[0140] In the granulation section of poly 4-methyl-1-pentene, 0.21% of the above composite additive is added, and the extruder is used to melt extrude, draw and granulate, the extrusion temperature is 260°C, and the extrusion rate is 10r / min. Then the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0141] Embodiment 3:

[0142] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheological body were put into a high-speed mixer in a mass ratio of 1:0.25:0.25:0.1, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to a powder extruder for extrusion to obtain a composite additive package.

[0143] In the granulation section of poly 4-methyl-1-pentene, 0.26% of the above composite additive is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0144] Embodiment 4:

[0145] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheological body were put into a high-speed mixer in a mass ratio of 1:0.35:0.35:0.15, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to a powder extruder for extrusion to obtain a composite additive package.

[0146] In the granulation section of poly 4-methyl-1-pentene, 0.21% of the above composite additive is added, and the extruder is used to melt extrude, draw and granulate, the extrusion temperature is 260°C, and the extrusion rate is 10r / min. Then the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0147] Embodiment 5:

[0148] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A2) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 1,14-tetradecanediamine in step a is replaced by 1,12-dodecanediamine, and the yield of step a is 93.4%.

[0149] The characterization data of the obtained thiamine antioxidant (A2) are: 1H NMR (CD3Cl, 400MHz): δ (ppm) 1.26-1.36 (m, 20H, -CH2-CH2-), 3.01 (t, 4H, N-CH2-), 2.67-2.69 (m ,16H,N-CH2-CH2-Ar),4.3(s,4H,NH-Ar),6.43-7.54(m,32H,Ar-H),7.36-7.88(m,28h,naph-H).

[0150]

[0151] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0152] Embodiment 6:

[0153] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A3) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 1,14-tetradecanediamine in step a is replaced by 1,10-decanediamine, and the yield of step a is 95.7%.

[0154] The characterization data of the obtained thiamine antioxidant (A3) are: 1 H NMR(CD3Cl,400MHz): δ(ppm)1.29-1.36(m,16H,-CH2-CH2-),3.01(t,4H,N-CH2-),2.67-2.69(m ,16H,N-CH2-CH2-Ar),4.3(s,4H,NH-Ar),6.43-7.54(m,32H,Ar-H),7.36-7.88(m,28h,naph-H).

[0155]

[0156]

[0157] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0158] Embodiment 7:

[0159] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A4) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 1,14-tetradecanediamine in step a is replaced by 1,8-octanediamine, and the yield of step a is 96.1%.

[0160] The characterization data of the obtained thiamine antioxidant (A4) are: 1 H NMR(CD3Cl,400MHz): δ(ppm)1.29-1.36(m,12H,-CH2-CH2-),3.01(t,4H,N-CH2-),2.67-2.69(m ,16H,N-CH2-CH2-Ar),4.3(s,4H,NH-Ar),6.43-7.54(m,32H,Ar-H),7.36-7.88(m,28h,naph-H).

[0161]

[0162] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0163] Embodiment 8:

[0164] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A5) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 1,14-tetradecanediamine in step a is replaced by 1,6-hexanediamine, and the yield of step a is 96.9%.

[0165] The characterization data of the obtained thiamine antioxidant (A5) are: 1 H NMR (CD3Cl, 400MHz): δ (ppm) 1.26-1.36 (m, 8H, -CH2-CH2-), 3.01 (t, 4H, N-CH2-), 2.67-2.69 (m, 16H,N-CH2-CH2-Ar),4.0(s,4H,NH-Ar),6.43-7.54(m,32H,Ar-H),7.36-7.88(m,28h,naph-H).

[0166]

[0167] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0168] Embodiment 9:

[0169] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A6) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 1,14-tetradecanediamine in step a is replaced by 1,4-butanediamine, and the yield of step a is 98.4%.

[0170] The characterization data of the obtained thiamine antioxidant (A6) are: 1 H NMR (CD3Cl, 400MHz): δ (ppm) 1.76 (t, 4H, -CH 2 -CH 2 -),3.01(t,4H,N-CH 2 -), 2.67-2.69(m,16H,N-CH 2 -CH 2 -Ar),4.2(s,4H,NH-Ar),6.43-7.54(m,32H,Ar-H),7.36-7.88(m,28h,naph-H).

[0171]

[0172] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0173] Embodiment 10:

[0174] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A7) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 1,14-tetradecanediamine in step a is replaced by ethylenediamine, and the yield of step a is 98.6%.

[0175] The characterization data of the obtained thiamine antioxidant (A7) are: 1H NMR (CD3Cl, 400MHz): δ (ppm) 2.37 (t, 4H, N-CH2-), 2.67-2.69 (m, 16H, N-CH2-CH2 -Ar),4.0(s,4H,NH-Ar),6.43-7.54(m,32H,Ar-H),7.36-7.88(m,28h,naph-H).

[0176]

[0177] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0178] Embodiment 11:

[0179] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A8) of this example are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 2-iodonaphthalene in step c is replaced by iodobenzene, and the yield of step c is 84.1%.

[0180]

[0181] The thiamine composite antioxidant (A8) synthesized in this example was analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry. The results are as follows: Figure 3 ,and Figure 4 As shown. Figure 3 It can be seen that the characterization data of thiamine antioxidant (A8) are: 1 H NMR(CD3Cl,400MHz): δ(ppm)1.29-1.36(m,24H,-CH2-CH2-),3.01(t,4H,N-CH2-),2.67-2.69(m,1 6H,N-CH2-CH2-Ar),4.0(s,4H,NH-Ar),6.43(d,8H,N-Ar-H),7.54(d,8H,S-Ar-H),6.81(t,4H,N-Ar para-H),7.09-7.28(m,32H,Ar-H). Depend on Figure 4 It can be seen that m / z=1442.2 is the molecular ion peak of thiamine complex antioxidant (A8).

[0182] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0183] Embodiment 12:

[0184] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A9) of this example are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 2-iodonaphthalene in step c is replaced by 2-iodopropane, and the yield of step c is 90.5%.

[0185] The thiamine composite antioxidant (A9) synthesized in this example was analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry. The results are as follows: Figure 5 ,and Figure 6 As shown. Figure 5 It can be seen that the characterization data of thiamine antioxidant (A9) are: 1 H NMR(CD3Cl,400MHz): δ(ppm)1.29-1.36(m,24H,-CH2-CH2-),3.01(t,4H,N-CH2-),2.67-2.69(m,16H,N-CH2-CH2-Ar),4.0( s,4H,NH-Ar),1.20(d,24H,C(CH3)2),3.95(m,4H,CH),6.40(d,8H,N-Ar-H),7.54(d,8H,S-Ar-H),7.09-7.19(d,16H,Ar-H). Depend on Figure 6 It can be seen that m / z=1304.7 is the molecular ion peak of thiamine complex antioxidant (A9).

[0186] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0187]

[0188] Embodiment 13:

[0189] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A10) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 2-iodonaphthalene in step c is replaced by 2-methyl-2-iodopropane, and the yield of step c is 92.7%.

[0190] The thiamine composite antioxidant (A10) synthesized in this example was analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry. The results are as follows: Figure 7 ,and Figure 8 As shown. Figure 7 It can be seen that the characterization data of thiamine antioxidant (A10) are: 1 H NMR(CD3Cl,400MHz): δ(ppm)1.29-1.36(m,24H,-CH2-CH2-),3.01(t,4H,N-CH2-),2.67-2.69(m,16H,N-CH2-CH2-A r),4.0(s,4H,NH-Ar),1.40(s,24H,C(CH3)3),6.40(d,8H,N-Ar-H),7.54(d,8H,S-Ar-H),7.09-7.19(d,16H,Ar-H). Depend on Figure 8 It can be seen that m / z=1360.5 is the molecular ion peak of thiamine complex antioxidant (A10).

[0191]

[0192] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0193] Embodiment 14:

[0194] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheology body (model FX5920A) were put into a high-speed mixer according to a mass ratio of 1:0.15:0.15:0.05, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to a powder extruder for extrusion to obtain a composite additive package.

[0195] In the granulation section of poly 4-methyl-1-pentene, 0.21% of the above composite additive is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 250° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0196] Embodiment 15:

[0197] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheology body (model FX5920A) were put into a high-speed mixer according to a mass ratio of 1:0.15:0.15:0.05, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to a powder extruder for extrusion to obtain a composite additive package.

[0198] In the granulation section of poly 4-methyl-1-pentene, 0.21% of the above composite additive is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 270°C and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0199] Embodiment 16:

[0200] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheology body (model FX5920A) were put into a high-speed mixer according to a mass ratio of 1:0.15:0.15:0.05, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to a powder extruder for extrusion to obtain a composite additive package.

[0201] In the granulation section of poly 4-methyl-1-pentene, 0.21% of the above composite additive is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 5 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0202] Embodiment 17:

[0203] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheology body (model FX5920A) were put into a high-speed mixer according to a mass ratio of 1:0.15:0.15:0.05, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to a powder extruder for extrusion to obtain a composite additive package.

[0204] In the granulation section of poly 4-methyl-1-pentene, 0.21% of the above composite additive is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 15 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0205] Comparative Example 1:

[0206] In the poly-4-methyl-1-pentene granulation section, 0.1% (based on the total mass of poly-4-methyl-1-pentene as 100%, the same below) of antioxidant DNP is added thereto to replace the composite antioxidant of the present invention, and according to the extrusion granulation process of Example 1, wire drawing and granulation are performed by a twin-screw extruder, the extrusion temperature is 260° C., and the extrusion rate is 10 r / min. Then the oxidation induction period and mechanical properties of poly-4-methyl-1-pentene are tested. The test results of the poly-4-methyl-1-pentene are shown in Table 1.

[0207]

[0208] Comparative Example 2:

[0209] In the poly-4-methyl-1-pentene granulation section, 0.1% antioxidant D is added thereto to replace the composite antioxidant of the present invention, and according to the extrusion granulation process of Example 1, the twin-screw extruder is used for extrusion drawing and granulation, the extrusion temperature is 260°C, and the extrusion rate is 10r / min. Then, the oxidation induction period and mechanical properties of the poly-4-methyl-1-pentene are tested. The test results of the poly-4-methyl-1-pentene are shown in Table 1.

[0210]

[0211] Comparative Example 3:

[0212] In the poly-4-methyl-1-pentene granulation section, 0.1% of didodecanol thiodipropionate was added thereto to replace the composite antioxidant of the present invention, and the extrusion granulation process of Example 1 was followed by extrusion, drawing and granulation by a twin-screw extruder, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the oxidation induction period and mechanical properties of the poly-4-methyl-1-pentene were tested. The test results of the poly-4-methyl-1-pentene are shown in Table 1.

[0213] Test Case

[0214] OIT analysis was carried out in accordance with GB / T 2951.1-1994 in a nitrogen atmosphere, with the temperature rising to 200°C at 20°C / min, held constant for 5 min, and then the nitrogen was replaced by oxygen and dropped to 25°C at -20°C / min.

[0215] Mechanical properties test was carried out in accordance with GB / T 1040-2006. Poly-4-methyl-1-pentene pellets were made into 5A dumbbell-shaped specimens by compression molding and placed at a temperature of (23±2)°C and a relative humidity of (50±5)% for 24 hours. The tensile rate was 50 mm / min.

[0216] The above OIT analysis results and mechanical properties test results are shown in Table 1:

[0217] Table 1 Analysis and test results of poly 4-methyl-1-pentene

[0218]

[0219]

[0220] It can be seen from the data in Table 1 that the thiamine composite antioxidants A1-A10 prepared by the present invention can effectively improve the mechanical properties and oxidation induction period of poly-4-methyl-1-pentene materials, and antioxidants A1 and A10 have the best antioxidant effects. At the same time, the antioxidant effect of the synthesized thiamine composite antioxidant is significantly better than that of commercial amine and thioether antioxidants when compared with commercial antioxidants.

[0221] The present invention provides a thiamine composite antioxidant, which contains both the naphthylamine group of the main antioxidant and the thioether group of the auxiliary antioxidant, and can realize the synergistic effect of the main and auxiliary antioxidants in the molecule, that is, the free radical chain reaction can be quickly terminated, and the hydroperoxide produced by the chain reaction can be decomposed, and there is a very excellent antioxidant effect. At the same time, the thiamine composite antioxidant has a large molecular weight, is not easy to precipitate during processing and use, has good extraction resistance, has multiple rigid benzene ring structures in the molecular structure, and a linking group that is not easy to hydrolyze, is not easy to hydrolyze and thermally decompose into small molecules during processing and use, and the stability of the antioxidant is better. It is applied to high-end resins such as polybutene-1 and poly-4-methyl-1-pentene, and the antioxidant properties of the material can be effectively improved, which has important guiding significance for the development and use of high-end resin additives.

Claims

1. Thiamine compound represented by formula (I): in, R1 is C2-C 20 of alkylene; R2, R3, R4 and R5 are each independently selected from the following general formula: Wherein R6 is an alkylene group; R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 Each is independently selected from hydrogen or C1-C6 alkyl; R 15 Selected from C6-C 20 Aryl or C1-C 10 A branched or straight chain alkyl group.

2. The thiamine compound according to claim 1, wherein R1 is C2-C 14 of alkylene.

3. The thiamine compound according to any one of claims 1 to 2, wherein R6 is a C2-C5 straight chain alkylene group.

4. The thiamine compound according to any one of claims 1 to 3, wherein R2, R3, R4 and R5 have the same structure.

5. The thiamine compound according to any one of claims 1 to 4, wherein R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 Independently selected from hydrogen or C1-C4 alkyl; preferably hydrogen.

6. The thiamine compound according to claim 1, wherein The compound is a compound represented by the following formula (II):

7. The thiamine compound according to any one of claims 1 to 6, wherein R 15 Selected from C6-C 14 or a C1-C6 branched or straight chain alkyl group.

8. The thiamine compound according to any one of claims 1 to 7, wherein R1 is C2-C 14 of alkylene; R 15 is selected from phenyl, naphthyl, isopropyl, isobutyl or isopentyl.

9. The thiamine compound according to any one of claims 1 to 8, wherein R1 is C8-C 14 of alkylene.

10. The thiamine compound according to any one of claims 1 to 9, wherein R 15 is selected from phenyl, naphthyl, isopropyl or isobutyl.

11. The thiamine compound according to claim 1, wherein The compound is selected from the following compounds:

12. Use of the thiamine compound according to any one of claims 1 to 11 in the preparation of an antioxidant.

13. The use according to claim 12, wherein: The antioxidant is an antioxidant for polyolefins.

14. A polyolefin antioxidant composite auxiliary agent, wherein: The composite auxiliary agent comprises the thiamine compound according to any one of claims 1 to 11, a heat stabilizer and a rheological agent; the mass ratio of the thiamine compound, the heat stabilizer and the rheological agent is 1: (0.25-0.75): (0.05-0.15).

15. A polyolefin material, wherein: The polyolefin material comprises: 100 parts by mass of a polyolefin resin and 0.1-0.26 parts by mass of the polyolefin antioxidant composite auxiliary agent according to claim 14.

16. The polyolefin material according to claim 15, wherein The heat stabilizer is selected from one or a combination of at least two of calcium stearate, magnesium stearate, zinc stearate and aluminum stearate; and the rheological agent is a fluorine rheological agent.

17. The polyolefin material according to claim 15 or 16, wherein The polyolefin is polyethylene, polypropylene, poly-4-methyl-1-pentene or polybutene-1.

18. The method for preparing the polyolefin material according to any one of claims 15 to 17, comprising fully mixing the polyolefin resin with the polyolefin antioxidant composite auxiliary agent according to claim 14 and then extruding and granulating to obtain the polyolefin material, wherein: The temperature of extrusion granulation is 250-270°C, and the extrusion rate is 5-15r / min.

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