Intramolecular composite antioxidant and poly (4-methyl-1-pentene) material

Abstract

The invention discloses an intramolecular composite antioxidant and a poly (4-methyl-1-pentene) material, the intramolecular composite antioxidant contains phenolic hydroxyl groups of a main antioxidant and thioether groups of an auxiliary antioxidant, and can realize a synergistic effect of the main and auxiliary antioxidants in molecules, namely, a free radical chain reaction can be quickly terminated; according to the present invention, the chain reaction can be inhibited, the hydroperoxide generated by the chain reaction can be decomposed, the anti-oxidation effect of the antioxidant can be effectively improved, the molecular structure has a plurality of rigid benzene ring structures and the linking group not easy to hydrolyze so as not to easily hydrolyze and thermally decompose into small molecules during the processing and using process, and the antioxidant has characteristics of good stability and low cost. And when being applied to a high-end polyolefin material, in particular to a poly (4-methyl-1-pentene) material, the antioxidant has a very excellent antioxidant effect.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis and relates to an antioxidant, in particular to an intramolecular composite antioxidant and a poly 4-methyl-1-pentene material containing the antioxidant. Background Art

[0002] Polyolefin materials are widely used in various fields such as production and life due to their excellent mechanical properties and chemical inertness. In recent years, the polymer material 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 shearing and heavy metal ions, causing 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 antioxidants with a single function cannot meet the various performance requirements of high-end polyolefin materials, and composite antioxidants have low cost, good comprehensive performance, short development cycle, and multiple additives fully exerting synergistic effects, they can meet the various performance requirements of high-end polyolefin materials. Therefore, multifunctional and compound antioxidants have become one of the main trends in the 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 high-efficiency antioxidant effect, allowing various antioxidants to complement each other and synergistically exert antioxidant properties. However, there are few reports on intramolecular composite antioxidants.

[0004] Chinese patent CN102516157B reports a hindered phenol / hindered amine molecular composite antioxidant, which first uses 3,5-dialkyl-4-hydroxybenzoic acid and dichlorothionyl to undergo substitution reaction to prepare an antioxidant intermediate, and then the antioxidant intermediate is subjected to amidation reaction with N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine, and then an acid binding agent is added, and the reaction is continued. After the reaction is completed, the hindered phenol / hindered amine intramolecular composite antioxidant is obtained. And it is added to polyamide resin, and it is found in long-term aging tests that the new antioxidant can significantly delay the degradation of polyamide resin. However, the antioxidant structure provided by this technology only contains hindered phenol units as the main antioxidant, so it does not play a synergistic role of the main and auxiliary antioxidants in terms of the mechanism of action.

[0005] Chinese patent CN201910752684.3 reports a hindered phenol and amide intramolecular composite bifunctional antioxidant and its synthesis method. The antioxidant is first made into an ethylenediamine dendritic molecular skeleton by ethylenediamine, methanol, and methyl acrylate, and then the end group of the ethylenediamine dendritic molecular skeleton is sealed with DtBHP to obtain the antioxidant. The antioxidant terminates the chain reaction by capturing the generated free radicals and forming relatively stable free radicals by itself. It can directly, effectively and quickly capture free radicals and has high antioxidant capacity. However, the hindered phenol and amine active units contained in the antioxidant structure of this technology are both main antioxidants, so the synergistic effect of the main and auxiliary antioxidants is not achieved in terms of the mechanism of action.

[0006] Chinese patent CN 108164750 B Hindered amine antioxidant and polyethylene material, the invention discloses a hindered amine antioxidant and polyethylene material, the hindered amine antioxidant of the invention has good compatibility with polymers, good anti-migration and anti-solvent extraction performance, can be applied to the anti-aging of various polymer materials, and the hindered amine antioxidant is lighter in color and not easy to color. However, the amine antioxidant provided by the technology is a typical primary antioxidant, which can only terminate free radicals by providing hydrogen protons, and cannot eliminate the hydroperoxides generated during the reaction. Hydroperoxides will further trigger the occurrence of oxidation reactions, so the antioxidant effect is limited. Summary of the invention

[0007] In order to solve the problems that the antioxidants for high-end polyolefins have a single antioxidant mechanism, limited antioxidant effects, resulting in poor antioxidant effects, and antioxidants are easily decomposed at high temperatures during processing and application, and have poor stability, the present invention provides an intramolecular composite antioxidant. The intramolecular composite antioxidant contains both the phenolic hydroxyl group of a main antioxidant and the thioether group of an auxiliary antioxidant, and can achieve the synergistic effect of the main and auxiliary antioxidants in the molecule, that is, it can quickly terminate the free radical chain reaction, and can decompose the hydroperoxides produced by the chain reaction, and has the effect of effectively improving the antioxidant effect of the antioxidant. At the same time, there are multiple rigid benzene ring structures and non-hydrolyzable connecting groups in the molecular structure, so that it is not easy to be hydrolyzed and thermally decomposed into small molecules during processing and use, and the antioxidant has better stability. The intramolecular composite antioxidant contains both the phenolic hydroxyl group of a main antioxidant and the thioether group of an auxiliary antioxidant, and can achieve the synergistic effect of the main and auxiliary antioxidants in the molecule, and can quickly terminate the free radical chain reaction, and can decompose the hydroperoxides produced by the chain reaction, and has the effect of effectively improving the antioxidant effect. At the same time, there are multiple rigid benzene ring structures and non-hydrolyzable connecting groups in the molecular structure, so that it is not easy to be hydrolyzed and thermally decomposed into small molecules during processing and use, and the antioxidant has better stability. The antioxidant is applied to high-end polyolefin materials, especially poly-4-methyl-1-pentene materials, and has a very excellent antioxidant effect.

[0008] To achieve the above object, the present invention provides an intramolecular composite antioxidant, which has the following structure:

[0009]

[0010] Wherein, R1, R2, R3, R4 are independently selected from hydrogen or alkyl, and R5 is selected from the following general formula:

[0011]

[0012] Wherein, R6, R7, R8, and R9 are independently selected from hydrogen or alkyl, R 10 , R 11 Independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.

[0013] In the intramolecular composite antioxidant of the present invention, R1, R2, R3 and R4 are independently selected from hydrogen, methyl, ethyl, n-propyl and isopropyl.

[0014] In the intramolecular composite antioxidant of the present invention, R6, R7, R8 and R9 are independently selected from hydrogen, methyl, ethyl, n-propyl and isopropyl.

[0015] The intramolecular composite antioxidant of the present invention, wherein the intramolecular composite antioxidant preferably has the following general formula:

[0016]

[0017] The present invention also provides a poly-4-methyl-1-pentene material, which contains the intramolecular composite antioxidant.

[0018] The poly 4-methyl-1-pentene material of the present invention comprises:

[0019] 100 parts by mass of poly-4-methyl-1-pentene resin;

[0020] Composite additives 0.1-0.19 parts by mass;

[0021] The composite auxiliary agent comprises an antioxidant, a heat stabilizer and a rheological agent, and the antioxidant is an intramolecular composite antioxidant.

[0022] In the poly-4-methyl-1-pentene material of the present invention, the heat stabilizer is one or more selected from the group consisting of calcium stearate, magnesium stearate, zinc stearate and aluminum stearate.

[0023] The poly-4-methyl-1-pentene material of the present invention, wherein the rheological agent is a fluorine rheological agent.

[0024] The poly 4-methyl-1-pentene material of the present invention comprises the antioxidant, the heat stabilizer and the rheological agent in a mass ratio of 1:0.25-0.75:0.05-0.15.

[0025] The poly 4-methyl-1-pentene material of the present invention, wherein during the preparation process of the poly 4-methyl-1-pentene material, the extrusion temperature is 250-270°C.

[0026] The intramolecular composite antioxidant of the present invention can be prepared according to the following method:

[0027] (1) 4-Mercaptobenzoic acid undergoes oxidative coupling reaction under the action of an oxidant to generate intermediate I;

[0028] (2) Intermediate I undergoes an amide substitution reaction with p-phenylenediamine to produce intermediate II;

[0029] (3) Intermediate II reacts with 4-mercapto-2,6-dialkylphenol under the action of a catalyst to undergo a thiolamine condensation reaction to obtain an intramolecular composite antioxidant. The reaction formula of the preparation method is as follows: Figure 1 shown.

[0030] The preparation method of the intramolecular composite antioxidant of the present invention comprises the following steps: the reaction of step (1) is to add an oxidant to 4-mercaptobenzoic acid for reaction, and the reaction is carried out in an alkaline condition and in a solvent; the oxidant is selected from an aqueous solution of iodine or an aqueous solution of hydrogen peroxide; the molar amount of the oxidant is 0.8-1.5 times the molar amount of 4-mercaptobenzoic acid; the alkaline condition is to add one of ethylamine, ethylenediamine, dimethylamine and 4-methylaminopyridine, wherein the molar amount of the alkaline substance is 1-2 times the molar amount of 4-mercaptobenzoic acid; the solvent is selected from one of a mixture of dichloromethane and water, a methanol aqueous solution or a mixture of acetone and water, and the mass of the solvent is 20-50 times the total mass of the reactants.

[0031] The method for preparing the intramolecular composite antioxidant of the present invention is preferably that in the reaction of step (1), the molar amount of the oxidant is 1-1.2 times the molar amount of 4-mercaptobenzoic acid, and the molar amount of the alkaline substance is 1.4-1.6 times the molar amount of 4-mercaptobenzoic acid.

[0032] In the method for preparing the intramolecular composite antioxidant of the present invention, the reaction temperature of step (1) is 0-50°C, and the reaction time is 1-6h. Preferably, the reaction temperature is room temperature-30°C, and the reaction time is 2-4h.

[0033] The preparation method of the intramolecular composite antioxidant of the present invention comprises the following steps: the reaction of step (2) is carried out under the protection of an inert gas, the intermediate I is reacted under the action of an alkaline catalyst and a non-polar solvent; the molar amount of the p-phenylenediamine is 2-5 times the molar amount of the intermediate I; the molar amount of the alkaline catalyst is 0.02-0.4 times the molar amount of the intermediate I; the mass of the non-polar solvent is 5-9 times the total mass of the intermediate I and the p-phenylenediamine; the alkaline catalyst is selected from one of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, triethanolamine and N,N-diisopropylethylamine; and the non-polar solvent is selected from at least one of benzene, toluene and ethylbenzene.

[0034] In the method for preparing the intramolecular composite antioxidant of the present invention, preferably, the molar amount of the p-phenylenediamine is 3-4 times the molar amount of the intermediate I; the molar amount of the alkaline catalyst is 0.15-0.2 times the molar amount of the intermediate I.

[0035] The preparation method of the intramolecular composite antioxidant of the present invention comprises the following steps: the p-phenylenediamine solution is dripped into the intermediate I for reaction, the reaction temperature is 80-140°C, the reaction time is 4-12h, preferably, the reaction temperature is 90-100°C, and the reaction time is 6-8h.

[0036] The method for preparing an intramolecular composite antioxidant of the present invention comprises the following steps: the reaction in step (3) is carried out under the protection of an inert gas, and the intermediate II and 4-mercapto-2,6-dialkylphenol undergo a condensation reaction under the action of a catalyst, pyridine; the molar amount of the pyridine is 0.05-0.12 times the molar amount of the intermediate II; and the molar amount of the 4-mercapto-2,6-dialkylphenol is 2-5 times the molar amount of the intermediate II.

[0037] In the method for preparing the intramolecular composite antioxidant of the present invention, preferably, the molar amount of pyridine is 0.08-0.10 times the molar amount of intermediate II; the molar amount of 4-mercapto-2,6-dialkylphenol is 3-4 times the molar amount of intermediate II.

[0038] The preparation method of the intramolecular composite antioxidant of the present invention comprises the following steps: step (3) is to drip 4-mercapto-2,6-dialkylphenol solution into intermediate II for reaction, the reaction temperature is 80-140°C, the reaction time is 5-10h, preferably, the reaction temperature is 90-110°C, and the reaction time is 6-8h.

[0039] The preparation method of the poly 4-methyl-1-pentene material of the present invention can be carried out according to the following steps:

[0040] In the granulation section of the poly 4-methyl-1-pentene resin, 4-methyl-1-pentene and a composite auxiliary agent with a mass percentage of 0.1-0.19% of 4-methyl-1-pentene are added. The composite auxiliary agent is prepared by an antioxidant, a heat stabilizer and a rheological agent in a mass ratio of 1:0.25-0.75:0.05-0.15, and the antioxidant is the above-mentioned intramolecular composite antioxidant.

[0041] Research has found that the introduction of thioether bonds in hindered phenolic primary antioxidants allows the antioxidants to not only terminate free radicals by providing hydrogen protons, but also react with hydroperoxides to achieve the dual role of primary and secondary antioxidants. In addition, the para position of the antioxidant active group phenolic hydroxyl is a thioether bond. Due to the electron-withdrawing induction effect, the electron cloud density at the para benzene ring of the secondary amine group is reduced, making it easier for the hydrogen on the phenolic hydroxyl group to leave, resulting in a free radical termination reaction, thereby significantly enhancing the antioxidant effect. At the same time, there is a pair of lone pairs of electrons on the secondary amine group, which can also combine with free radicals to terminate the free radical chain reaction.

[0042] The present invention has at least the following beneficial effects:

[0043] (1) The intramolecular composite antioxidant molecule introduces a thioether bond into the main antioxidant such as hindered phenol, so that the antioxidant can not only terminate free radicals by providing hydrogen protons, but also react with hydroperoxides to achieve the dual role of main and auxiliary antioxidants. In addition, the introduced thioether bond is located at the para position of the phenolic hydroxyl group. 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 phenolic hydroxyl group is reduced, thereby making it easier for the hydrogen on the phenolic hydroxyl group to leave, resulting in a free radical termination reaction, thereby significantly enhancing the antioxidant effect.

[0044] (2) The molecular structure of the intramolecular composite antioxidant contains multiple rigid benzene ring structures, which are not easy to decompose during processing, have better thermal stability, and are not easy to decompose into small molecules. Therefore, they have better thermal stability and can effectively improve the mechanical properties and oxidation induction period of polyolefin materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 This is the reaction formula for the preparation method of intramolecular composite antioxidant.

[0046] Figure 2This is the H-NMR spectrum of the intramolecular composite antioxidant obtained in Example 1.

[0047] Figure 3 This is the mass spectrum of the intramolecular composite antioxidant obtained in Example 1.

[0048] Figure 4 This is the H-NMR spectrum of the intramolecular composite antioxidant obtained in Example 5.

[0049] Figure 5 This is the H-NMR spectrum of the intramolecular composite antioxidant obtained in Example 7.

[0050] Figure 6 This is the mass spectrum of the intramolecular composite antioxidant obtained in Example 7.

[0051] Figure 7 This is the H-NMR spectrum of the intramolecular composite antioxidant obtained in Example 11.

[0052] Figure 8 This is the mass spectrum of the intramolecular composite antioxidant obtained in Example 11. DETAILED DESCRIPTION

[0053] The technical solution of the present invention is described in detail below through specific embodiments.

[0054] Embodiment 1:

[0055] The preparation process of the antioxidant intermediate and the intramolecular composite antioxidant A1 of this embodiment is as follows:

[0056] The preparation route is as follows:

[0057]

[0058] a. Synthesis of Intermediate I: Accurately weigh 100 mL of 0.1 mol / L 4-mercaptobenzoic acid methanol solution, add 0.015 mol of ethylenediamine, slowly dropwise add 22 mL of 0.5 mol / L iodine aqueous solution while stirring at room temperature, and react for 3 hours at constant room temperature. Add NH4Cl aqueous solution to the reaction mixture, filter and wash with water 2-3 times to obtain Intermediate I.

[0059] b. Synthesis of intermediate II: Accurately weigh 100 mL of 0.1 mol / L toluene solution of intermediate I, add 0.002 mol of catalyst 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide under nitrogen protection, slowly add 80 mL of 0.5 mol / L toluene solution of p-phenylenediamine at 0°C, heat to 100°C and react for 8 hours after the addition is completed, 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 intermediate II.

[0060] c. Synthesis of intramolecular composite antioxidant A1: accurately weigh 100 mL of 0.1 mol / L intermediate II toluene solution, add 0.001 mol of pyridine under nitrogen protection, slowly add 80 mL of 0.5 mol / L 4-mercapto-2,6-di-tert-butylphenol toluene solution dropwise while stirring at 25°C, heat to 110°C and react for 7 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, using the eluent petroleum ether:ethyl acetate volume ratio of 6:1 to obtain intramolecular composite antioxidant A1.

[0061] The intramolecular composite antioxidant A1 synthesized in this example was analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry. The results are as follows: Figure 2 ,and Figure 3 As shown. Figure 2 It can be seen that the characterization data of the intramolecular composite antioxidant are: 1 H NMR(CD3Cl,400MHz): δ(ppm)1.35(s,C(CH3)3,36H),9.15(s,NH,2H),5.35(s,OH,2H),7.26(s ,OH-Ar-H,4H),7.39(d,OH-Ar-S-Ar-H,4H),8.05(d,O=C-Ar-H,4H),7.86-7.89(t,Ar-H,8H). Figure 3 It can be seen that m / z=928.4 is the molecular ion peak of the intramolecular composite antioxidant A1.

[0062] In the granulation section of the poly 4-methyl-1-pentene material, 0.1wt% of the intramolecular composite antioxidant A1 was added, and the extruder was melt-extruded, drawn and granulated, and the extrusion temperature was 260°C. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin were tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0063] Embodiment 2:

[0064] The intramolecular 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 1:0.1:0.15:0.1, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to a powder extruder for extrusion to obtain a composite auxiliary agent.

[0065] In the granulation section of poly 4-methyl-1-pentene, 0.13wt% of the above composite additive is added, and the extruder is melt-extruded, drawn and granulated, and the extrusion temperature is 260°C. 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.

[0066] Embodiment 3:

[0067] The intramolecular composite antioxidant was synthesized according to the reaction in Example 1. The intramolecular composite antioxidant, calcium stearate, zinc stearate and fluorine rheological body were placed in a high-speed mixer at 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 auxiliary agent.

[0068] In the granulation section of poly 4-methyl-1-pentene, 0.16wt% of the above composite additive is added, and the extruder is melt-extruded, drawn and granulated, and the extrusion temperature is 260°C. 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.

[0069] Embodiment 4:

[0070] The intramolecular composite antioxidant was synthesized according to the reaction in Example 1. The intramolecular composite antioxidant, calcium stearate, zinc stearate and fluorine rheological body were placed in a high-speed mixer at a mass ratio of 1:0.35:0.35:0.1, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to a powder extruder for extrusion to obtain a composite auxiliary agent.

[0071] In the granulation section of poly 4-methyl-1-pentene, 0.18wt% of the above composite additive is added, and the extruder is melt-extruded, drawn and granulated, and the extrusion temperature is 260°C. 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.

[0072] Embodiment 5:

[0073] The preparation steps of the antioxidant intermediate and the intramolecular composite antioxidant A2 of this embodiment are basically the same as the preparation steps of the intramolecular composite antioxidant described in Example 1, except that the 4-mercapto-2,6-di-tert-butylphenol in step c is replaced by 4-mercapto-2,6-diisobutylphenol.

[0074] The structural formula of intramolecular composite antioxidant A2 is as follows:

[0075]

[0076] The intramolecular composite antioxidant A2 synthesized in this example was analyzed by nuclear magnetic resonance spectroscopy, and the results are as follows: Figure 4 shown. 1 HNMR (CD3Cl, 400MHz): δ (ppm) 9.15 (s, NH, 2H), 5.35 (s, OH, 2H), 0.91 (d, CH3, 24H), 1.82 (m, CH, 4H), 2.54 (d, C H2,8H),7.11(s,OH-Ar-H,4H),7.39(d,OH-Ar-S-Ar-H,4H),8.05(d,O=C-Ar-H,4H),7.86-7.89(t,Ar-H,8H).

[0077] In the granulation section of the poly 4-methyl-1-pentene material, 0.1wt% of the intramolecular composite antioxidant A2 was added, and the extruder was melt-extruded, drawn and granulated, and the extrusion temperature was 260°C. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin were tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0078] Embodiment 6:

[0079] The preparation steps of the antioxidant intermediate and the intramolecular composite antioxidant A3 of this embodiment are basically the same as the preparation steps of the intramolecular composite antioxidant recorded in Example 1, except that the 4-mercapto-2,6-di-tert-butylphenol in step c is replaced by 4-mercapto-2,6-di-n-butylphenol.

[0080] The structural formula of intramolecular composite antioxidant A3 is as follows:

[0081]

[0082] In the granulation section of the poly 4-methyl-1-pentene material, 0.1wt% of the intramolecular composite antioxidant A3 was added, and the extruder was melt-extruded, drawn and granulated, and the extrusion temperature was 260°C. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin were tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0083] Embodiment 7:

[0084] The preparation steps of the antioxidant intermediate and the intramolecular composite antioxidant A4 of this embodiment are basically the same as the preparation steps of the intramolecular composite antioxidant recorded in Example 1, except that the 4-mercapto-2,6-di-tert-butylphenol in step c is replaced by 4-mercapto-2,6-diisopropylphenol.

[0085] The structural formula of intramolecular composite antioxidant A4 is as follows:

[0086]

[0087] The intramolecular composite antioxidant A4 synthesized in this example was analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry. The results are as follows: Figure 5 and Figure 6 shown. 1 H NMR (CD3Cl, 400MHz): δ (ppm) 1.20 (d, CH3, 24H), 3.05 (m, CH, 2H), 9.15 (s, NH, 2H), 5.35 (s, OH, 2H), 7 .12(s,OH-Ar-H,4H),7.39(d,OH-Ar-S-Ar-H,4H),8.05(d,O=C-Ar-H,4H),7.86-7.89(t,Ar-H,8H). Figure 6 It can be seen that m / z=872.7 is the molecular ion peak of the intramolecular composite antioxidant (A4).

[0088] In the granulation section of the poly 4-methyl-1-pentene material, 0.1wt% of the intramolecular composite antioxidant A4 was added, and the extruder was melt-extruded, drawn and granulated, and the extrusion temperature was 260°C. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin were tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0089] Embodiment 8:

[0090] The preparation steps of the antioxidant intermediate and the intramolecular composite antioxidant A5 of this embodiment are basically the same as the preparation steps of the intramolecular composite antioxidant recorded in Example 1, except that the 4-mercapto-2,6-di-tert-butylphenol in step c is replaced by 4-mercapto-2,6-di-n-propylphenol.

[0091] The structural formula of intramolecular composite antioxidant A5 is as follows:

[0092]

[0093] In the granulation section of the poly 4-methyl-1-pentene material, 0.1wt% of the intramolecular composite antioxidant A5 was added, and the extruder was melt-extruded, drawn and granulated, and the extrusion temperature was 260°C. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin were tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0094] Embodiment 9:

[0095] The preparation steps of the antioxidant intermediate and the intramolecular composite antioxidant A6 of this embodiment are basically the same as the preparation steps of the intramolecular composite antioxidant described in Example 1, except that the 4-mercapto-2,6-di-tert-butylphenol in step c is replaced by 4-mercapto-2,6-diethylphenol.

[0096] The structural formula of intramolecular composite antioxidant A6 is as follows:

[0097]

[0098] In the granulation section of the poly 4-methyl-1-pentene material, 0.1wt% of the intramolecular composite antioxidant A6 was added, and the extruder was melt-extruded, drawn and granulated, and the extrusion temperature was 260°C. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin were tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0099] Embodiment 10:

[0100] The preparation steps of the antioxidant intermediate and the intramolecular composite antioxidant A7 of this embodiment are basically the same as the preparation steps of the intramolecular composite antioxidant described in Example 1, except that 4-mercapto-2,6-di-tert-butylphenol in step c is replaced by 4-mercapto-2,6-dimethylphenol.

[0101] The structural formula of intramolecular composite antioxidant A7 is as follows:

[0102]

[0103] In the granulation section of the poly 4-methyl-1-pentene material, 0.1wt% of the intramolecular composite antioxidant A7 was added, and the extruder was melt-extruded, drawn and granulated, and the extrusion temperature was 260°C. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin were tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0104] Embodiment 11:

[0105] The preparation steps of the antioxidant intermediate and the intramolecular composite antioxidant A8 in this example are basically the same as the preparation steps of the intramolecular composite antioxidant described in Example 1, except that the 4-mercapto-2,6-di-tert-butylphenol in step c is replaced by 4-mercapto-2-methyl-6-tert-butylphenol.

[0106] The structural formula of intramolecular composite antioxidant A8 is as follows:

[0107]

[0108] The intramolecular composite antioxidant A8 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 intramolecular composite antioxidant A8 are: 1 H NMR(CD3Cl,400MHz): δ(ppm)1.35(s,C(CH3)3,18H),2.15(s,CH3,6H),9.15(s,NH,2H),5.35(s,OH,2H),7.03(s,O H-Ar-H,2H),7.27(s,OH-Ar-H,2H),7.39(d,OH-Ar-S-Ar-H,4H),8.05(d,O=C-Ar-H,4H),7.86-7.89(t,Ar-H,8H). Figure 8 It can be seen that m / z=845.9 is the molecular ion peak of the intramolecular composite antioxidant A8.

[0109] In the granulation section of the poly 4-methyl-1-pentene material, 0.1wt% of the intramolecular composite antioxidant A8 was added, and the extruder was melt-extruded, drawn and granulated, and the extrusion temperature was 260°C. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin were tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0110] Embodiment 12:

[0111] The preparation steps of the antioxidant intermediate and the intramolecular composite antioxidant A9 of this embodiment are basically the same as the preparation steps of the intramolecular composite antioxidant recorded in Example 1, except that the 4-mercapto-2,6-di-tert-butylphenol in step c is replaced by 4-mercapto-2-ethyl-6-tert-butylphenol.

[0112] The structural formula of intramolecular composite antioxidant A9 is as follows:

[0113]

[0114] In the granulation section of the poly 4-methyl-1-pentene material, 0.1wt% of the intramolecular composite antioxidant A9 was added, and the extruder was melt-extruded, drawn and granulated, and the extrusion temperature was 260°C. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin were tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0115] Embodiment 13:

[0116] The preparation steps of the antioxidant intermediate and the intramolecular composite antioxidant A10 in this embodiment are basically the same as the preparation steps of the intramolecular composite antioxidant recorded in Example 1, except that the 4-mercapto-2,6-di-tert-butylphenol in step c is replaced by 4-mercapto-2-isopropyl-6-tert-butylphenol.

[0117] The structural formula of intramolecular composite antioxidant A10 is as follows:

[0118]

[0119] In the granulation section of the poly 4-methyl-1-pentene material, 0.1wt% of the intramolecular composite antioxidant A10 was added, and the extruder was melt-extruded, drawn and granulated, and the extrusion temperature was 260°C. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin were tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0120] Embodiment 14:

[0121] In the granulation section of the poly 4-methyl-1-pentene material, 0.1wt% of the intramolecular composite antioxidant A1 was added, and the extruder was melt-extruded, drawn and granulated, and the extrusion temperature was 250°C. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin were tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0122] Embodiment 15:

[0123] In the granulation section of the poly 4-methyl-1-pentene material, 0.1wt% of the intramolecular composite antioxidant A1 was added, and the extruder was melt-extruded, drawn and granulated, and the extrusion temperature was 270°C. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin were tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0124] Comparative Example 1:

[0125] In the granulation section of the poly-4-methyl-1-pentene material, 0.1wt% of 2,6-di-tert-butyl-4-methylphenol was added thereto, and the material was extruded, drawn and granulated by a twin-screw extruder at an extrusion temperature of 260°C. The oxidation induction period and mechanical properties of the poly-4-methyl-1-pentene material were then tested. The test results are shown in Table 1.

[0126] Comparative Example 2:

[0127] In the granulation section of the poly-4-methyl-1-pentene material, 0.1wt% of didodecanol thiodipropionate was added thereto, and the material was extruded, drawn and granulated by a twin-screw extruder at an extrusion temperature of 260°C. Then, the oxidation induction period and mechanical properties of the poly-4-methyl-1-pentene material were tested. The test results are shown in Table 1.

[0128] Table 1 Analysis and test results of poly 4-methyl-1-pentene materials

[0129]

[0130]

[0131] It can be seen from the data in Table 1 that the intramolecular composite antioxidants A1-A10 provided by the present invention can effectively improve the mechanical properties and oxidation induction period of polyolefin materials, and antioxidants A1 and A10 have the best antioxidant effects. At the same time, the intramolecular composite antioxidants synthesized by the present invention are compared with commercial hindered phenol and thioether antioxidants, and the antioxidant effect of the intramolecular composite antioxidants synthesized by the present invention is significantly better than that of the commercial antioxidants.

[0132] In summary, the intramolecular composite antioxidant provided by the present invention, the antioxidant contains both the phenolic hydroxyl group of the main antioxidant and the thioether group of the auxiliary antioxidant, can realize the synergistic effect of the main and auxiliary antioxidants in the molecule, can quickly terminate the free radical chain reaction, can decompose the hydroperoxide produced by the chain reaction, and has a very excellent antioxidant effect. At the same time, there are multiple rigid benzene ring structures in the molecular structure of the intramolecular composite antioxidant synthesized by the method, and a linking group that is not easily hydrolyzed, and is not easily hydrolyzed and thermally decomposed 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, poly-4-methyl-1-pentene, etc., 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.

[0133] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the protection scope of the present invention.

Claims

1. An intramolecular composite antioxidant, characterized in that: It has the following structure: Wherein, R1, R2, R3, R4 are independently selected from hydrogen or alkyl, and R5 is selected from the following general formula: Wherein, R6, R7, R8, and R9 are independently selected from hydrogen or alkyl, R 10 , R 11 Independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.

2. The intramolecular composite antioxidant according to claim 1, characterized in that R1, R2, R3, and R4 are independently selected from hydrogen, methyl, ethyl, n-propyl, and isopropyl.

3. The intramolecular composite antioxidant according to claim 1, characterized in that R6, R7, R8, and R9 are independently selected from hydrogen, methyl, ethyl, n-propyl, and isopropyl.

4. The intramolecular composite antioxidant according to claim 1, characterized in that The intramolecular composite antioxidant has the following general formula:

5. A poly 4-methyl-1-pentene material, characterized in that: The poly 4-methyl-1-pentene material comprises the intramolecular composite antioxidant according to any one of claims 1-4.

6. The poly 4-methyl-1-pentene material according to claim 5, characterized in that: The poly 4-methyl-1-pentene material comprises: 100 parts by mass of poly-4-methyl-1-pentene resin; Composite additives 0.1-0.19 parts by weight; The composite auxiliary agent comprises an antioxidant, a heat stabilizer and a rheological agent, and the antioxidant is an intramolecular composite antioxidant.

7. The poly 4-methyl-1-pentene material according to claim 6, characterized in that: The heat stabilizer is one or more of the group consisting of calcium stearate, magnesium stearate, zinc stearate and aluminum stearate.

8. The poly 4-methyl-1-pentene material according to claim 6, characterized in that: The rheological agent is a fluorine rheological agent.

9. The poly 4-methyl-1-pentene material according to claim 6, characterized in that: The mass ratio of the antioxidant, the heat stabilizer and the rheological agent is 1:0.25-0.75:0.05-0.

15.

10. The poly 4-methyl-1-pentene material according to claim 5, characterized in that: During the preparation of the poly 4-methyl-1-pentene material, the extrusion temperature is 250-270°C.

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