A polyolefin antioxidant compound and preparation and application thereof

Abstract

The present application provides a kind of polyolefin antioxidant compound and its preparation and application, the compound can be used to prepare polyolefin antioxidant.The molecular structure of the compound of the present application contains flexible alkyl long chain (non-polar group), which can effectively increase the compatibility of antioxidant in non-polar polymer material, reduce the migration and precipitation of antioxidant caused by poor compatibility, and further improve the performance of antioxidant.

Description

Technical Field

[0001] This invention relates to the field of chemical engineering, and more specifically, to a polyolefin antioxidant compound and its preparation and application. Background Technology

[0002] Polyolefin materials, due to their excellent mechanical properties and chemical inertness, are widely used in various fields of production and daily life. In recent years, the polymer materials industry has developed rapidly, especially with a continuously increasing shortage of high-end products, such as highly transparent medical resin poly4-methyl-1-pentene and high-end polybutene-1 tubing materials. However, during processing and use, they are inevitably subjected to light, heat, oxygen, mechanical shear, and heavy metal ions, leading to aging and degradation, ultimately resulting in the loss of their commercial and usability. For most polyolefin materials, adding antioxidants is a simple and effective way to improve their antioxidant properties. Especially for PMP materials, which have extremely high melting points and higher processing and use temperatures, higher demands are placed on the performance of antioxidants. Therefore, based on the properties and mechanisms of action of antioxidants, their structures are optimized to meet application requirements. Based on their different mechanisms of action, antioxidants are mainly classified into two categories: primary antioxidants and secondary antioxidants. Primary antioxidants inhibit chain propagation by providing hydrogen protons to terminate free radical chain reactions or by capturing free radicals to generate inert products. Commonly used primary antioxidants are hindered phenols and aryl secondary amines. Secondary antioxidants terminate oxidation reactions by decomposing hydroperoxides generated during chain propagation. Commonly used secondary antioxidants are phosphites and thioethers. Because primary and secondary antioxidants have different mechanisms of action, they are usually mixed and added to polyolefin materials to produce a synergistic antioxidant effect and achieve better antioxidant performance.

[0003] Because single-function antioxidants cannot meet the diverse performance requirements of high-end polyolefin materials, composite antioxidants, with their low cost, excellent comprehensive performance, short development cycle, and synergistic effect of multiple additives, can satisfy the multifaceted performance needs of high-end polyolefin materials. Therefore, multifunctional and compound antioxidants have become one of the main trends in antioxidant development. Intermolecular composite antioxidants are formed by uniformly mixing primary and secondary antioxidants in a certain proportion. These composite antioxidants have highly efficient antioxidant effects, allowing various antioxidants to complement each other and synergistically exert their antioxidant properties. However, intramolecular composite antioxidants are more suitable for applications in the high-end polyolefin field due to their lower additive requirements, lower volatility, and higher heat resistance, but there are relatively few reports on intramolecular composite antioxidants.

[0004] Chinese patent CN202211160592.4 discloses a diphenylamine-based hindered phenolic antioxidant, its preparation method, and its application, relating to the field of antioxidant technology. The preparation method includes: subjecting a diphenylamine compound and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride to an amidation condensation reaction to obtain the diphenylamine-based hindered phenolic antioxidant having two hindered phenolic units. The diphenylamine-based hindered phenolic antioxidant prepared by this invention exhibits good processing stability, thermo-oxidative stability, and antioxidant properties in polyolefin resins, improves their mechanical properties, and has a simple synthesis process.

[0005] Chinese patent CN201910752684.3 reports a hindered phenol and amide intramolecular composite bifunctional antioxidant and its synthesis method. This antioxidant is prepared by first constructing an ethylenediamine dendritic molecular backbone from ethylenediamine, methanol, and methyl acrylate, and then sealing the end groups of the ethylenediamine dendritic molecular backbone with DtBHP. This antioxidant terminates the chain reaction by capturing generated free radicals and forming relatively stable free radicals itself, thus directly, effectively, and rapidly capturing free radicals and exhibiting high antioxidant capacity. The antioxidant structures reported in the above two patents contain both hindered phenol and amine active units as primary antioxidants; therefore, they do not demonstrate a synergistic effect between primary and secondary antioxidants in their mechanism of action. Summary of the Invention

[0006] To address the technical problems of antioxidants easily decomposing, migrating, and precipitating at high processing temperatures, and the limited antioxidant effect and difficulty in meeting processing and usage requirements when primary and secondary antioxidants are added alone to polyolefin materials due to their antioxidant mechanisms, this invention provides a compound that can be used as an antioxidant. This compound contains both the phenolic hydroxyl group of the primary antioxidant and the thioether and phosphite groups of the secondary antioxidants, enabling synergistic effects of the primary and secondary antioxidants within the molecule. This allows for the rapid termination of free radical chain reactions and the decomposition of hydroperoxides generated by the chain reactions, resulting in excellent antioxidant effects. Furthermore, the presence of multiple flexible alkyl long chains in the molecular structure of this compound effectively increases the compatibility of the antioxidant in non-polar polymer materials, reducing antioxidant migration and precipitation caused by poor compatibility.

[0007] One object of the present invention is to provide a compound that can be used as an antioxidant;

[0008] Another object of the present invention is to provide a method for preparing the said compound;

[0009] Another object of the present invention is to provide the use of the said compound in the preparation of antioxidants;

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

[0011] To achieve the above objectives, in one aspect, the present invention provides a compound (composite antioxidant) represented by formula (I).

[0012]

[0013] in,

[0014] R1 and R2 are each independently selected from substituted or unsubstituted C4-C. 20 Alkyl; when substituted, it is replaced by H, F, Cl, Br, I, C1-C4 alkyl, hydroxyl, carboxyl, amino, nitro or cyano groups;

[0015] R4 and R5 are each independently selected from substituted or unsubstituted C1-C6 alkyl groups; when substituted, they are substituted by H, F, Cl, Br, I, C1-C4 alkyl, hydroxyl, carboxyl, amino, nitro or cyano groups.

[0016] This invention discovers that introducing phosphite groups, thioether groups, and hindered phenolic groups into the same antioxidant structure can achieve synergistic effects between intramolecular primary and secondary antioxidants, effectively improving the antioxidant performance. Simultaneously, in the molecular structure design, a thioether bond is introduced at the para-position of the phenolic hydroxyl group, which is an antioxidant active group. Due to the electron-withdrawing inductive effect, the electron cloud density at the para-position of the secondary amine group on the benzene ring is reduced, making it easier for hydrogen on the phenolic hydroxyl group to leave, resulting in a free radical termination reaction, thus significantly enhancing the antioxidant effect.

[0017] The present invention also found that introducing flexible alkyl long chains (non-polar groups) into the antioxidant structure can effectively increase the compatibility of antioxidants in non-polar polymer materials, reduce the migration and precipitation of antioxidants caused by poor compatibility, and further improve the performance of antioxidants.

[0018] According to some specific embodiments of the present invention, R1 and R2 are each independently selected from substituted or unsubstituted C8-C. 16 Alkyl; when substituted, it is substituted by H, F, Cl, Br, I or C1-C4 alkyl.

[0019] According to some specific embodiments of the present invention, R1 and R2 are each independently selected from C8 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C8 alkyl, C9 ... 10 Alkyl, C 12 Alkyl, C 14 Alkyl or C 16 alkyl.

[0020] According to some specific embodiments of the present invention, R4 and R5 are each independently selected from substituted or unsubstituted C1-C4 alkyl groups; when substituted, they are substituted by H, F, Cl, Br, I or C1-C4 alkyl groups.

[0021] According to some specific embodiments of the present invention, R4 and R5 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.

[0022] According to some specific embodiments of the present invention, R1 and R2 are each independently selected from C8 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C8 alkyl, C9 ... 10 Alkyl, C 12 Alkyl, C 14 Alkyl or C 16 Alkyl; R4 and R5 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0023] According to some specific embodiments of the present invention, R1 and R2 are the same; R4 and R5 are the same.

[0024] According to some specific embodiments of the present invention, R1 and R2 are simultaneously C8 alkyl and C6 alkyl. 10 Alkyl, C 12 Alkyl, C 14 Alkyl or C 16 Alkyl; R4 and R5 are simultaneously methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0025] According to some specific embodiments of the present invention, the compound is selected from one of the following structures:

[0026]

[0027] On the other hand, the present invention also provides a method for preparing the compound of the present invention, wherein the method comprises preparing the compound of formula (I) from the compounds of formula (II) and formula (III):

[0028]

[0029] According to some specific embodiments of the present invention, the compound of formula (II) and the compound of formula (III) undergo an addition reaction to prepare the compound of formula (I).

[0030] According to some specific embodiments of the present invention, the compounds of formula (II) and (III) are prepared by reacting under an inert gas atmosphere to obtain the compound of formula (I).

[0031] According to some specific embodiments of the present invention, in the step of preparing compound (I) from compounds (II) and (III) as raw materials, compound (III) is added dropwise to a mixed solution of compound (II) and reaction solvent.

[0032] According to some specific embodiments of the present invention, the compound of formula (III) is added dropwise to a mixed solution of the compound of formula (II) and the reaction solvent at a rate of 5-10 ml / min.

[0033] According to some specific embodiments of the present invention, the compounds of formula (II) and (III) are prepared in the presence of an alkaline substance to obtain the compound of formula (I).

[0034] According to some specific embodiments of the present invention, the alkaline substance is selected from one or more combinations of trimethylamine, triethylamine, diethylamine and pyridine.

[0035] According to some specific embodiments of the present invention, the alkaline substance is selected from triethylamine and / or pyridine.

[0036] According to some specific embodiments of the present invention, in the step of preparing compound (I) from compounds (II) and (III) as raw materials, the reaction solvent is selected from one or a mixture of several of benzene, toluene and ethylbenzene.

[0037] According to some specific embodiments of the present invention, the molar ratio of compound (III) and compound (II) is (1-1.5):1.

[0038] According to some specific embodiments of the present invention, the molar ratio of compound (III) to compound (II) is (1.1-1.3):1.

[0039] According to some specific embodiments of the present invention, the amount of the alkaline substance is 0.1-0.4 times the amount of the compound of formula (II).

[0040] According to some specific embodiments of the present invention, the amount of the alkaline substance is 0.15-0.20 times the amount of the compound of formula (II).

[0041] According to some specific embodiments of the present invention, the amount of the reaction solvent is 5-15 times the total mass of the reactants.

[0042] According to some specific embodiments of the present invention, the compounds of formula (II) and (III) are prepared by reacting at 30-70°C to obtain the compound of formula (I).

[0043] According to some specific embodiments of the present invention, the compounds of formula (II) and (III) are prepared by reacting at 40-50°C to obtain the compound of formula (I).

[0044] According to some specific embodiments of the present invention, the reaction time of the compound of formula (II) and the compound of formula (III) is 12-48 h.

[0045] According to some specific embodiments of the present invention, the reaction time of the compound of formula (II) and the compound of formula (III) is 18-24 h.

[0046] According to some specific embodiments of the present invention, the method further includes the step of preparing compound (II) from compounds of formula (IV) and formula (V):

[0047]

[0048] R3 is selected from substituted or unsubstituted C4-C. 20 Alkyl; when substituted, it is replaced by H, F, Cl, Br, I, C1-C4 alkyl, hydroxyl, carboxyl, amino, nitro or cyano; X is F, Cl, Br or I.

[0049] According to some specific embodiments of the present invention, R1, R2 and R3 are the same.

[0050] According to some specific embodiments of the present invention, compound (IV) and compound (V) undergo an Avbuzov reaction to prepare compound (II).

[0051] According to some specific embodiments of the present invention, the compounds of formula (IV) and (V) are prepared by reaction under inert gas protection to obtain the compound of formula (II).

[0052] According to some specific embodiments of the present invention, the compound of formula (V) is 3-iodopropene, 3-bromopropene or 3-chloropropene.

[0053] According to some specific embodiments of the present invention, the compound of formula (IV) is trioctyl phosphite, tridecyl phosphite, tri(dodecyl) phosphite, tri(tetradecyl) phosphite, or tri(hexadecyl) phosphite.

[0054] According to some specific embodiments of the present invention, compounds of formula (IV) and (V) are prepared by reacting in the presence of a catalyst to obtain compound (II); said catalyst is selected from benzenesulfonic acid, p-toluenesulfonic acid, methyl p-toluenesulfonate, and p-trifluoromethylbenzenesulfonic acid.

[0055] According to some specific embodiments of the present invention, the compounds of formula (IV) and (V) are prepared by reacting in a solvent to obtain the compound of formula (II).

[0056] According to some specific embodiments of the present invention, in the step of preparing compound (II) from compounds (IV) and (V) as raw materials, the solvent is selected from one or a mixture of methanol, ethanol, tetrahydrofuran and diethyl ether.

[0057] According to some specific embodiments of the present invention, the molar ratio of compound (V) to compound (IV) is (1-1.5):1.

[0058] According to some specific embodiments of the present invention, the molar ratio of compound (V) to compound (IV) is (1.1-1.2):1.

[0059] According to some specific embodiments of the present invention, the molar amount of the catalyst is 0.01-0.1 times the amount of the compound of formula (IV).

[0060] According to some specific embodiments of the present invention, the molar amount of the catalyst is 0.02-0.04 times the amount of the compound of formula (IV).

[0061] According to some specific embodiments of the present invention, the amount of solvent used is 7-15 times the total mass of the reactants (compounds of formula (V) and (IV)).

[0062] According to some specific embodiments of the present invention, the compounds of formula (IV) and (V) are prepared by reacting at 180-240°C to obtain the compound of formula (II).

[0063] According to some specific embodiments of the present invention, the compounds of formula (IV) and (V) are prepared by reacting at 190-210°C to obtain the compound of formula (II).

[0064] According to some specific embodiments of the present invention, the reaction time of compound (IV) and compound (V) is 10-24 h.

[0065] According to some specific embodiments of the present invention, the reaction time of the compound of formula (IV) and the compound of formula (V) is 13-16 h.

[0066] According to some specific embodiments of the present invention, the method includes the following steps:

[0067]

[0068] The raw materials of this invention can be commercially available or prepared according to existing known methods. For example, the raw materials tri(dodecyl) phosphite, tridecyl phosphite, and trioctyl phosphite were all purchased from Aladdin Reagent Co., Ltd.

[0069] For example, tri(hexadecyl) phosphite and tri(tetradecyl) phosphite can be prepared by the following reaction:

[0070] PCl3+3C 14 H 29 OH→(C 14 H 29 O)3P+3HCl

[0071] PCl3+3C 16 H 33 OH→(C 16 H 33 O)3P+3HCl

[0072] For example, the raw materials 4-mercapto-2,6-di-tert-butylphenol, 4-mercapto-2,6-dimethylphenol, and 4-mercapto-2,6-diethylphenol were purchased from Aladdin Reagent Co., Ltd. 4-mercapto-2,6-di-n-butylphenol, 4-mercapto-2,6-diisobutylphenol, 4-mercapto-2,6-diisopropylphenol, 4-mercapto-2-methyl-6-tert-butylphenol, 4-mercapto-2-ethyl-6-tert-butylphenol, and 4-mercapto-2-isopropyl-6-tert-butylphenol can be synthesized using the methods described in the literature.

[0073] Tanaka, Hideo, Tokumaru, et al. Chemo-and Product-selective Electrooxidation of 3-(Arylthiomethyl)-Δ3-cephems. Synthesis, 2009.

[0074] Furthermore, the present invention also provides the application of the compounds described herein in the preparation of antioxidants.

[0075] According to some specific embodiments of the present invention, the antioxidant is an antioxidant for polyolefins.

[0076] In another aspect, the present invention also provides a polyolefin material, wherein the polyolefin material comprises: 100 parts by weight of polyolefin resin and 0.05-0.15 parts by weight of the compound described in the present invention.

[0077] According to some specific embodiments of the present invention, the polyolefin is poly4-methyl-1-pentene or polybutene-1.

[0078] In another aspect, the present invention also provides a method for preparing the polyolefin material, comprising fully mixing the polyolefin resin with the compound of the present invention and then extruding and granulating it to obtain the polyolefin material, wherein the extrusion granulation temperature is 250-270℃ and the extrusion rate is 5-15 r / min.

[0079] According to some specific embodiments of the present invention, the mixing time for thoroughly mixing the polyolefin resin with the compound of the present invention is 5-20 minutes.

[0080] According to some specific embodiments of the present invention, the method includes simultaneously adding a polyolefin resin and the compound of the present invention into a high-speed mixer for thorough mixing, and then transferring the mixture to a twin-screw extruder for extrusion granulation to obtain the polyolefin material, wherein the mixing time is 5-20 min, the extrusion temperature is 250-270 °C, and the extrusion rate is 5-15 r / min.

[0081] In summary, this invention provides a compound for antioxidant purposes in polyolefins, its preparation, and its application. The technical solution of this invention has the following advantages:

[0082] (1) The compound molecules of the present invention introduce thioether bonds and phosphite groups into hindered phenols as primary antioxidants, so that the antioxidants can not only terminate free radicals by providing hydrogen protons, but also decompose hydrogen peroxides, thus achieving the dual role of primary and secondary antioxidants. Furthermore, the thioether bond introduced at the para position of the phenolic hydroxyl group has an electron-withdrawing effect, which reduces the electron cloud density at the position where the benzene ring is connected to the phenolic hydroxyl group, making it easier for hydrogen on the phenolic hydroxyl group to leave and undergo a free radical termination reaction, thereby significantly enhancing the antioxidant effect.

[0083] (2) The molecular structure of the compound of the present invention contains a flexible alkyl long chain (non-polar group), which can effectively increase the compatibility of antioxidants in non-polar polymer materials, reduce the migration and precipitation of antioxidants caused by poor compatibility, and further improve the performance of antioxidants.

[0084] (3) The compounds of the present invention are prepared by using allyl-type haloalkanes, trialkyl phosphites and 4-mercapto-2,6-dialkylphenol as raw materials, through only two steps of Avbuzov and addition reaction. The process is simple, easy to operate, the reaction conditions are mild, the raw materials are readily available, and it is easy to industrialize. Attached Figure Description

[0085] Figure 1 The hydrogen spectrum of the composite antioxidant (A1) prepared in Example 1;

[0086] Figure 2 The mass spectrum of the composite antioxidant (A1) prepared in Example 1;

[0087] Figure 3 The hydrogen spectrum of the composite antioxidant (A2) prepared in Example 2;

[0088] Figure 4 The hydrogen spectrum of the composite antioxidant (A4) prepared in Example 4;

[0089] Figure 5 The mass spectrum of the composite antioxidant (A4) prepared in Example 4;

[0090] Figure 6 The hydrogen spectrum of the composite antioxidant (A7) prepared in Example 7;

[0091] Figure 7 The mass spectrum of the composite antioxidant (A7) prepared in Example 7;

[0092] Figure 8 The hydrogen spectrum of the composite antioxidant (A11) prepared in Example 11;

[0093] Figure 9 The mass spectrum of the composite antioxidant (A11) prepared in Example 11;

[0094] Figure 10 The hydrogen spectrum of the composite antioxidant (A12) prepared in Example 12;

[0095] Figure 11 The mass spectrum of the composite antioxidant (A12) prepared in Example 12. Detailed Implementation

[0096] The following detailed embodiments illustrate the implementation process and beneficial effects of the present invention, aiming to help readers better understand the essence and characteristics of the present invention, and are not intended to limit the scope of implementation of this case.

[0097] Example 1

[0098] The preparation process of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment is as follows:

[0099] The preparation route is shown below:

[0100]

[0101] a. Synthesis of antioxidant intermediate A1-3: 100 mL of a 0.1 mol / L tetrahydrofuran solution of tris(hexadecyl) phosphite was accurately weighed. Under nitrogen protection, 0.3 mmol of p-toluenesulfonic acid was added. 22 mL of a 0.5 mol / L tetrahydrofuran solution of 3-iodopropene was slowly added dropwise while stirring at 0 °C. The reaction was carried out at a constant temperature of 200 °C for 16 hours. The resulting mixture was concentrated under reduced pressure, then dissolved in ethyl acetate. Separation was performed by column chromatography, with the eluent ratio of ethyl acetate to hexane being 5:1. The eluent was subjected to reduced pressure distillation and vacuum drying to obtain a white solid, antioxidant intermediate A1-3, in 92.7% yield.

[0102] b. Synthesis of the composite antioxidant (A1): Accurately weigh 100 mL of a 0.1 mol / L toluene solution of antioxidant intermediate A1-3, add 0.002 mol of triethylamine under nitrogen protection, and slowly add 60 mL of a 0.2 mol / L toluene solution of 4-mercapto-2,6-di-tert-butylphenol while stirring at 0 °C. The mixture is heated to 50 °C and reacted for 22 hours. The resulting mixture is concentrated under vacuum, and a solid precipitates upon the addition of n-heptane. The solid is filtered, washed 2-3 times with n-heptane, and dried under vacuum to obtain a white solid, which is the composite antioxidant (A1), with a yield of 96.9%.

[0103] The composite antioxidant (A1) synthesized in this embodiment was analyzed by 1H NMR and mass spectrometry, and the results are as follows: Figure 1 ,and Figure 2 As shown. By Figure 1 The characterization data of the compound antioxidant can be seen as follows: 1 H NMR(CD3Cl,400MHz): δ(ppm)0.88(t,CH3,6H),1.26-1.31(m,CH2,48H),1.35(s,C(CH3)3,18H),1.43(m,CH2 ,4H),1.71-1.77(m,CH2,8H),2.94(t,CH2-S,2H),4.07(m,CH2-O,4H),5.35(s,-OH,1H),7.24(s,Ar-H,2H). Figure 2 It can be seen that m / z = 809.3 is the molecular ion peak of the composite antioxidant (A1).

[0104] Example 2:

[0105] The preparation steps of the antioxidant intermediate and the composite antioxidant (A2) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that 4-mercapto-2,6-di-tert-butylphenol in step b is replaced with 4-mercapto-2,6-diisobutylphenol, and the yield of step b is 92.4%.

[0106] Compound antioxidant A2

[0107]

[0108] The intramolecular composite antioxidant (A2) synthesized in this embodiment was analyzed by 1H NMR spectroscopy, and the results are as follows: Figure 3 As shown. 1 H NMR (CD3Cl, 400MHz): δ (ppm) 0.88 (t, CH3, 6H), 0.91 (d, CH3, 12H), 1.26-1.31 (m, CH2, 48H), 1.43 (m, CH2, 4H), 1.71-1.77 (m ,CH2,8H),1.82(m,CH,2H),2.54(d,CH2,4H),2.94(t,CH2-S,2H),4.07(m,CH2-O,4H),5.35(s,-OH,1H),7.09(s,Ar-H,2H).

[0109] Example 3:

[0110] The preparation steps of the antioxidant intermediate and the composite antioxidant (A3) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that 4-mercapto-2,6-di-tert-butylphenol in step b is replaced with 4-mercapto-2,6-di-n-butylphenol, and the yield of step b is 97.5%.

[0111] Compound Antioxidant A3

[0112]

[0113] Example 4:

[0114] The preparation steps of the antioxidant intermediate and the composite antioxidant (A4) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that 4-mercapto-2,6-di-tert-butylphenol in step b is replaced with 4-mercapto-2,6-diisopropylphenol, and the yield of step b is 96.2%.

[0115] Compound Antioxidant A4

[0116]

[0117] The composite antioxidant (A4) synthesized in this embodiment was analyzed by 1H NMR and mass spectrometry, and the results are as follows: Figure 4 and Figure 5 As shown. 1H NMR (CD3Cl, 400MHz): δ (ppm) 0.88 (t, CH3, 6H), 1.20 (d, CH3, 12H), 1.26-1.31 (m, CH2, 48H), 1.43 (m, CH2 ,4H),1.71-1.77(m,CH2,8H),3.05(m,CH,2H),4.07(m,CH2-O,4H),5.35(s,-OH,1H),7.10(s,Ar-H,2H). Figure 5 It can be seen that m / z = 781.2 is the molecular ion peak of the composite antioxidant (A4).

[0118] Example 5:

[0119] The preparation steps of the antioxidant intermediate and the composite antioxidant (A5) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that 4-mercapto-2,6-di-tert-butylphenol in step b is replaced with 4-mercapto-2,6-di-n-propylphenol, and the yield of step b is 93.7%.

[0120] Compound Antioxidant A5

[0121]

[0122] Example 6:

[0123] The preparation steps of the antioxidant intermediate and the composite antioxidant (A6) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that 4-mercapto-2,6-di-tert-butylphenol in step b is replaced with 4-mercapto-2,6-diethylphenol, and the yield of step b is 94.8%.

[0124] Compound antioxidant A6

[0125]

[0126] Example 7:

[0127] The preparation steps of the antioxidant intermediate and the composite antioxidant (A7) in this embodiment are basically the same as those of the composite antioxidant described in Example 1, except that 4-mercapto-2,6-di-tert-butylphenol in step b is replaced with 4-mercapto-2,6-dimethylphenol, and the yield of step b is 98.3%. Figure 6 As can be seen, the characterization data of the compound antioxidant (A7) are as follows: 1H NMR (CD3Cl, 400MHz): δ (ppm) 0.88 (t, CH3, 6H), 1.26-1.31 (m, CH2, 48H), 1.43 (m, CH2, 4H), 1.71 -1.77(m,CH2,8H),2.15(s,CH3,6H),4.07(m,CH2-O,4H),5.35(s,-OH,1H),7.02(s,Ar-H,2H). Figure 7 It can be seen that m / z = 725.1 is the molecular ion peak of the composite antioxidant (A7).

[0128] Compound antioxidant A7

[0129]

[0130] Example 8:

[0131] The preparation steps of the antioxidant intermediate and the composite antioxidant (A8) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the tri(hexadecyl) phosphite in step a is replaced with tri(tetradecyl) phosphite, and the yield of step a is 93.4%.

[0132] Compound Antioxidant A8

[0133]

[0134] Example 9:

[0135] The preparation steps of the antioxidant intermediate and the composite antioxidant (A9) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the tri(hexadecyl) phosphite in step a is replaced with tri(dodecyl) phosphite, and the yield of step a is 93.8%.

[0136] Compound antioxidant A9

[0137]

[0138] Example 10:

[0139] The preparation steps of the antioxidant intermediate and the composite antioxidant (A10) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the tri(hexadecyl) phosphite in step a is replaced with tridecyl phosphite, and the yield of step a is 93.7%.

[0140] Compound antioxidant A10

[0141]

[0142] Example 11:

[0143] The preparation steps of the antioxidant intermediate and the composite antioxidant (A11) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the tri(hexadecyl) phosphite in step a is replaced with trioctyl phosphite, and the yield of step a is 95.1%.

[0144] Compound antioxidant A11

[0145]

[0146] The composite antioxidant (A11) synthesized in this embodiment was analyzed by 1H NMR and mass spectrometry, and the results are as follows: Figure 8 ,and Figure 9 As shown. By Figure 8 The characterization data of the compound antioxidant can be seen as follows: 1 H NMR (CD3Cl, 400MHz): δ (ppm) 0.88 (t, CH3, 6H), 1.29-1.31 (m, CH2, 16H), 1.35 (s, C (CH3) 3, 18H), 1.43 (m, CH2 ,4H),1.71-1.77(m,CH2,6H),2.94(t,CH2-S,2H),4.07(m,CH2-O,4H),5.35(s,-OH,1H),7.24(s,Ar-H,2H). Figure 9 It can be seen that m / z = 584.8 is the molecular ion peak of the composite antioxidant (A11).

[0147] Example 12:

[0148] The preparation steps of the antioxidant intermediate and the composite antioxidant (A12) in this embodiment are basically the same as those of the composite antioxidant described in Example 1, except that tri(hexadecyl) phosphite in step a is replaced with trioctyl phosphite, and the yield of step a is 95.1%. In step b, 4-mercapto-2,6-di-tert-butylphenol is replaced with 4-mercapto-2-methyl-6-tert-butylphenol, and the yield of step b is 92.4%.

[0149] Compound antioxidant A12

[0150]

[0151] The composite antioxidant (A12) synthesized in this embodiment was analyzed by 1H NMR and mass spectrometry, and the results are as follows: Figure 10 ,and Figure 11 As shown. By Figure 10 The characterization data for the composite antioxidant (A12) are as follows: 1H NMR(CD3Cl,400MHz): δ(ppm)0.88(t,CH3,6H),1.29-1.43(m,CH2,20H),1.35(s,C(CH3)3,9H),1.71-1.77(m,CH 2,8H),2.94(t,CH2-S,2H),2.15(s,Ar-CH3,9H),4.07(t,CH2-O,4H),5.35(s,-OH,1H),7.01-7.25(s,Ar-H,2H). Figure 11 It can be seen that m / z = 542.3 is the molecular ion peak of the composite antioxidant (A12).

[0152] Example 13:

[0153] The preparation steps of the antioxidant intermediate and the composite antioxidant (A13) in this embodiment are basically the same as those of the composite antioxidant described in Example 1, except that tris(hexadecyl) phosphite in step a is replaced with tris(dodecyl) phosphite, and the yield of step a is 93.8%. In step b, 4-mercapto-2,6-di-tert-butylphenol is replaced with 4-mercapto-2-ethyl-6-tert-butylphenol, and the yield of step b is 93.7%.

[0154] Compound antioxidant A13

[0155]

[0156] Example 14:

[0157] The preparation steps of the antioxidant intermediate and the composite antioxidant (A14) in this embodiment are basically the same as those of the composite antioxidant described in Example 1, except that tri(hexadecyl) phosphite in step a is replaced with tri(hexadecyl) phosphite, and the yield of step a is 92.7%. In step b, 4-mercapto-2,6-di-tert-butylphenol is replaced with 4-mercapto-2-isopropyl-6-tert-butylphenol, and the yield of step b is 94.6%.

[0158] Compound antioxidant A14

[0159]

[0160] Example 15:

[0161] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the catalyst p-toluenesulfonic acid in step a is replaced with methyl p-toluenesulfonate, and the yield of step a is 73.1%. The triethylamine in step b is replaced with trimethylamine, and the yield of step b is 62.7%.

[0162] Example 16:

[0163] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the catalyst p-methylbenzenesulfonic acid in step a is replaced with benzenesulfonic acid, and the yield of step a is 86.7%.

[0164] Example 17:

[0165] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the catalyst p-methylbenzenesulfonic acid in step a is replaced with p-trifluoromethylbenzenesulfonic acid, and the yield of step a is 70.5%.

[0166] Example 18:

[0167] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that 3-iodopropene in step a is replaced with 3-chloropropene, and the yield of step a is 41.5%. Triethylamine in step b is replaced with diethylamine, and the yield of step b is 74.3%.

[0168] Example 19:

[0169] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the amount of tetrahydrofuran of 3-iodopropene added in step a is 20 ml, and the yield of step a is 90.4%. The amount of toluene solution of 4-mercapto-2,6-di-tert-butylphenol added in step b is 50 ml, and the yield of step b is 93.7%.

[0170] Example 20:

[0171] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as those of the composite antioxidant described in Example 1. The difference is that the amount of tetrahydrofuran of 3-iodopropene added in step a is 26 ml, and the yield of step a is 93.6%. The amount of toluene solution of 4-mercapto-2,6-di-tert-butylphenol added in step b is 75 ml, and the yield of step b is 97.2%.

[0172] Example 21:

[0173] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the amount of tetrahydrofuran of 3-iodopropene added in step a is 30 ml, and the yield of step a is 93.8%. The amount of triethylamine added in step b is 0.001 mol, and the yield of step b is 91.6%.

[0174] Example 22:

[0175] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the amount of p-toluenesulfonic acid added in step a is 0.1 mmol, and the yield of step a is 87.5%. The amount of triethylamine added in step b is 0.004 mol, and the yield of step b is 97.3%.

[0176] Example 23:

[0177] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the amount of p-toluenesulfonic acid added in step a is 0.6 mmol, the yield of step a is 93.0%, the reaction temperature in step b is 30°C, and the yield of step b is 72.8%.

[0178] Example 24:

[0179] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the reaction temperature of step a is 180°C and the yield of step a is 87.9%, the reaction time of step b is 12h and the yield of step b is 59.5%.

[0180] Example 25:

[0181] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the reaction temperature of step a is 240°C and the yield of step a is 90.6%, the reaction time of step b is 48 hours and the yield of step b is 97.6%.

[0182] Example 26:

[0183] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the reaction temperature of step a is 240°C and the yield of step a is 91.9%.

[0184] Example 27:

[0185] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the reaction time of step a is 10 hours and the yield of step a is 72.0%.

[0186] Example 28:

[0187] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) in this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1. The difference is that the reaction time of step a is 24 hours and the yield of step a is 93.4%.

[0188] Example 29:

[0189] In the poly-4-methyl-1-pentene granulation section, 0.1% of antioxidants A1-A14 prepared in Examples 1-14 were added respectively. The mixture was extruded, drawn into fibers, and granulated using a twin-screw extruder. The mixing temperature was room temperature, the mixing time was 10 min, the extrusion temperature was 260℃, and the extrusion rate was 10 r / min. The oxidation induction period and mechanical properties of poly-4-methyl-1-pentene were then tested, and the test results are shown in Table 1.

[0190] Comparative Example 1:

[0191] In the poly(4-methyl-1-pentene) granulation section, 0.1% of 2,6-di-tert-butyl-4-methylphenol was added as an antioxidant to replace the antioxidant of the present invention. The mixture was extruded, drawn into fibers, and granulated using a twin-screw extruder according to the method of Example 29. The mixing temperature was room temperature, the mixing time was 10 min, the extrusion temperature was 260°C, and the extrusion rate was 10 r / min. The oxidation induction period and mechanical properties of poly(4-methyl-1-pentene) were then tested. The test results are shown in Table 1.

[0192] Comparative Example 2:

[0193] In the poly(4-methyl-1-pentene) granulation section, 0.1% of disododecyl thiodipropionate was added as an antioxidant to replace the antioxidant of the present invention. The mixture was extruded, drawn into fibers, and granulated using a twin-screw extruder according to the method of Example 29. The mixing temperature was room temperature, the mixing time was 10 min, the extrusion temperature was 260°C, and the extrusion rate was 10 r / min. The oxidation induction period and mechanical properties of poly(4-methyl-1-pentene) were then tested. The test results are shown in Table 1.

[0194] Comparative Example 3:

[0195] In the poly-4-methyl-1-pentene granulation section, 0.1% of tris(2,4-di-tert-butylphenyl) phosphite was added as an antioxidant to replace the antioxidant of the present invention. The mixture was extruded, drawn into fibers, and granulated using a twin-screw extruder according to the method of Example 29. The mixing temperature was room temperature, the mixing time was 10 min, the extrusion temperature was 260°C, and the extrusion rate was 10 r / min. The oxidation induction period and mechanical properties of poly-4-methyl-1-pentene were then tested. The test results are shown in Table 1.

[0196] Test case

[0197] OIT analysis was performed according to GB / T 2951.1-1994, under a nitrogen atmosphere, with the temperature increased to 200℃ at 20℃ / min, held at that temperature for 5 min, and then replaced with oxygen to decrease the temperature to 25℃ at -20℃ / min.

[0198] Mechanical property tests were conducted according to GB / T 1040-2006. Poly(4-methyl-1-pentene) granules were molded into 5A dumbbell-shaped specimens using compression molding and placed at a temperature of (23±2)℃ and a relative humidity of (50±5)% for 24 hours. The tensile rate was 50 mm / min.

[0199] The results of the OIT analysis and mechanical property tests are shown in Table 1:

[0200] Table 1. Analytical results of poly-4-methyl-1-pentene

[0201]

[0202]

[0203] As can be seen from the data in Table 1, the intramolecular composite antioxidants A1-A14 prepared in this invention can effectively improve the mechanical properties and oxidation induction period of polyolefin materials, among which antioxidants A1, A8, and A14 all exhibit excellent antioxidant effects. Furthermore, compared with commercially available hindered phenolic, thioether, and phosphite antioxidants, the synthesized composite antioxidants show significantly better antioxidant effects.

[0204] This invention provides a composite antioxidant synthesized from allyl-type haloalkanes, trialkyl phosphites, and 4-mercapto-2,6-dialkylphenol as raw materials via a two-step reaction involving Avbuzov and addition. This composite antioxidant molecule introduces thioether bonds and phosphite groups into hindered phenol-type primary antioxidants, achieving synergistic effects between primary and secondary antioxidants within the molecule. This rapidly terminates free radical chain reactions and decomposes the hydroperoxides produced by the chain reaction, resulting in excellent antioxidant effects. Furthermore, the molecular structure of this composite antioxidant contains flexible alkyl long chains (non-polar groups), effectively increasing its compatibility with non-polar polymers and reducing antioxidant migration and precipitation caused by poor compatibility, further improving antioxidant performance. The synthesis process of this invention is simple, easy to operate, has mild reaction conditions, and uses readily available raw materials, making it easy to industrialize. Applying the synthesized product to high-end resins such as polybutene-1 and poly4-methyl-1-pentene can effectively improve the antioxidant properties of the materials, and has important guiding significance for the development and use of high-end resin additives.

Claims

1. A compound represented by the following formula (I), （I） wherein, R1and R2are each independently selected from the group consisting of substituted or unsubstituted C4-C 20 alkyl; when substituted, is substituted with H, F, Cl, Br, I, C1-C4alkyl, hydroxyl, carboxyl, amino, nitro, or cyano; R4 and R5 are each independently selected from substituted or unsubstituted C1-C6 alkyl; when substituted, H, F, Cl, Br, I, C1-C4 alkyl, hydroxy, carboxyl, amino, nitro or cyano.

2. The compound of claim 1, wherein, R1and R2are each independently selected from the group consisting of substituted or unsubstituted C8-C 16 alkyl; when substituted, is substituted with H, F, Cl, Br, I, or C1-C4alkyl.

3. The compound of claim 1 or 2, wherein, R1and R2are each independently selected from the group consisting of C8alkyl, C 10 alkyl, C 12 alkyl, C 14 alkyl or C 16 alkyl.

4. The compound of claim 1 or 2, wherein, R4 and R5 are each independently selected from substituted or unsubstituted C1-C4 alkyl; when substituted, H, F, Cl, Br, I or C1-C4 alkyl.

5. The compound of claim 1 or 2, wherein, R4 and R5 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.

6. The compound of claim 1, wherein, The compound is selected from one of the following structures:

7. A process for the preparation of a compound according to any one of claims 1 to 6, wherein, The method comprises preparing the compound of formula (I) from a compound of formula (II) and a compound of formula (III): (II) (III).

8. The production method according to claim 7, wherein The compound of formula (II) and the compound of formula (III) are prepared in the presence of a basic substance.

9. The production method according to claim 7 or 8, wherein The compound of formula (II) and the compound of formula (III) are prepared by reacting at 30-70°C.

10. The production method according to claim 7 or 8, wherein The method further comprises a step of preparing the compound of formula (II) from a compound of formula (IV) and a compound of formula (V): (IV) (V) wherein, R3 is selected from substituted or unsubstituted C4-C20 alkyl; when substituted, H, F, Cl, Br, I, C1-C4 alkyl, hydroxy, carboxyl, amino, nitro or cyano; and X is F, Cl, Br or I.

11. The preparation method according to claim 10, wherein the compound of formula (IV) and the compound of formula (V) are prepared by reacting in the presence of a catalyst; the catalyst is selected from one of benzenesulfonic acid, p-toluenesulfonic acid, methyl p-toluenesulfonate and p-trifluoromethylbenzenesulfonic acid.

12. The preparation method according to claim 10, wherein the compound of formula (IV) and the compound of formula (V) are prepared by reacting at 180-240°C.

13. Use of the compound according to any one of claims 1-6 in the preparation of an antioxidant.

14. Use according to claim 13, wherein, The antioxidant is an antioxidant for polyolefin.

15. A polyolefin material, wherein, The polyolefin material comprises: 100 parts by mass of a polyolefin resin, and 0.05-0.15 parts by mass of the compound according to any one of claims 1-6.

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

17. The method of producing the polyolefin material according to any one of claims 15 to 16, comprising extrusion granulation after sufficiently mixing the polyolefin resin with the compound according to any one of claims 1 to 6, to obtain the polyolefin material, wherein, The temperature for extrusion granulation is 250-270°C, and the extrusion rate is 5-15 r / min.

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