Polyolefin antioxidant compound and preparation and application thereof

Abstract

The invention provides a polyolefin antioxidant compound as well as preparation and application thereof. The compound can be used for preparing an antioxidant for polyolefin. The molecular structure of the compound contains a flexible alkyl long chain (non-polar group), so that the compatibility of the antioxidant in a non-polar high polymer material can be effectively improved, the migration and precipitation of the antioxidant caused by poor compatibility of the antioxidant are reduced, and the performance of the antioxidant is further improved. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of chemical industry, in particular to a polyolefin antioxidant compound and its preparation and application. 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 materials industry has developed rapidly, especially the gap in high-end products has continued to increase, such as highly transparent medical resin poly-4-methyl-1-pentene and high-end polybutene-1 tube materials. However, during its processing and use, it is inevitably affected by light, heat, oxygen, mechanical shearing and heavy metal ions, which cause it to age and degrade until it loses its commercial value and use value. For most polyolefin materials, adding antioxidants is a simple and effective way to improve its antioxidant properties. Especially for PMP materials, the material has an extremely high melting point, and higher processing and use temperatures put forward higher requirements on the performance of antioxidants. Therefore, according to the properties and mechanism of action of the antioxidant, the structure of the antioxidant is optimized and designed to meet the use requirements. 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, 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, intramolecular composite antioxidants are more suitable for applications in the field of high-end polyolefins due to their lower additive addition amount, lower volatility, and higher heat resistance, but there are few reports on intramolecular composite antioxidants.

[0004] Chinese patent CN202211160592.4 reports a diphenylamine hindered phenol antioxidant and its preparation method and application, which relates to the field of antioxidant technology. The preparation method comprises: subjecting a diphenylamine compound and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride to an amidation condensation reaction to obtain the diphenylamine hindered phenol antioxidant having two hindered phenol units. The diphenylamine hindered phenol antioxidant prepared by the present invention has good processing stability, thermal oxygen stability and antioxidant properties in polyolefin resins, can improve its 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. The antioxidant is first made of ethylenediamine, methanol, and methyl acrylate into an ethylenediamine dendritic molecular skeleton, 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. The antioxidant structures reported in the above two patents contain hindered phenols and amine active units, both of which are main antioxidants, so they do not play a synergistic role as main and auxiliary antioxidants in terms of action mechanism. Summary of the invention

[0006] In order to solve the technical problems that antioxidants are prone to decomposition, migration and precipitation at high processing temperatures, and that when primary and auxiliary antioxidants are added separately to polyolefin materials, the antioxidant effect is limited due to the antioxidant mechanism and it is difficult to meet processing and use requirements, the present invention provides a compound that can be used as an antioxidant. The compound contains both phenolic hydroxyl groups of the primary antioxidant and thioether groups and phosphite groups of the auxiliary antioxidant, and can achieve the synergistic effect of the primary and auxiliary antioxidants in the molecule, that is, it can quickly terminate the free radical chain reaction and decompose the hydroperoxides generated by the chain reaction, and has a very excellent antioxidant effect; at the same time, the compound has multiple flexible alkyl long chains in the molecular structure, which can effectively increase the compatibility of the antioxidant in non-polar polymer materials and reduce the migration and precipitation of the antioxidant caused by poor compatibility of the antioxidant.

[0007] One object of the present invention is to provide a compound which can be used for anti-oxidation;

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

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

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

[0011] To achieve the above object, on the one hand, 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 substituted by H, F, Cl, Br, I, C1-C4 alkyl, hydroxy, carboxyl, amino, nitro or cyano;

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

[0016] The present invention finds that by introducing a phosphite group, a thioether group and a hindered phenol group into the same antioxidant structure, the synergy of the main and auxiliary antioxidants in the molecule can be achieved, and the antioxidant performance of the antioxidant can be effectively improved; at the same time, in the molecular structure design, a thioether bond is introduced at the para position of the antioxidant active group phenolic hydroxyl group, and due to the electron-withdrawing induction effect, the electron cloud density at the para benzene ring of the secondary amine group is reduced, so that the hydrogen on the phenolic hydroxyl group is easier to leave, and a free radical termination reaction occurs, thereby significantly enhancing the antioxidant effect.

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

[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, C 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; when substituted, they are substituted by H, F, Cl, Br, I or C1-C4 alkyl.

[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, C 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 both C8 alkyl, C 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 using the compound of formula (II) and the compound of formula (III) as raw materials to prepare the compound of formula (I):

[0028]

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

[0030] According to some specific embodiments of the present invention, the compound of formula (II) and the compound of formula (III) are reacted under the protection of an inert gas to prepare the compound of formula (I).

[0031] According to some specific embodiments of the present invention, in the step of preparing the compound of formula (I) using the compound of formula (II) and the compound of formula (III) as raw materials, the compound of formula (III) is added dropwise to a mixed solution of the compound of formula (II) and a 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 a reaction solvent at a rate of 5-10 ml / min.

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

[0034] According to some specific embodiments of the present invention, the alkaline substance is selected from a combination of one or more 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, the reaction solvent in the step of preparing the compound of formula (I) using the compound of formula (II) and the compound of formula (III) as raw materials is selected from one or a mixture of benzene, toluene and ethylbenzene.

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

[0038] According to some specific embodiments of the present invention, the molar ratio of the compound of formula (III) to the compound of formula (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 compound of formula (II) and the compound of formula (III) are reacted at 30-70° C. to prepare the compound of formula (I).

[0043] According to some specific embodiments of the present invention, the compound of formula (II) and the compound of formula (III) are reacted at 40-50° C. to prepare 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 hours.

[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 hours.

[0046] According to some specific embodiments of the present invention, the method further comprises the step of preparing a compound of formula (II) using a compound of formula (IV) and a compound of formula (V) as raw materials:

[0047]

[0048] Wherein R3 is selected from substituted or unsubstituted C4-C 20 Alkyl; when substituted, it is substituted by H, F, Cl, Br, I, C1-C4 alkyl, hydroxy, 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, the compound of formula (II) is prepared by Avbuzov reaction of the compound of formula (IV) and the compound of formula (V).

[0051] According to some specific embodiments of the present invention, the compound of formula (IV) and the compound of formula (V) are reacted under the protection of an inert gas 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, tridodecyl phosphite, tritetradecyl phosphite or trihexadecyl phosphite.

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

[0055] According to some specific embodiments of the present invention, the compound of formula (IV) and the compound of formula (V) are reacted in a solvent to prepare the compound of formula (II).

[0056] According to some specific embodiments of the present invention, the solvent in the step of preparing the compound of formula (II) from the compound of formula (IV) and the compound of formula (V) as raw materials 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 the compound of formula (V) to the compound of formula (IV) is (1-1.5):1.

[0058] According to some specific embodiments of the present invention, the molar ratio of the compound of formula (V) to the compound of formula (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 mass amount of the solvent is 7-15 times the total mass of the reactants (the compound of formula (V) and the compound of formula (IV)).

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

[0063] According to some specific embodiments of the present invention, the compound of formula (IV) and the compound of formula (V) are reacted 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 the compound of formula (IV) and the compound of formula (V) is 10-24 hours.

[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 hours.

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

[0067]

[0068] The raw materials of the present invention can be obtained from the market or prepared according to the known methods. For example, the raw materials tridodecyl phosphite, tridecyl phosphite and trioctyl phosphite are all purchased from Aladdin Reagent Co., Ltd.

[0069] For another example, trihexadecyl phosphite and tritetradecyl 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 another example, the raw materials 4-mercapto-2,6-di-tert-butylphenol, 4-mercapto-2,6-dimethylphenol, and 4-mercapto-2,6-diethylphenol are purchased from Aladdin Reagent Co., Ltd., and 4-mercapto-2,6-di-n-butylphenol, 4-mercapto-2,6-diisobutylphenol, 4-mercapto-2,6-diisopropylphenol, 4-mercapto-2,6-di-n-propylphenol, 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 in the manner described in the literature:

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

[0074] In another aspect, the present invention also provides use of the compound of the present invention in the preparation of an antioxidant.

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

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

[0077] According to some specific embodiments of the present invention, the polyolefin is poly-4-methyl-1-pentene or polybutene-1.

[0078] On the other hand, the present invention also provides a method for preparing the polyolefin material, which comprises fully mixing the polyolefin resin with the compound 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.

[0079] According to some specific embodiments of the present invention, the mixing time for fully 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 comprises adding a polyolefin resin and the compound of the present invention simultaneously into a high-speed mixer and mixing them thoroughly, and then transferring them into 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, the present invention provides a polyolefin antioxidant compound and its preparation and application. The technical solution of the present invention has the following advantages:

[0082] (1) The compound molecules of the present invention introduce thioether bonds and phosphite groups into primary antioxidants such as hindered phenols, so that the antioxidants can not only terminate free radicals by providing hydrogen protons, but also decompose hydroperoxides, thereby achieving the dual role of primary and secondary antioxidants. In addition, the thioether bonds introduced are 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.

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

[0084] (3) The compound of the present invention uses allyl halogenated hydrocarbons, trialkyl phosphites and 4-mercapto-2,6-dialkylphenol as raw materials and is prepared by only two steps of Avbuzov and addition reactions. The process is simple, easy to operate, the reaction conditions are mild, the raw materials are easily available, and it is easy to realize industrialization. BRIEF DESCRIPTION OF THE DRAWINGS

[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 This is the hydrogen spectrum of the composite antioxidant (A11) prepared in Example 11;

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

[0094] Fig.10 This is the hydrogen spectrum of the composite antioxidant (A12) prepared in Example 12;

[0095] Fig.11 This is the mass spectrum of the composite antioxidant (A12) prepared in Example 12. DETAILED DESCRIPTION

[0096] 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.

[0097] Example 1

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

[0099] The preparation route is as follows:

[0100]

[0101] a. Synthesis of antioxidant intermediate A1-3: Accurately weigh 100 mL of 0.1 mol / L tri(hexadecyl)phosphite tetrahydrofuran solution, add 0.3 mmol of p-toluenesulfonic acid under nitrogen protection, slowly dropwise add 22 mL of 0.5 mol / L 3-iodopropylene tetrahydrofuran solution at 0°C while stirring, and react for 16 hours at a constant temperature of 200°C. The mixed solution after the reaction was concentrated under reduced pressure, then dissolved in ethyl acetate, separated by column chromatography, eluent V ethyl acetate: V hexane = 5:1, and the eluted product was distilled under reduced pressure and dried in vacuo to obtain a white solid, which is the antioxidant intermediate A1-3, with a yield of 92.7%.

[0102] b. Synthesis of composite antioxidant (A1): Accurately weigh 100 mL of 0.1 mol / L antioxidant intermediate A1-3 toluene solution, add 0.002 mol of triethylamine under nitrogen protection, slowly add 60 mL of 0.2 mol / L 4-mercapto-2,6-di-tert-butylphenol toluene solution dropwise while stirring at 0°C, heat to 50°C and react for 22 hours, concentrate the reaction mixture under vacuum, add n-heptane to precipitate solid, filter and wash with n-heptane 2-3 times, and vacuum dry to obtain a white solid, which is composite antioxidant (A1) with a yield of 96.9%.

[0103] The composite antioxidant (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 the composite antioxidant are: 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] Embodiment 2:

[0105] The preparation steps of the antioxidant intermediate and the composite antioxidant (A2) of this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1, except that 4-mercapto-2,6-di-tert-butylphenol in step b is replaced by 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 example was analyzed by nuclear magnetic resonance spectroscopy, and the results are as follows: Figure 3 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] Embodiment 3:

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

[0111] Compound Antioxidant A3

[0112]

[0113] Embodiment 4:

[0114] The preparation steps of the antioxidant intermediate and the composite antioxidant (A4) of this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1, except that 4-mercapto-2,6-di-tert-butylphenol in step b is replaced by 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 example was analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry. The results are as follows: Figure 4 and Figure 5 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] Embodiment 5:

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

[0120] Compound Antioxidant A5

[0121]

[0122] Embodiment 6:

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

[0124] Compound Antioxidant A6

[0125]

[0126] Embodiment 7:

[0127] The preparation steps of the antioxidant intermediate and the composite antioxidant (A7) of this example are basically the same as the preparation steps of the composite antioxidant described in Example 1, except that 4-mercapto-2,6-di-tert-butylphenol in step b is replaced by 4-mercapto-2,6-dimethylphenol, and the yield of step b is 98.3%. Figure 6 It can be seen that the characterization data of the composite antioxidant (A7) are: 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] Embodiment 8:

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

[0132] Compound Antioxidant A8

[0133]

[0134] Embodiment 9:

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

[0136] Compound Antioxidant A9

[0137]

[0138] Embodiment 10:

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

[0140] Compound Antioxidant A10

[0141]

[0142] Embodiment 11:

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

[0144] Compound Antioxidant A11

[0145]

[0146] The composite antioxidant (A11) synthesized in this example was analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry. The results are as follows: Figure 8 ,and Fig. 9 As shown. Figure 8 It can be seen that the characterization data of the composite antioxidant are: 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). Fig. 9 It can be seen that m / z=584.8 is the molecular ion peak of the composite antioxidant (A11).

[0147] Embodiment 12:

[0148] The preparation steps of the antioxidant intermediate and the composite antioxidant (A12) of this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1, except that trihexadecyl phosphite in step a is replaced by trioctyl phosphite, and the yield of step a is 95.1%. 4-mercapto-2,6-di-tert-butylphenol in step b is replaced by 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 example was subjected to nuclear magnetic resonance spectroscopy and mass spectrometry analysis, and the results are as follows: Fig.10 ,and Fig.11 As shown. Fig.10 It can be seen that the characterization data of the composite antioxidant (A12) are: 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). Fig.11 It can be seen that m / z=542.3 is the molecular ion peak of the composite antioxidant (A12).

[0152] Embodiment 13:

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

[0154] Compound Antioxidant A13

[0155]

[0156] Embodiment 14:

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

[0158] Compound Antioxidant A14

[0159]

[0160] Embodiment 15:

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

[0162] Embodiment 16:

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

[0164] Embodiment 17:

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

[0166] Embodiment 18:

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

[0168] Embodiment 19:

[0169] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1, except that the amount of tetrahydrofuran added to 3-iodopropylene in step a is 20 ml, and the yield of step a is 90.4%, and 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] Embodiment 20:

[0171] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1, except that the amount of tetrahydrofuran added to 3-iodopropylene in step a is 26 ml, and the yield of step a is 93.6%, and 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] Embodiment 21:

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

[0174] Embodiment 22:

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

[0176] Embodiment 23:

[0177] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1, except 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 of step b is 30°C, and the yield of step b is 72.8%.

[0178] Embodiment 24:

[0179] The preparation steps of the antioxidant intermediate and the composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the composite antioxidant described in Example 1, except that the reaction temperature of step a is 180°C, 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] Embodiment 25:

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

[0182] Embodiment 26:

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

[0184] Embodiment 27:

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

[0186] Embodiment 28:

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

[0188] Embodiment 29:

[0189] In the poly-4-methyl-1-pentene granulation section, 0.1% of the antioxidants A1-A14 prepared in Examples 1-14 were added thereto, respectively, and extruded, drawn and granulated by a twin-screw extruder, with a mixing temperature of room temperature, a mixing time of 10 minutes, 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, 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 thereto as an antioxidant to replace the antioxidant of the present invention, and the twin-screw extruder was used for extrusion, drawing and granulation according to the method of Example 29, with a mixing temperature of room temperature, a mixing time of 10 minutes, an extrusion temperature of 260°C, and an extrusion rate of 10 r / min. Then, the oxidation induction period and mechanical properties of poly-4-methyl-1-pentene were 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 didodecanol thiodipropionate was added as an antioxidant to replace the antioxidant of the present invention, and the mixture was extruded, drawn and granulated by a twin-screw extruder according to the method of Example 29, with a mixing temperature of room temperature, a mixing time of 10 minutes, 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 are shown in Table 1.

[0194] Comparative Example 3:

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

[0196] Test Case

[0197] 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.

[0198] 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.

[0199] The above OIT analysis results and mechanical properties test results are shown in Table 1:

[0200] Table 1 Analysis and test results of poly 4-methyl-1-pentene

[0201]

[0202]

[0203] It can be seen from the data in Table 1 that the intramolecular composite antioxidants A1-A14 prepared by the present invention can effectively improve the mechanical properties and oxidation induction period of polyolefin materials, wherein antioxidants A1, A8 and A14 all have excellent antioxidant effects. At the same time, the synthesized composite antioxidants are compared with commercial hindered phenols, thioether antioxidants and phosphite antioxidants, and their antioxidant effects are significantly better than those of commercial antioxidants.

[0204] The invention provides a composite antioxidant, which uses allyl halogenated hydrocarbons, trialkyl phosphites and 4-mercapto-2,6-dialkylphenol as raw materials, and synthesizes the composite antioxidant only through Avbuzov and addition two-step reactions. The composite antioxidant molecule introduces a thioether bond and a phosphite group into a main antioxidant such as hindered phenol, which can achieve the synergistic effect of the main and auxiliary antioxidants in the molecule, can quickly terminate the free radical chain reaction, and can decompose the hydroperoxides generated by the chain reaction, and has a very excellent antioxidant effect. At the same time, the molecular structure of the composite antioxidant contains a flexible alkyl long chain (non-polar group), which can effectively increase the compatibility of the antioxidant in non-polar polymer materials, reduce the migration and precipitation of the antioxidant caused by poor compatibility of the antioxidant, and further improve the performance of the antioxidant. The synthesis process of the invention is simple, easy to operate, has mild reaction conditions, and readily available raw materials, and is easy to industrialize. The synthetic product is applied to high-end resins such as polybutene-1 and poly-4-methyl-1-pentene, which can effectively improve the antioxidant properties of the material and has important guiding significance for the development and use of high-end resin additives.

Claims

1. A compound represented by formula (I), in, R1 and R2 are each independently selected from substituted or unsubstituted C4-C 20 Alkyl; when substituted, it is substituted by H, F, Cl, Br, I, C1-C4 alkyl, hydroxy, carboxyl, amino, nitro or cyano; R4 and R5 are each independently selected from substituted or unsubstituted C1-C6 alkyl; when substituted, they are substituted by H, F, Cl, Br, I, C1-C4 alkyl, hydroxy, carboxyl, amino, nitro or cyano.

2. The compound according to claim 1, wherein 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.

3. The compound according to claim 1 or 2, wherein R1 and R2 are each independently selected from C8 alkyl, C 10 Alkyl, C 12 Alkyl, C 14 Alkyl or C 16 alkyl.

4. The compound according to any one of claims 1 to 3, wherein R4 and R5 are each independently selected from substituted or unsubstituted C1-C4 alkyl; when substituted, they are substituted by H, F, Cl, Br, I or C1-C4 alkyl.

5. The compound according to any one of claims 1 to 4, wherein R4 and R5 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.

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

7. The method for preparing the compound according to any one of claims 1 to 6, wherein The method comprises using a compound of formula (II) and a compound of formula (III) as raw materials to prepare a compound of formula (I):

8. The preparation 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 to obtain the compound of formula (I).

9. The preparation method according to claim 7 or 8, wherein: The compound of formula (II) and the compound of formula (III) are reacted at 30-70°C to obtain the compound of formula (I).

10. The preparation method according to any one of claims 7 to 9, wherein: The method further comprises the step of using the compound of formula (IV) and the compound of formula (V) as raw materials to prepare the compound of formula (II): Wherein, R3 is selected from substituted or unsubstituted C4-C20 alkyl; when substituted, it is substituted by H, F, Cl, Br, I, C1-C4 alkyl, hydroxyl, carboxyl, amino, nitro or cyano; 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 reacted in the presence of a catalyst to prepare the compound of formula (II); 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 or 11, wherein the compound of formula (IV) and the compound of formula (V) are reacted at 180-240°C to prepare the compound of formula (II).

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

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

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 to 6.

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

17. The method for preparing the polyolefin material according to any one of claims 15 to 16, comprising fully mixing the polyolefin resin with the compound according to any one of claims 1 to 6 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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