Thiamine compounds and uses thereof

Abstract

The present application provides thiamine compounds shown in formula (I) and application thereof. The thiamine compounds of the present application can be used for preparing polyolefin antioxidants. The thiamine compounds of the present application introduce sulfide bonds in aryl secondary amine, so that the antioxidant contains naphthylamine groups of primary antioxidants and sulfide groups of auxiliary antioxidants, which not only can terminate free radicals by providing hydrogen protons, but also can react with hydroperoxides, so as to achieve the dual effects of primary and auxiliary antioxidants, and thus the antioxidant effect is significantly enhanced.

Description

Technical Field

[0001] This invention relates to the field of chemical materials, and more specifically, to a thiamine compound and its applications. 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 growing shortage of high-end products, such as high-end polyethylene pipe materials, high-transparency medical resin poly4-methyl-1-pentene, and high-end polybutene-1 pipe 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 until they lose their commercial and usability. For most polyolefin materials, adding antioxidants is a simple and effective way to improve their antioxidant properties. 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, while composite antioxidants offer advantages such as low cost, excellent overall performance, short development cycle, and synergistic effects of multiple additives, they can satisfy the multifaceted performance needs of high-end polyolefin materials. Therefore, multifunctional, 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.

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

[0005] To address the issues of poor antioxidant performance in high-end polyolefins due to their limited antioxidant mechanism, poor stability at high temperatures during processing, poor resistance to migration and extraction, and easy precipitation, antioxidants are applied to polyolefin materials such as poly4-methyl-1-pentene, resulting in excellent antioxidant effects.

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

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

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

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

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

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

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

[0013]

[0014] Where R1 is C2-C 20 Alkylene;

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

[0016]

[0017] R6 is a hydrocarbon group;

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

[0019] R 15 Selected from C6-C 20 aryl or C1-C 10 Branched or straight-chain alkyl groups.

[0020] The thiamine compound of the present invention contains both a naphthylamine group, which is the main antioxidant, and a thioether group, which is the auxiliary antioxidant. This allows for the synergistic effect of the main and auxiliary antioxidants within the molecule, which can quickly terminate the free radical chain reaction and decompose the hydroperoxides produced by the chain reaction, thus exhibiting excellent antioxidant effects.

[0021] The thiamine compounds of this invention have a large molecular weight, making them less prone to precipitation during processing and use. They also exhibit good extraction resistance. The molecular structure contains multiple rigid benzene ring structures and non-hydrolyzable linker groups, making them less susceptible to hydrolysis and thermal decomposition into smaller molecules during processing and use. Furthermore, the thiamine compounds of this invention have better stability. When applied to high-end polyolefin materials, especially poly4-methyl-1-pentene resin, they can effectively improve the antioxidant properties of the materials.

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

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

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

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

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

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

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

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

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

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

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

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

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

[0035] R1 is C2-C 14 Alkylene;

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

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

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

[0039]

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

[0041] R1 is C2-C 14 Alkylene;

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

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

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

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

[0046]

[0047]

[0048]

[0049]

[0050] On the other hand, the present invention also provides a method for preparing the thiamine compound of the present invention, the method comprising using a compound of formula (III) and R 15 X is the thiamine compound of formula (I) prepared from raw materials, and X is selected from F, Cl, Br or I.

[0051]

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

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

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

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

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

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

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

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

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

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

[0062] According to some specific embodiments of the present invention, wherein the compound of formula (III) and R 15 The step of preparing the thiamine compound of formula (I) from X as a raw material includes R 15 Solution X is added dropwise to the reaction system to initiate the reaction.

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

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

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

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

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

[0068] According to some specific embodiments of the present invention, the method further includes preparing the compound of formula (III) from compounds of formula (IV) and formula (V):

[0069]

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

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

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

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

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

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

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

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

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

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

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

[0081] According to some specific embodiments of the present invention, in the step of preparing the compound shown in formula (III) from compounds of formula (IV) and formula (V), the reaction temperature is 80-140°C.

[0082] According to some specific embodiments of the present invention, in the step of preparing the compound shown in formula (III) from compounds of formula (IV) and formula (V), the reaction temperature is 90-100°C.

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

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

[0085] According to some specific embodiments of the present invention, the method further includes preparing the compound shown in formula (IV) from compounds of formula (VI) and formula (VII):

[0086]

[0087] R 16 It is an alkylene group with two fewer carbon atoms than R6.

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

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

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

[0091] According to some specific embodiments of the present invention, the compounds of formula (VI) and (VII) are reacted in a nonpolar solvent in the presence of a catalyst to give the compound shown in formula (IV).

[0092] According to some specific embodiments of the present invention, the catalyst used in the step of preparing the compound shown in formula (IV) from compounds of formula (VI) and (VII) is a diazabicyclohexahydropyridine.

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

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

[0095] According to some specific embodiments of the present invention, the amount of nonpolar solvent used in the step of preparing the compound of formula (IV) from compounds of formula (VI) and (VII) is 7-12 times the total mass of compounds of formula (VI) and (VII).

[0096] According to some specific embodiments of the present invention, the nonpolar solvent used in the step of preparing the compound of formula (IV) from compounds of formula (VI) and formula (VII) is one or a mixture of benzene, toluene and ethylbenzene.

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

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

[0099] According to some specific embodiments of the present invention, the step of preparing the compound shown in formula (IV) from the compounds of formula (VI) and formula (VII) includes adding the compound of formula (VII) dropwise into the reaction system and then carrying out the reaction.

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

[0101] According to some specific embodiments of the present invention, the reaction temperature of the step of preparing the compound shown in formula (IV) from compounds of formula (VI) and formula (VII) is room temperature to 50°C.

[0102] According to some specific embodiments of the present invention, the reaction temperature for the step of preparing the compound shown in formula (IV) from compounds of formula (VI) and formula (VII) is room temperature to 30°C.

[0103] According to some specific embodiments of the present invention, the reaction time for the step of preparing the compound shown in formula (IV) from compounds of formula (VI) and formula (VII) is 6-14 h.

[0104] According to some specific embodiments of the present invention, the reaction time for the step of preparing the compound shown in formula (IV) from compounds of formula (VI) and formula (VII) is 6-8 hours.

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

[0106]

[0107] Furthermore, the present invention also provides the application of the thiamine compounds described herein in the preparation of antioxidants.

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

[0109] In another aspect, the present invention also provides a polyolefin antioxidant composite additive, wherein the composite additive includes the thiamine compound, heat stabilizer and rheology modifier described in any one of the present invention; the mass ratio of the thiamine compound, heat stabilizer and rheology modifier is 1:(0.25-0.75):(0.05-0.15).

[0110] In another aspect, the present invention also provides a polyolefin material, wherein the polyolefin material comprises: 100 parts by weight of polyolefin resin and 0.1-0.26 parts by weight of the polyolefin antioxidant composite additive of the present invention.

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

[0112] According to some specific embodiments of the present invention, the polyolefin is poly4-methyl-1-pentene or polybutene-1.

[0113] In another aspect, the present invention also provides a method for preparing the polyolefin material, wherein the method includes fully mixing the polyolefin resin with the polyolefin antioxidant composite additive of the present invention and then extruding and granulating to obtain the polyolefin material, wherein the extrusion granulation temperature is 250-270℃ and the extrusion rate is 5-15 r / min.

[0114] According to some specific embodiments of the present invention, the mixing time for thoroughly mixing the polyolefin resin with the polyolefin antioxidant composite additive of the present invention is 5-20 minutes.

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

[0116] It is understood that, without contradiction, the various specific embodiments of the present invention can be combined arbitrarily with each other.

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

[0118] (1) The thiamine compound of the present invention has a large molecular weight, up to 1641, and has excellent extraction resistance. At the same time, the molecular structure has a flexible long chain, multiple rigid benzene ring structures, and a linking group that is not easily hydrolyzed. It is not easily hydrolyzed or thermally decomposed into small molecules during processing and use, which enhances its compatibility with polymer materials. Therefore, antioxidants are not easily precipitated during material processing and use, and migration loss is small.

[0119] (2) The thioamine compound of the present invention introduces a thioether bond into the main antioxidant such as aryl secondary amine, so that the antioxidant contains both the naphthylamine group of the main antioxidant and the thioether group of the auxiliary antioxidant. It can not only terminate free radicals by providing hydrogen protons, but also react with hydroperoxides to achieve the dual role of main and auxiliary antioxidants. Furthermore, the thioether bond introduced at the para position of the aryl secondary amine has an electron-withdrawing effect, which reduces the electron cloud density at the position where the benzene ring is connected to the secondary amine group, making it easier for hydrogen on the secondary amine group to leave and cause a free radical termination reaction. This can quickly terminate the free radical chain reaction and decompose the hydroperoxides produced by the chain reaction, thus significantly enhancing the antioxidant effect. Attached Figure Description

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

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

[0122] Figure 3 The 1H NMR spectrum of the thiamine composite antioxidant prepared in Example 11;

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

[0124] Figure 5 The 1H NMR spectrum of the thiamine composite antioxidant prepared in Example 12;

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

[0126] Figure 7 The 1H NMR spectrum of the thiamine composite antioxidant prepared in Example 13;

[0127] Figure 8 The mass spectrum of the thiamine composite antioxidant prepared in Example 13 is shown. Detailed Implementation

[0128] 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.

[0129] Example 1

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

[0131] The preparation route is shown below:

[0132]

[0133] a. Synthesis of antioxidant intermediate (I): 100 mL of a 0.1 mol / L methanol solution of 4-mercaptostyrene was accurately weighed. Under nitrogen protection, 0.0003 mol of hexahydropyridine catalyst was added. 30 mL of a 0.1 mol / L methanol solution of 1,14-tetradecanediamine was slowly added dropwise while stirring at room temperature. The reaction was carried out for 8 hours at constant room temperature. Methanol was removed by vacuum distillation, followed by washing three times with ethyl acetate:diethyl ether = 1:10. The product was then dried under vacuum at 30 °C for 24 h to obtain antioxidant intermediate (I) in 91.2% yield.

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

[0135] c. Synthesis of thiamine composite antioxidant (A1): 100 mL of 0.1 mol / L antioxidant intermediate (II) toluene solution was accurately weighed. Under nitrogen protection, 0.001 mol of catalyst bis(triphenylphosphine)-palladium dichloride and 0.0005 mol of promoter N,N-diisopropylethylamine were added dropwise while stirring at 0 °C. The mixture was heated to 80 °C and reacted for 5 hours. The reaction mixture was concentrated under vacuum. The crude product was dissolved in a mixed solvent of ethyl acetate and tetrahydrofuran. After washing the solution, the resulting organic phase was subjected to chromatography to obtain thiamine composite antioxidant (A1) with a yield of 83.4%.

[0136] The thiamine composite antioxidant (thiamine compound, 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 for thiamine antioxidants are as follows: 1 HNMR(CD3Cl,400MHz): δ(ppm)1.29-1.36(m,24H,-CH2-CH2-),3.01(t,4H,N-CH2-),2.67-2.69(m ,16H,N-CH2-CH2-Ar),4.0(s,4H,NH-Ar),6.43-7.54(m,32H,Ar-H),7.36-7.88(m,28h,naph-H). Depend on Figure 2 It can be seen that m / z = 1641.8 is the molecular ion peak of the thiamine composite antioxidant.

[0137] In the granulation section of the poly(4-methyl-1-pentene) material, 0.1% (based on the total mass of poly(4-methyl-1-pentene) being added to the above-mentioned thiamine composite antioxidant, the material was melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly(4-methyl-1-pentene) resin were then tested. The test results of the physical properties of this poly(4-methyl-1-pentene) material are shown in Table 1.

[0138] Example 2:

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

[0140] In the granulation section of poly-4-methyl-1-pentene, 0.21% of the above-mentioned composite additive was added, and the mixture was melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly-4-methyl-1-pentene resin were then tested. The test results of the physical properties of this poly-4-methyl-1-pentene resin are shown in Table 1.

[0141] Example 3:

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

[0143] In the granulation section of poly-4-methyl-1-pentene, 0.26% of the above-mentioned composite additive was added, and the mixture was melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly-4-methyl-1-pentene resin were then tested. The test results of the physical properties of this poly-4-methyl-1-pentene resin are shown in Table 1.

[0144] Example 4:

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

[0146] In the granulation section of poly-4-methyl-1-pentene, 0.21% of the above-mentioned composite additive was added, and the mixture was melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly-4-methyl-1-pentene resin were then tested. The test results of the physical properties of this poly-4-methyl-1-pentene resin are shown in Table 1.

[0147] Example 5:

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

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

[0150]

[0151] In the granulation section of the poly(4-methyl-1-pentene) material, 0.1% of the aforementioned thioamine composite antioxidant was added. The mixture was then melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly(4-methyl-1-pentene) resin were then tested. The test results of the physical properties of this poly(4-methyl-1-pentene) material are shown in Table 1.

[0152] Example 6:

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

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

[0155]

[0156]

[0157] In the granulation section of the poly(4-methyl-1-pentene) material, 0.1% of the aforementioned thioamine composite antioxidant was added. The mixture was then melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly(4-methyl-1-pentene) resin were then tested. The test results of the physical properties of this poly(4-methyl-1-pentene) material are shown in Table 1.

[0158] Example 7:

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

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

[0161]

[0162] In the granulation section of the poly(4-methyl-1-pentene) material, 0.1% of the aforementioned thioamine composite antioxidant was added. The mixture was then melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly(4-methyl-1-pentene) resin were then tested. The test results of the physical properties of this poly(4-methyl-1-pentene) material are shown in Table 1.

[0163] Example 8:

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

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

[0166]

[0167] In the granulation section of the poly(4-methyl-1-pentene) material, 0.1% of the aforementioned thioamine composite antioxidant was added. The mixture was then melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly(4-methyl-1-pentene) resin were then tested. The test results of the physical properties of this poly(4-methyl-1-pentene) material are shown in Table 1.

[0168] Example 9:

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

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

[0171]

[0172] In the granulation section of the poly(4-methyl-1-pentene) material, 0.1% of the aforementioned thioamine composite antioxidant was added. The mixture was then melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly(4-methyl-1-pentene) resin were then tested. The test results of the physical properties of this poly(4-methyl-1-pentene) material are shown in Table 1.

[0173] Example 10:

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

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

[0176]

[0177] In the granulation section of the poly(4-methyl-1-pentene) material, 0.1% of the aforementioned thioamine composite antioxidant was added. The mixture was then melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly(4-methyl-1-pentene) resin were then tested. The test results of the physical properties of this poly(4-methyl-1-pentene) material are shown in Table 1.

[0178] Example 11:

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

[0180]

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

[0182] In the granulation section of the poly(4-methyl-1-pentene) material, 0.1% of the aforementioned thioamine composite antioxidant was added. The mixture was then melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly(4-methyl-1-pentene) resin were then tested. The test results of the physical properties of this poly(4-methyl-1-pentene) material are shown in Table 1.

[0183] Example 12:

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

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

[0186] In the granulation section of the poly(4-methyl-1-pentene) material, 0.1% of the aforementioned thioamine composite antioxidant was added. The mixture was then melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly(4-methyl-1-pentene) resin were then tested. The test results of the physical properties of this poly(4-methyl-1-pentene) material are shown in Table 1.

[0187]

[0188] Example 13:

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

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

[0191]

[0192] In the granulation section of the poly(4-methyl-1-pentene) material, 0.1% of the aforementioned thioamine composite antioxidant was added. The mixture was then melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly(4-methyl-1-pentene) resin were then tested. The test results of the physical properties of this poly(4-methyl-1-pentene) material are shown in Table 1.

[0193] Example 14:

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

[0195] In the granulation section of poly-4-methyl-1-pentene, 0.21% of the above-mentioned composite additive was added, and the mixture was melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 250℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly-4-methyl-1-pentene resin were then tested. The test results of the physical properties of this poly-4-methyl-1-pentene resin are shown in Table 1.

[0196] Example 15:

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

[0198] In the granulation section of poly-4-methyl-1-pentene, 0.21% of the above-mentioned composite additive was added, and the mixture was melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 270℃ and an extrusion rate of 10 r / min. The mechanical properties and oxidation induction period of the poly-4-methyl-1-pentene resin were then tested. The test results of the physical properties of this poly-4-methyl-1-pentene resin are shown in Table 1.

[0199] Example 16:

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

[0201] In the granulation section of poly-4-methyl-1-pentene, 0.21% of the above-mentioned composite additive was added, and the mixture was melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 5 r / min. The mechanical properties and oxidation induction period of the poly-4-methyl-1-pentene resin were then tested. The test results of the physical properties of this poly-4-methyl-1-pentene resin are shown in Table 1.

[0202] Example 17:

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

[0204] In the granulation section of poly-4-methyl-1-pentene, 0.21% of the above-mentioned composite additive was added, and the mixture was melt-extruded, drawn into fibers, and granulated using an extruder at an extrusion temperature of 260℃ and an extrusion rate of 15 r / min. The mechanical properties and oxidation induction period of the poly-4-methyl-1-pentene resin were then tested. The test results of the physical properties of this poly-4-methyl-1-pentene resin are shown in Table 1.

[0205] Comparative Example 1:

[0206] In the poly-4-methyl-1-pentene granulation section, 0.1% (based on 100% of the total mass of poly-4-methyl-1-pentene, the same below) of antioxidant DNP was added to replace the composite antioxidant of the present invention. Following the extrusion granulation process of Example 1, the poly-4-methyl-1-pentene was extruded, drawn into fibers, and granulated using a twin-screw extruder at an extrusion temperature of 260°C and an extrusion rate of 10 r / min. The oxidation induction period and mechanical properties of the poly-4-methyl-1-pentene were then tested. The test results for the poly-4-methyl-1-pentene are shown in Table 1.

[0207]

[0208] Comparative Example 2:

[0209] In the poly-4-methyl-1-pentene granulation section, 0.1% of antioxidant D was added to replace the composite antioxidant of the present invention. Following the extrusion granulation process of Example 1, the poly-4-methyl-1-pentene was extruded, drawn into fibers, and granulated using a twin-screw extruder at an extrusion temperature of 260°C and an extrusion rate of 10 r / min. The oxidation induction period and mechanical properties of the poly-4-methyl-1-pentene were then tested. The test results for this poly-4-methyl-1-pentene are shown in Table 1.

[0210]

[0211] Comparative Example 3:

[0212] In the poly(4-methyl-1-pentene) granulation section, 0.1% of dodecanol thiodipropionate was added to replace the composite antioxidant of the present invention. Following the extrusion granulation process of Example 1, the poly(4-methyl-1-pentene) was extruded, drawn into fibers, and granulated using a twin-screw extruder at an extrusion temperature of 260°C and an extrusion rate of 10 r / min. The oxidation induction period and mechanical properties of the poly(4-methyl-1-pentene) were then tested. The test results for the poly(4-methyl-1-pentene) are shown in Table 1.

[0213] Test case

[0214] 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.

[0215] 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.

[0216] The results of the OIT analysis and mechanical property tests are shown in Table 1:

[0217] Table 1. Analytical results of poly-4-methyl-1-pentene

[0218]

[0219]

[0220] As can be seen from the data in Table 1, the thioamine composite antioxidants A1-A10 prepared in this invention can effectively improve the mechanical properties and oxidation induction period of poly-4-methyl-1-pentene materials, and antioxidants A1 and A10 exhibit the best antioxidant effects. Furthermore, compared with commercially available amine and thioether antioxidants, the synthesized thioamine composite antioxidants show significantly better antioxidant effects.

[0221] This invention provides a thiamine composite antioxidant containing both a naphthylamine group (primary antioxidant) and a thioether group (auxiliary antioxidant), achieving a synergistic effect between the primary and auxiliary antioxidants within the molecule. This allows for the rapid termination of free radical chain reactions and the decomposition of hydroperoxides generated during these reactions, resulting in excellent antioxidant performance. Furthermore, this thiamine composite antioxidant has a large molecular weight, making it less prone to precipitation during processing and use, exhibiting good extraction resistance. Its molecular structure contains multiple rigid benzene rings and non-hydrolyzable linker groups, further enhancing its stability and preventing hydrolysis and thermal decomposition into smaller molecules during processing and use. Applying this antioxidant to high-end resins such as polybutene-1 and poly4-methyl-1-pentene can effectively improve the antioxidant properties of these materials, providing important guidance for the development and use of high-end resin additives.

Claims

1. The thiamine compound represented by formula (I): in, R1 is C2-C 20 Alkylene; R2, R3, R4, and R5 are each independently selected from the following general formula: R6 is a C2-C5 straight-chain alkylene group; R7, R8, R9, R 10 R 11 R 12 R 13 R 14 Each is independently selected from hydrogen or C1-C6 alkyl groups; R 15 Selected from C6-C 20 aryl or C1-C 10 Branched or straight-chain alkyl groups.

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

3. The thiamine compound according to claim 1, wherein, R2, R3, R4, and R5 have the same structure.

4. The thiamine compound according to claim 1, wherein, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 Independently selected from hydrogen or C1-C4 alkyl.

5. The thiamine compound according to claim 1, wherein, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 It is hydrogen.

6. The thiamine compound according to claim 1, wherein, The compound is the compound shown in formula (II) below:

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

8. The thiamine compound according to any one of claims 1 to 6, wherein, R1 is C2-C 14 Alkylene; R 15 It is selected from phenyl, naphthyl, isopropyl, isobutyl or isopentyl.

9. The thiamine compound according to any one of claims 1 to 6, wherein, R1 is C8-C 14 Alkylene.

10. The thiamine compound according to any one of claims 1 to 6, wherein, R 15 Selected from phenyl, naphthyl, isopropyl or isobutyl.

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

12. The use of the thiamine compound according to any one of claims 1 to 11 in the preparation of antioxidants.

13. The application according to claim 12, wherein, The antioxidant is a polyolefin antioxidant.

14. A polyolefin antioxidant composite additive, wherein, The composite additive includes the thiamine compound, heat stabilizer and rheology modifier as described in any one of claims 1 to 11; the mass ratio of the thiamine compound, heat stabilizer and rheology modifier is 1:(0.25-0.75):(0.05-0.15).

15. A polyolefin material, wherein, The polyolefin material comprises: 100 parts by weight of polyolefin resin and 0.1-0.26 parts by weight of the polyolefin antioxidant composite additive as described in claim 14.

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

17. The polyolefin material according to claim 15 or 16, wherein, The polyolefin is polyethylene, polypropylene, poly4-methyl-1-pentene, or polybutene-1.

18. A method for preparing the polyolefin material according to any one of claims 15 to 17, comprising thoroughly mixing the polyolefin resin with the polyolefin antioxidant composite additive according to claim 14, followed by extrusion granulation to obtain the polyolefin material, wherein, The extrusion granulation temperature is 250-270℃, and the extrusion rate is 5-15 r / min.

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