Process for the preparation of a thiamine compound

Abstract

The present application provides a preparation method of thiamine compound shown in formula (I), wherein the method comprises using compound of formula (III) and R 15 X is used to prepare thiamine compound shown in formula (I),

Description

Technical Field

[0001] This invention relates to the field of chemical materials, and more specifically, to a method for preparing a thiamine compound. Background Technology

[0002] 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. To improve the service life and processing performance of these high-end materials, various additives can be added, with antioxidants being one of the most important. However, for materials with high melting points and high transparency, higher requirements are placed on the performance and colorability of antioxidants. To meet market demands, the research and application of intramolecular composite antioxidants with superior performance are receiving increasing attention. These antioxidants generally contain primary and secondary antioxidant groups. They can inhibit chain growth reactions by providing hydrogen protons to terminate free radical chain reactions or by capturing free radicals to generate inert products (primary antioxidant groups: hindered phenols and aryl amines), or by decomposing the hydroperoxides generated in chain growth reactions to terminate oxidation reactions (secondary antioxidant groups: thioether bonds and phosphite groups). Because the primary and secondary antioxidant groups produce a synergistic antioxidant effect, they exhibit better antioxidant performance.

[0003] Research on the preparation of intramolecular composite antioxidants mainly uses amidation, transesterification, nitration, and reduction reactions. The yield of the prepared antioxidants is generally less than 80%, and the purity of the products is not high.

[0004] For example, Chinese patent CN102516157B reports a hindered phenol / hindered amine molecular composite antioxidant. This patent first prepares an antioxidant intermediate by reacting 3,5-dialkyl-4-hydroxybenzoic acid with sulfoxide in a substitution reaction. Then, the antioxidant intermediate undergoes an amidation reaction with N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine. An acid-binding agent is then added, and the reaction continues. After the reaction is complete, the mixture is filtered, washed, and vacuum dried to obtain the hindered phenol / hindered amine intramolecular composite antioxidant. When added to polyamide resin, long-term aging tests showed that the novel antioxidant significantly delayed the degradation of the polyamide resin.

[0005] Chinese patent CN201910752684.3 reports a hindered phenol and amide intramolecular composite bifunctional antioxidant and its synthesis method. The antioxidant is prepared by first preparing an ethylenediamine dendritic molecular skeleton from ethylenediamine, methanol, and methyl acrylate, and then blocking the end groups of the ethylenediamine dendritic molecular skeleton with DtBHP. This antioxidant terminates the chain reaction by capturing the generated free radicals and forming relatively stable free radicals itself. It can directly, effectively, and rapidly capture free radicals and has high antioxidant capacity.

[0006] Wang Jian et al. synthesized an intramolecular composite antioxidant, [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate dioctadecyl phosphate], via transesterification using methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (MPC), diethyl phosphite, and octadecyl alcohol as raw materials. The results showed that the product had a melting point of 47.7-49.2℃ and a yield exceeding 75%. When applied to polypropylene (PP), the oxidation induction period was 41.351 min, 1.3 times that of antioxidant 1076, and the melt flow rate was 1.932 g / 10 min, significantly improving the flowability of PP resin (Wang Jian, Ji Wei, Zhang Xuejia, et al. Synthesis and performance evaluation of an intramolecular composite antioxidant. Fine Chemicals, 2008, 25(7)).

[0007] Li Cuiqin et al. synthesized a novel intramolecular composite primary antioxidant, 2,6-di-tert-butyl-p-aminophenol, from 2,6-di-tert-butylphenol as a raw material through nitration and reduction reactions. The product yield was over 80%, and the melting range was 112.2-113.3℃. The novel antioxidant effectively inhibited the oxidative degradation of polyethylene during processing and use. (Li Cuiqin, Wang Jun, Zhang Zhiqi, et al. Synthesis and properties of novel intramolecular composite primary antioxidant. Chemical Industry and Engineering Progress, 2010(11)).

[0008] The antioxidants reported above contain hindered phenol, aryl amine, or phosphite active units, but the synthesis and application of intramolecular complex antioxidants with thiamine have not been reported. Meanwhile, increasing research indicates that high molecular weight antioxidants possess advantages such as low volatility, extraction resistance, and high temperature resistance, which can reduce losses during high-temperature polymer processing and applications. Therefore, researching high-performance high molecular weight antioxidants has become a trend in the field of antioxidant research. Summary of the Invention

[0009] The purpose of this invention is to provide a method for preparing thiamine compounds.

[0010] To achieve the above objectives, the present invention provides a method for preparing a thiamine compound of formula (I), wherein the method comprises preparing a compound of formula (III) and R. 15 X is the thiamine compound shown in formula (I) prepared from raw materials.

[0011]

[0012] R6 is a hydrocarbon group;

[0013] R7, R8, R9, R 10 R 11 R 12 R 13 R 14 Each is independently selected from hydrogen or C1-C6 alkyl groups;

[0014] R 15 Selected from C6-C 20 aryl or C1-C 10 Branched or straight-chain alkyl groups;

[0015] X is selected from F, Cl, Br, or I.

[0016] 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), wherein the catalyst is palladium dichloride bis(triphenylphosphine) and / or palladium acetate.

[0017] 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).

[0018] 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).

[0019] 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 and a promoter to prepare the thioamine compound shown in formula (I), wherein the promoter is N,N-diisopropylethylamine.

[0020] 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).

[0021] 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).

[0022] 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).

[0023] According to some specific embodiments of the present invention, wherein R15 The molar amount of X is 6-7 times the molar amount of compound (III).

[0024] 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℃.

[0025] 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℃.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] According to some specific embodiments of the present invention, wherein R 15 The dripping rate of solution X is 5-10 ml / min.

[0030] 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) using X as a raw material, the compound of formula (III) and R... 15 Formula X undergoes a substitution reaction in the presence of a catalyst and a promoter to prepare the thiamine compound shown in formula (I). The molar amount of the promoter is 0.01-0.07 times that of the compound in formula (III), and the molar amount of the catalyst is 0.05-0.12 times that of the compound in formula (III). 15 The molar amount of X is 5-10 times that of the compound of formula (III), and the reaction time is 2-6 h.

[0031] According to some specific embodiments of the present invention, the method further includes preparing the compound shown in formula (III) from compounds of formula (IV) and formula (V):

[0032]

[0033] According to some specific embodiments of the present invention, compounds of formula (IV) and (V) are prepared in the presence of a basic catalyst, wherein the basic catalyst is pyridine.

[0034] 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).

[0035] 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).

[0036] According to some specific embodiments of the present invention, the molar amount of compound (V) is 5-10 times that of compound (IV).

[0037] According to some specific embodiments of the present invention, the molar amount of compound (V) is 5-7 times that of compound (IV).

[0038] 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).

[0039] 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).

[0040] 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).

[0041] According to some specific embodiments of the present invention, the nonpolar solvent is one or a mixture of several of benzene, toluene, and ethylbenzene.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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), wherein the molar amount of the basic catalyst is 0.02-0.4 times that of the compound of formula (IV), the molar amount of the compound of formula (V) is 5-10 times that of the compound of formula (IV), and the reaction time is 4-12 h.

[0047] 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):

[0048]

[0049] R 16 It is an alkylene group with two fewer carbon atoms than R6.

[0050] 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).

[0051] 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).

[0052] 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), wherein the catalyst is a diazabicyclohexane or hexahydropyridine.

[0053] According to some specific embodiments of the present invention, the molar amount of 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).

[0054] 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 0.1-0.15 times the molar amount of compound (VI).

[0055] 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).

[0056] 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).

[0057] 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.

[0058] According to some specific embodiments of the present invention, in the step of preparing the compound shown in formula (IV) using compounds of formula (VI) and formula (VII) as raw materials, the molar amount of compound (VII) is 2-4 times that of compound (VI).

[0059] According to some specific embodiments of the present invention, the molar amount of compound (VII) is 3-4 times that of compound (VI).

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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 h.

[0064] 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.

[0065] According to some specific embodiments of the present invention, the dripping rate of the compound of formula (VII) is 5-10 ml / min.

[0066] According to some specific embodiments of the present invention, compounds of formula (VI) and (VII) are reacted in a nonpolar solvent in the presence of a catalyst to obtain the compound shown in formula (IV), wherein the molar amount of the catalyst is 0.05-0.2 times the molar amount of compound (VI), and the reaction time is 6-14 h.

[0067] According to some specific embodiments of the present invention, wherein,

[0068] R1 is C2-C 14 Alkylene;

[0069] R6 is a C2-C5 straight-chain alkylene group;

[0070] R7, R8, R9, R 10 R 11 R 12 R 13 R 14 Each is independently selected from hydrogen or C1-C4 alkyl groups;

[0071] R 15 Selected from C6-C 16 It is an aryl group or a C1-C6 branched or straight-chain alkyl group.

[0072] 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.

[0073] According to some specific embodiments of the present invention, R6 is a C2-C3 straight-chain alkylene group.

[0074] According to some specific embodiments of the present invention, R6 is a C2 straight-chain alkylene group.

[0075] According to some specific embodiments of the present invention, wherein R7, R8, R9, R 10 R 11 R 12 R13 R 14 Each is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0076] According to some specific embodiments of the present invention, wherein R7, R8, R9, R 10 R 11 R 12 R 13 R 14 It is hydrogen.

[0077] 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.

[0078] 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.

[0079] According to some specific embodiments of the present invention, wherein,

[0080] R1 is C2-C 14 Alkylene;

[0081] R7, R8, R9, R 10 R 11 R 12 R 13 R 14 It is hydrogen;

[0082] R 15 Selected from phenyl, naphthyl, isopropyl or isobutyl.

[0083] According to some specific embodiments of the present invention, the compound is a compound of the following formula (II):

[0084]

[0085] According to some specific embodiments of the present invention, wherein,

[0086] R1 is C2-C 14 Alkylene;

[0087] R 15 It is selected from phenyl, naphthyl, isopropyl, isobutyl or isopentyl.

[0088] According to some specific embodiments of the present invention, R1 is C8-C 14 Alkylene.

[0089] According to some specific embodiments of the present invention, wherein R 15 Selected from phenyl, naphthyl, isopropyl or isobutyl.

[0090] According to some specific embodiments of the present invention, wherein R 15 Selected from naphthyl or isobutyl.

[0091] According to some specific embodiments of the present invention, the thiamine compound is selected from the following compounds:

[0092]

[0093]

[0094]

[0095] According to some specific embodiments of the present invention, the method for preparing the compound of formula (I) is as follows:

[0096]

[0097] In summary, this invention provides a thiamine compound and its applications. The thiamine compound of this invention has the following advantages:

[0098] (1) The reaction conditions and processes of the thiamine composite antioxidant prepared by the present invention are simple, which greatly reduces the reaction difficulty of the antioxidant preparation process. At the same time, the raw materials are readily available, which effectively reduces the raw material and production costs and makes it easy to achieve industrial production.

[0099] (2) The thioamine composite antioxidant prepared by this invention introduces a thioether bond at the para position of the naphthylamine group, the main antioxidant group. The substituentability of the benzene ring greatly enriches the types of antioxidants and provides a new idea for the design and preparation of novel and efficient intramolecular antioxidants.

[0100] (3) The thiamine composite antioxidant provided by the present invention has a high molecular weight, which improves the antioxidant’s ability to resist migration in polymer materials. At the same time, the antioxidant contains multiple aromatic ring structures, which effectively improves its thermal stability. Attached Figure Description

[0101] Figure 1 The 1H NMR spectrum of the thiamine composite antioxidant prepared in Example 1;

[0102] Figure 2 The mass spectrum of the thiamine composite antioxidant prepared in Example 1;

[0103] Figure 3 The 1H NMR spectrum of the thiamine composite antioxidant prepared in Example 11;

[0104] Figure 4The mass spectrum of the thiamine composite antioxidant prepared in Example 11;

[0105] Figure 5 The 1H NMR spectrum of the thiamine composite antioxidant prepared in Example 12;

[0106] Figure 6 The mass spectrum of the thiamine composite antioxidant prepared in Example 12;

[0107] Figure 7 The 1H NMR spectrum of the thiamine composite antioxidant prepared in Example 13;

[0108] Figure 8 The mass spectrum of the thiamine composite antioxidant prepared in Example 13 is shown. Detailed Implementation

[0109] 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.

[0110] Example 1

[0111] The preparation process of the antioxidant intermediate and the thiamine complex antioxidant (A1) in this embodiment is as follows:

[0112] The preparation route is shown below:

[0113]

[0114] 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.

[0115] 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%.

[0116] 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 bis(triphenylphosphine)-palladium dichloride catalyst and 0.0005 mol of N,N-diisopropylethylamine promoter were added. 120 mL of 0.5 mol / L 2-iodonaphthalene toluene solution was slowly added dropwise while stirring at 0 °C. The mixture was heated to 80 °C and reacted for 5 hours. The resulting 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%.

[0117] 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.

[0118] 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.

[0119] Example 2:

[0120] 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.

[0121] 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.

[0122] Example 3:

[0123] 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.

[0124] 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.

[0125] Example 4:

[0126] 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.

[0127] 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.

[0128] Example 5:

[0129] 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%.

[0130]

[0131] Thiamine compound antioxidant A2

[0132] The characterization data of the obtained thiamine antioxidant (A2) are as follows: 1 H 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).

[0133] 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.

[0134] Example 6:

[0135] 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%.

[0136]

[0137] Thiamine compound antioxidant A3

[0138] 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).

[0139] 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.

[0140] Example 7:

[0141] 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%.

[0142]

[0143] Thiamine compound antioxidant A4

[0144] 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).

[0145] 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.

[0146] Example 8:

[0147] 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%.

[0148]

[0149] Thiamine compound antioxidant A5

[0150] The characterization data of the obtained thiamine antioxidant (A5) are as follows: 1H 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).

[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 9:

[0153] 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%.

[0154]

[0155] Thiamine compound antioxidant A6

[0156] The characterization data of the obtained thiamine antioxidant (A6) are as follows: 1H NMR (CD3Cl, 400MHz): δ (ppm) 1.76 (t, 4H, -CH2-CH2-), 3.01 (t, 4H, N-CH2-), 2.67-2.69 (m, 16H, N-CH2-CH2-Ar), 4.2 (s, 4H, NH-Ar), 6.43-7.54 (m, 32H, Ar-H), 7.36-7.88 (m, 28h, naph-H).

[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 10:

[0159] 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%.

[0160]

[0161] Thiamine compound antioxidant A7

[0162] The characterization data of the obtained thiamine antioxidant (A7) are as follows: 1 H 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).

[0163] 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.

[0164] Example 11:

[0165] 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%.

[0166]

[0167] Thiamine compound antioxidant A8

[0168] 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: 1H 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).

[0169] 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.

[0170] Example 12:

[0171] 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%.

[0172] 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).

[0173] 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.

[0174]

[0175] Thiamine compound antioxidant A9

[0176] Example 13:

[0177] 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%.

[0178] 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).

[0179]

[0180] Thiamine compound antioxidant A10

[0181] 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.

[0182] Example 14:

[0183] 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.

[0184] 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.

[0185] Example 15:

[0186] 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.

[0187] 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.

[0188] Example 16:

[0189] 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.

[0190] 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.

[0191] Example 17:

[0192] 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.

[0193] 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.

[0194] Example 18:

[0195] The preparation steps of the antioxidant intermediate and the thiamine complex antioxidant (A1) in this embodiment are basically the same as those of the thiamine complex antioxidant described in Example 1. The differences are: in step a, the amount of 1,14-tetradecanediamine methanol solution added is 25 ml, and the yield of step a is 87.6%; in step b, the amount of p-phenylenediamine toluene solution added is 150 ml, and the yield of step b is 79.9%; and in step c, the amount of 2-iodonaphthalene toluene solution added is 100 ml, and the yield of step c is 76.1%. The proton NMR and mass spectra of the obtained products are respectively compared with... Figure 1 and Figure 2 same.

[0196] Example 19:

[0197] The preparation steps of the antioxidant intermediate and the thiamine complex antioxidant (A1) in this embodiment are basically the same as those of the thiamine complex antioxidant described in Example 1. The differences are as follows: in step a, the amount of 1,14-tetradecanediamine methanol solution added is 40 ml, and the yield of step a is 91.6%; in step b, the amount of p-phenylenediamine toluene solution added is 300 ml, and the yield of step b is 85.0%; in step c, the amount of 2-iodonaphthalene toluene solution added is 170 ml, and the yield of step c is 83.6%. The proton NMR and mass spectra of the obtained products are respectively compared with... Figure 1 and Figure 2 same.

[0198] Example 20:

[0199] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A1) in this embodiment are basically the same as those of the thiamine composite antioxidant described in Example 1. The differences are as follows: in step a, the amount of hexahydropyridine catalyst added is 0.00015 mol, and the yield of step a is 67.4%; in step b, the amount of pyridine catalyst added is 0.00006 mol, and the yield of step b is 71.8%; in step c, the amount of 2-iodonaphthalene toluene solution added is 200 ml, and the yield of step c is 83.7%. The proton NMR and mass spectra of the obtained products are respectively compared with... Figure 1 and Figure 2 same.

[0200] Example 21:

[0201] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A1) in this embodiment are basically the same as those of the thiamine composite antioxidant described in Example 1. The differences are as follows: in step a, the amount of hexahydropyridine catalyst added is 0.0006 mol, and the yield of step a is 91.5%; in step b, the amount of pyridine catalyst added is 0.0006 mol, and the yield of step b is 85.1%; in step c, the amount of bis(triphenylphosphine)phosphine dichloride palladium catalyst added is 0.0005 mol, and the yield of step c is 74.5%. The proton NMR and mass spectra of the obtained products are respectively compared with... Figure 1 and Figure 2 same.

[0202] Example 22:

[0203] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A1) in this embodiment are basically the same as those of the thiamine composite antioxidant described in Example 1. The difference is that the catalyst in step a is diazabicyclic, and the yield of step a is 52.8%; the amount of pyridine catalyst added in step b is 0.0012 mol, and the yield of step b is 85.4%; the amount of bis(triphenylphosphine)phosphine dichloride catalyst added in step c is 0.0007 mol, and the yield of step c is 83.7%. The proton NMR and mass spectra of the obtained products are respectively compared with those of the catalysts in Example 1. Figure 1 and Figure 2 same.

[0204] Example 23:

[0205] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A1) in this embodiment are basically the same as those of the thiamine composite antioxidant described in Example 1. The differences are: the reaction temperature in step a is 40°C, and the yield of step a is 89.4%; the reaction temperature in step b is 80°C, and the yield of step b is 71.3%; the amount of catalyst bis(triphenylphosphine)-palladium dichloride added in step c is 0.0012 mol, and the yield of step c is 83.8%. The proton NMR and mass spectra of the obtained product are respectively compared with... Figure 1 and Figure 2 same.

[0206] Example 24:

[0207] The preparation steps of the antioxidant intermediate and the thiamine complex antioxidant (A1) in this embodiment are basically the same as those of the thiamine complex antioxidant described in Example 1. The differences are: the reaction temperature in step a is 50°C, and the yield of step a is 47.2%; the reaction temperature in step b is 140°C, and the yield of step b is 79.9%; the amount of N,N-diisopropylethylamine, the accelerator, added in step c is 0.0001 mol, and the yield of step c is 64.8%. The proton NMR and mass spectra of the obtained products are respectively compared with... Figure 1 and Figure 2 same.

[0208] Example 25:

[0209] The preparation steps of the antioxidant intermediate and the thiamine complex antioxidant (A1) in this embodiment are basically the same as those of the thiamine complex antioxidant described in Example 1. The differences are: the reaction time in step a is 6 hours, and the yield of step a is 79.4%; the reaction time in step b is 4 hours, and the yield of step b is 67.2%; and the amount of N,N-diisopropylethylamine, the accelerator, added in step c is 0.0003 mol, and the yield of step c is 77.5%. The proton NMR and mass spectra of the obtained product are respectively compared with... Figure 1 and Figure 2 same.

[0210] Example 26:

[0211] The preparation steps of the antioxidant intermediate and the thiamine complex antioxidant (A1) in this embodiment are basically the same as those of the thiamine complex antioxidant described in Example 1. The differences are: the reaction time in step a is 11 hours, and the yield of step a is 91.3%; the reaction time in step b is 12 hours, and the yield of step b is 85.3%; and the amount of N,N-diisopropylethylamine, the accelerator, added in step c is 0.0007 mol, and the yield of step c is 83.3%. The proton NMR and mass spectra of the obtained product are respectively compared with... Figure 1 and Figure 2 same.

[0212] Example 27:

[0213] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A1) in this embodiment are basically the same as those of the thiamine composite antioxidant described in Example 1. The difference is that the reaction time in step a is 14 hours, and the yield of step a is 91.5%; the catalyst in step c is palladium acetate, and the yield of step c is 71.1%. The proton NMR and mass spectra of the obtained products are compared with those of... Figure 1 and Figure 2 same.

[0214] Example 28:

[0215] The preparation steps of the antioxidant intermediate and the thiamine complex antioxidant (A4) in this embodiment are basically the same as those of the thiamine complex antioxidant described in Example 7, except that the reaction temperature in step c is 50°C and the yield in step c is 79.4%. The proton NMR spectrum of the obtained product is the same as that in Example 7.

[0216] Example 29:

[0217] The preparation steps of the antioxidant intermediate and the thiamine complex antioxidant (A7) in this embodiment are basically the same as those of the thiamine complex antioxidant described in Example 10, except that the reaction temperature in step c is 100°C and the yield in step c is 83.6%. The proton NMR spectrum of the obtained product is the same as that in Example 10.

[0218] Example 30:

[0219] The preparation steps of the antioxidant intermediate and the thiamine complex antioxidant (A8) in this embodiment are basically the same as those of the thiamine complex antioxidant described in Example 11, except that the reaction time in step c is 2 hours, and the yield in step c is 72.6%. The proton NMR and mass spectra of the obtained product are respectively compared with those of the previous embodiment. Figure 3 and Figure 4 same.

[0220] Example 31:

[0221] The preparation steps of the antioxidant intermediate and the thiamine complex antioxidant (A10) in this embodiment are basically the same as those of the thiamine complex antioxidant described in Example 13, except that the reaction time in step c is 6 hours, and the yield in step c is 92.9%. The proton NMR and mass spectra of the obtained product are respectively compared with those of the previous embodiment. Figure 7 and Figure 8 same.

[0222] Comparative Example 1:

[0223] 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.

[0224]

[0225] Anti-aging agent DNP

[0226] Comparative Example 2:

[0227] 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.

[0228]

[0229] Anti-aging agent D

[0230] Comparative Example 3:

[0231] 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.

[0232] Test case

[0233] 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.

[0234] 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.

[0235] The results of the OIT analysis and mechanical property tests are shown in Table 1:

[0236] Table 1. Analytical results of poly-4-methyl-1-pentene

[0237]

[0238]

[0239] 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.

[0240] 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. A method for preparing the thiamine compound shown in formula (I), wherein, The method includes using a compound of formula (III) and R 15 X is the thioamine compound prepared from the raw material shown in formula (I). (I) (III) R1 is C2-C 14 Alkylene; R6 is a C2-C5 hydrocarbon group; R7, R8, R9, R 10 R 11 R 12 R 13 R 14 Each is independently selected from hydrogen or C1-C4 alkyl groups; R 15 Selected from C6-C 14 Aryl or C1-C6 branched or straight-chain alkyl; X is selected from F, Cl, Br, or I; Compound (III) and R 15 Formula X undergoes a substitution reaction in the presence of a catalyst and a promoter to prepare the thioamine compound shown in Formula (I), wherein the catalyst is palladium dichloride bis(triphenylphosphine) and / or palladium acetate, and the promoter is N,N-diisopropylethylamine.

2. The preparation method according to claim 1, wherein, 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℃.

3. The preparation method according to claim 1, wherein, 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 compound of formula (III) and R 15 Formula X undergoes a substitution reaction in the presence of a catalyst and a promoter to prepare the thiamine compound shown in formula (I). The molar amount of the promoter is 0.01-0.07 times that of the compound in formula (III), and the molar amount of the catalyst is 0.05-0.12 times that of the compound in formula (III). 15 The molar amount of X is 5-10 times that of the compound of formula (III), and the reaction time is 2-6 h.

4. The preparation method according to claim 1, wherein, The method also includes preparing the compound shown in formula (III) from compounds of formula (IV) and formula (V): (IV) (V) 。 5. The preparation method according to claim 4, wherein, Compounds (IV) and (V) were prepared in the presence of a basic catalyst, namely pyridine, to obtain the compound shown in formula (III).

6. The preparation method according to claim 4, wherein, 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℃.

7. The preparation method according to claim 4, wherein, Compounds (IV) and (V) were prepared in a nonpolar solvent in the presence of a basic catalyst to obtain the compound shown in (III). The molar amount of the basic catalyst was 0.02-0.4 times that of compound (IV), and the molar amount of compound (V) was 5-10 times that of compound (IV). The reaction time was 4-12 h.

8. The preparation method according to claim 4, wherein, The method also includes preparing the compound of formula (IV) from compounds of formula (VI) and formula (VII): (VI) (VII) R 16 It is an alkylene group with two fewer carbon atoms than R6.

9. The preparation method according to claim 8, wherein, Compounds of formula (VI) and (VII) are reacted in the presence of a catalyst to give the compound shown in formula (IV), wherein the catalyst is diazabicyclo or hexahydropyridine.

10. The preparation method according to claim 8, wherein, In the steps of preparing the compound shown in formula (IV) from compounds of formula (VI) and formula (VII), the molar amount of compound (VII) is 2-4 times that of compound (VI).

11. The preparation method according to claim 8, wherein, The reaction temperature for preparing the compound shown in formula (IV) from compounds of formula (VI) and (VII) is from room temperature to 50°C.

12. The preparation method according to claim 8, wherein, Compounds (VI) and (VII) were reacted in a nonpolar solvent in the presence of a catalyst to give the compound shown in (IV), with the amount of catalyst being 0.05-0.2 times the molar amount of compound (VI), and the reaction time being 6-14 h.

13. The preparation method according to any one of claims 1 to 12, wherein, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 It is hydrogen.

14. The preparation method according to any one of claims 1 to 12, 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.

15. The preparation method according to any one of claims 1 to 12, wherein, The thiamine compound is selected from the following compounds: 。

Images