Preparation method of thiamine compound

Abstract

The invention provides a preparation method of a thiamine compound as shown in formula (I), which comprises the step of preparing the thiamine compound as shown in formula (I) by using a compound as shown in formula (III) and R15X as raw materials, # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of chemical materials, and in particular to a method for preparing a thiamine compound. Background Art

[0002] In recent years, the polymer materials industry has developed rapidly, especially the gap in high-end products has continued to increase, such as high-end polyethylene tube materials, highly transparent medical resin poly-4-methyl-1-pentene and high-end polybutene-1 tube materials. In order to improve the service life and processing and application performance of such high-end materials, various additives can be added, and antioxidants are one of the most important additives. However, for materials with high melting points and high transparency, higher requirements are placed on the performance and colorability of antioxidants. In order to meet the application needs of the market, the research and application of intramolecular composite antioxidants with better performance have received more and more attention. This type of antioxidant generally contains a main antioxidant group and an auxiliary antioxidant group, which can terminate the free radical chain reaction by providing hydrogen protons or capture free radicals to generate inert products, inhibit chain growth reactions (main antioxidant groups: hindered phenols and aromatic amines), and can also terminate the oxidation reaction by decomposing the hydroperoxides produced by the chain growth reaction (auxiliary antioxidant groups: thioether bonds and phosphite groups). Since the main and auxiliary antioxidant groups produce antioxidant synergistic effects, they have better antioxidant effects.

[0003] The research on the preparation of intramolecular composite antioxidants mainly adopts amidation reaction, transesterification reaction and nitration and reduction reaction. The yield of the prepared antioxidants is generally less than 80%, and the product purity is not high.

[0004] For example, Chinese patent CN102516157B reports a hindered phenol / hindered amine molecular composite antioxidant, which first uses 3,5-dialkyl-4-hydroxybenzoic acid and dichlorothionyl to undergo substitution reaction to prepare an antioxidant intermediate, then the antioxidant intermediate undergoes amidation reaction with N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine, then an acid-binding agent is added, the reaction continues, and after the reaction is completed, the hindered phenol / hindered amine intramolecular composite antioxidant is obtained. It is then added to polyamide resin, and it is found in long-term aging tests that the new antioxidant can significantly delay the degradation of polyamide resin.

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

[0006] Wang Jian et al. used 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (MPC), diethyl phosphite and octadecanol as raw materials to synthesize an intramolecular composite antioxidant [3-(3,5-di-tert-butyl-4-hydroxy)phenyl] propionyl phosphate distearyl ester by ester exchange reaction. The results showed that the melting point of the obtained product was 47.7-49.2℃, and the yield was over 75%. The product was applied to polypropylene (PP) and the test system had an oxidation induction period of 41.351min, which was 1.3 times that of antioxidant 1076. The melt flow rate was 1.932g / 10min, which improved the fluidity 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. used 2,6-di-tert-butylphenol as raw material to synthesize a new type of intramolecular composite primary antioxidant 2,6-di-tert-butyl-p-aminophenol through nitration and reduction reaction. The yield of the product is above 80%, and the melting range is 112.2-113.3℃. The new antioxidant can effectively inhibit the oxidative degradation of polyethylene during its processing and use. (Li Cuiqin, Wang Jun, Zhang Zhiqiu, et al. Synthesis and performance of new intramolecular composite primary antioxidant. Chemical Progress, 2010(11)).

[0008] The antioxidant structures reported above contain hindered phenol, arylamine or phosphite active units, but there is no report on the synthesis and application of thiamine intramolecular composite antioxidants. At the same time, more and more studies have shown that high molecular weight antioxidants have the advantages of low volatility, extraction resistance, high temperature resistance, etc., which can reduce their loss in high temperature processing and application of polymers. Therefore, the research of high molecular weight antioxidants with superior performance has become a trend in the field of antioxidant research. Summary of the invention

[0009] The object of the present invention is to provide a method for preparing a thiamine compound.

[0010] To achieve the above object, the present invention provides a method for preparing a thiamine compound represented by formula (I), wherein the method comprises: 15 X is a raw material for preparing a thiamine compound represented by formula (I),

[0011]

[0012] R6 is an alkylene 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;

[0014] R 15 Selected from C6-C 20 Aryl or C1-C 10 A branched or straight chain alkyl group;

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

[0016] According to some specific embodiments of the present invention, the compound of formula (III) and R 15 Formula X undergoes a substitution reaction in the presence of a catalyst to prepare a thiamine compound represented by formula (I), wherein the catalyst is bistriphenylphosphine palladium dichloride 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, 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 a thiamine compound represented by formula (I), wherein the promoter is N,N-diisopropylethylamine.

[0020] According to some specific embodiments of the present invention, the molar amount of the promoter 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 promoter 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 the compound of formula (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 the compound of formula (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 represented by formula (I) using X as a raw material, the reaction temperature is 50-100°C.

[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 represented by formula (I) using X as a raw material, the reaction temperature is 70-80°C.

[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 represented by formula (I) using X as a raw material, the reaction time is 2-6 hours.

[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 represented by formula (I) using X as a raw material, the reaction time is 4-5 hours.

[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 represented by formula (I) wherein X is a raw material comprises: 15 The X solution is dropped into the reaction system to react.

[0029] According to some specific embodiments of the present invention, wherein R 15 The dripping rate of X solution 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 represented by formula (I), 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 a thiamine compound represented by formula (I), wherein the molar amount of the promoter is 0.01-0.07 times the molar amount of the compound represented by formula (III), the molar amount of the catalyst is 0.05-0.12 times the molar amount of the compound represented by formula (III), and R 15 The molar amount of X is 5-10 times the molar amount of the compound of formula (III), and the reaction time is 2-6 hours.

[0031] According to some specific embodiments of the present invention, the method further comprises preparing a compound represented by formula (III) using compounds represented by formula (IV) and formula (V) as raw materials:

[0032]

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

[0034] According to some specific embodiments of the present invention, the compound of formula (IV) and the compound of formula (V) are prepared under an inert gas atmosphere to obtain the compound of formula (III).

[0035] According to some specific embodiments of the present invention, the compound of formula (IV) and the compound of formula (V) are prepared in a non-polar solvent in the presence of a basic catalyst to obtain the compound of formula (III).

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

[0037] According to some specific embodiments of the present invention, the molar amount of the compound of formula (V) is 5-7 times the molar amount of the compound of formula (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 mass amount of the non-polar solvent is 5-9 times the total mass of the compound of formula (V) and the compound of formula (IV).

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

[0042] According to some specific embodiments of the present invention, in the step of preparing the compound represented by formula (III) using the compound represented by formula (IV) and the compound represented by formula (V) as raw materials, the reaction temperature is 80-140°C.

[0043] According to some specific embodiments of the present invention, in the step of preparing the compound represented by formula (III) using the compound represented by formula (IV) and the compound represented by formula (V) as raw materials, the reaction temperature is 90-100°C.

[0044] According to some specific embodiments of the present invention, in the step of preparing the compound represented by formula (III) using the compound represented by formula (IV) and the compound represented by formula (V) as raw materials, the reaction time is 4-12 hours.

[0045] According to some specific embodiments of the present invention, in the step of preparing the compound represented by formula (III) using the compound represented by formula (IV) and the compound represented by formula (V) as raw materials, the reaction time is 6-8 hours.

[0046] According to some specific embodiments of the present invention, the compound of formula (IV) and the compound of formula (V) are prepared in a non-polar solvent in the presence of an alkaline catalyst to obtain a compound of formula (III), the molar amount of the alkaline catalyst is 0.02-0.4 times the molar amount of the compound of formula (IV), the molar amount of the compound of formula (V) is 5-10 times the molar amount of the compound of formula (IV), and the reaction time is 4-12 hours.

[0047] According to some specific embodiments of the present invention, the method further comprises preparing a compound represented by formula (IV) using a compound represented by formula (VI) and a compound represented by formula (VII) as raw materials:

[0048]

[0049] R 16 It is a bond or an alkylene group having 2 carbon atoms less than R6.

[0050] According to some specific embodiments of the present invention, the compound of formula (VI) and the compound of formula (VII) undergo Michael addition reaction to obtain the compound of formula (IV).

[0051] According to some specific embodiments of the present invention, the compound of formula (VI) and the compound of formula (VII) are reacted under an inert gas atmosphere to obtain the compound represented by formula (IV).

[0052] According to some specific embodiments of the present invention, the compound of formula (VI) and the compound of formula (VII) are reacted in the presence of a catalyst to obtain a compound of formula (IV), and the catalyst is a diazabicycle or hexahydropyridine.

[0053] According to some specific embodiments of the present invention, the molar amount of the catalyst used in the step of preparing the compound represented by formula (IV) from the compound represented by formula (VI) and the compound represented by formula (VII) is 0.05-0.2 times the molar amount of the compound represented by formula (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 represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is 0.1-0.15 times the molar amount of the compound represented by formula (VI).

[0055] According to some specific embodiments of the present invention, the compound of formula (VI) and the compound of formula (VII) are reacted in a non-polar solvent in the presence of a catalyst to obtain the compound represented by formula (IV).

[0056] According to some specific embodiments of the present invention, the mass amount of the non-polar solvent used in the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is 7-12 times the total mass of the compound represented by formula (VI) and the compound represented by formula (VII).

[0057] According to some specific embodiments of the present invention, the non-polar solvent used in the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is a mixture of one or more of benzene, toluene and ethylbenzene.

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

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

[0060] According to some specific embodiments of the present invention, the reaction temperature of the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is room temperature to 50°C.

[0061] According to some specific embodiments of the present invention, the reaction temperature of the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is room temperature to 30°C.

[0062] According to some specific embodiments of the present invention, the reaction time of the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is 6-14 hours.

[0063] According to some specific embodiments of the present invention, the reaction time of the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is 6-8 hours.

[0064] According to some specific embodiments of the present invention, the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials comprises dropping the compound represented by formula (VII) into the reaction system and then reacting.

[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, the compound of formula (VI) and the compound of formula (VII) are reacted in a non-polar solvent in the presence of a catalyst to obtain a compound of formula (IV), the molar amount of the catalyst is 0.05-0.2 times the molar amount of the compound of formula (VI), and the reaction time is 6-14h.

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

[0068] R1 is C2-C 14 of 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;

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

[0072] According to some specific embodiments of the present invention, 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, 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, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 For hydrogen.

[0077] According to some specific embodiments of the present invention, wherein R 15 Selected from C6-C 14 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 or a C1-C6 branched or straight chain alkyl group.

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

[0080] R1 is C2-C 14 of alkylene;

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

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

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

[0084]

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

[0086] R1 is C2-C 14 of alkylene;

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

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

[0089] According to some specific embodiments of the present invention, wherein R 15 is 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 preparation method of the compound of formula (I) is as follows:

[0096]

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

[0098] (1) The reaction conditions and process 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 easily available, which effectively reduces the raw material and production costs, and is easy to realize industrial production;

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

[0100] (3) The thiamine composite antioxidant provided by the present invention has a relatively high molecular weight, which improves the antioxidant's anti-migration ability in polymer materials. At the same time, the antioxidant structure contains multiple aromatic ring structures, which effectively improves its thermal stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0101] Figure 1 This is the H 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 This is the H-NMR spectrum of the thiamine composite antioxidant prepared in Example 11;

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

[0105] Figure 5 This is the H-NMR spectrum of the thiamine composite antioxidant prepared in Example 12;

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

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

[0108] Figure 8 This is the mass spectrum of the thiamine complex antioxidant prepared in Example 13. DETAILED DESCRIPTION

[0109] The implementation process of the present invention and the beneficial effects produced are described in detail below through specific embodiments, which is intended to help readers better understand the essence and characteristics of the present invention, and is not intended to limit the scope of implementation of the present invention.

[0110] Example 1

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

[0112] The preparation route is as follows:

[0113]

[0114] a. Synthesis of antioxidant intermediate (I): Accurately weigh 100 mL of 0.1 mol / L 4-mercaptostyrene methanol solution, add 0.0003 mol of the catalyst hexahydropyridine under nitrogen protection, slowly add 30 mL of 0.1 mol / L 1,14-tetradecanediamine methanol solution dropwise while stirring at room temperature, and react for 8 hours under constant room temperature conditions. Remove methanol by reduced pressure distillation, then wash three times with ethyl acetate: ether = 1:10, and vacuum dry at 30°C for 24 hours to obtain antioxidant intermediate (I), with a yield of 91.2%.

[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 catalyst pyridine, slowly add 200 mL of 0.1 mol / L p-phenylenediamine toluene solution at 60°C, heat to 100°C and react for 8 hours after the addition is complete, remove toluene by distillation under reduced pressure to obtain a crude product, and purify the crude product by silica gel column chromatography. The volume ratio of petroleum ether:ethyl acetate used as the eluent is 10:1 to obtain antioxidant intermediate (II) with a yield of 84.8%.

[0116] c. Synthesis of thiamine composite antioxidant (A1): Accurately weigh 100 mL of 0.1 mol / L toluene solution of antioxidant intermediate (II), add 0.001 mol of catalyst bistriphenylphosphine palladium dichloride and 0.0005 mol of promoter N,N-diisopropylethylamine under nitrogen protection, slowly add 120 mL of 0.5 mol / L toluene solution of 2-iodonaphthalene at 0°C while stirring, heat to 80°C and react for 5 hours, concentrate the reaction mixture under vacuum, dissolve the crude product in a mixed solvent of ethyl acetate and tetrahydrofuran, wash with the solution, and chromatograph the resulting organic phase to obtain thiamine composite antioxidant (A1) with a yield of 83.4%.

[0117] The thiamine composite antioxidant (thiamine compound, A1) synthesized in this example was analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry. The results are as follows: Figure 1 ,and Figure 2 As shown. Figure 1 It can be seen that the characterization data of thiamine antioxidant is: 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 thiamine complex antioxidant.

[0118] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% (based on the total mass of the poly 4-methyl-1-pentene as 100%, the same below) of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0119] Embodiment 2:

[0120] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheology body (model FX5920A) were put into a high-speed mixer according to a mass ratio of 1:0.15:0.15:0.05, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to 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 composite additive is added, and the extruder is used to melt extrude, draw and granulate, the extrusion temperature is 260°C, and the extrusion rate is 10r / min. Then the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0122] Embodiment 3:

[0123] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheological body were put into a high-speed mixer in a mass ratio of 1:0.25:0.25:0.1, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to a powder extruder for extrusion to obtain a composite additive package.

[0124] In the granulation section of poly 4-methyl-1-pentene, 0.26% of the above composite additive is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0125] Embodiment 4:

[0126] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheological body were put into a high-speed mixer in a mass ratio of 1:0.35:0.35:0.15, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to 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 composite additive is added, and the extruder is used to melt extrude, draw and granulate, the extrusion temperature is 260°C, and the extrusion rate is 10r / min. Then the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0128] Embodiment 5:

[0129] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A2) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 1,14-tetradecanediamine in step a is replaced by 1,12-dodecanediamine, and the yield of step a is 93.4%.

[0130]

[0131] Thiamine Complex Antioxidant A2

[0132] The characterization data of the obtained thiamine antioxidant (A2) are: 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 above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0134] Embodiment 6:

[0135] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A3) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 1,14-tetradecanediamine in step a is replaced by 1,10-decanediamine, and the yield of step a is 95.7%.

[0136]

[0137] Thiamine complex antioxidant A3

[0138] The characterization data of the obtained thiamine antioxidant (A3) are: 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 above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0140] Embodiment 7:

[0141] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A4) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 1,14-tetradecanediamine in step a is replaced by 1,8-octanediamine, and the yield of step a is 96.1%.

[0142]

[0143] Thiamine complex antioxidant A4

[0144] The characterization data of the obtained thiamine antioxidant (A4) are: 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 above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0146] Embodiment 8:

[0147] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A5) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 1,14-tetradecanediamine in step a is replaced by 1,6-hexanediamine, and the yield of step a is 96.9%.

[0148]

[0149] Thiamine complex antioxidant A5

[0150] The characterization data of the obtained thiamine antioxidant (A5) are: 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 above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0152] Embodiment 9:

[0153] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A6) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 1,14-tetradecanediamine in step a is replaced by 1,4-butanediamine, and the yield of step a is 98.4%.

[0154]

[0155] Thiamine complex antioxidant A6

[0156] The characterization data of the obtained thiamine antioxidant (A6) are: 1H NMR (CD3Cl, 400 MHz): 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 above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0158] Embodiment 10:

[0159] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A7) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 1,14-tetradecanediamine in step a is replaced by ethylenediamine, and the yield of step a is 98.6%.

[0160]

[0161] Thiamine complex antioxidant A7

[0162] The characterization data of the obtained thiamine antioxidant (A7) are: 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 above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0164] Embodiment 11:

[0165] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A8) of this example are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 2-iodonaphthalene in step c is replaced by iodobenzene, and the yield of step c is 84.1%.

[0166]

[0167] Thiamine complex antioxidant A8

[0168] The thiamine composite antioxidant (A8) synthesized in this example was analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry. The results are as follows: Figure 3 ,and Figure 4 As shown. Figure 3 It can be seen that the characterization data of thiamine antioxidant (A8) are: 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 thiamine complex antioxidant (A8).

[0169] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0170] Embodiment 12:

[0171] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A9) of this example are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 2-iodonaphthalene in step c is replaced by 2-iodopropane, and the yield of step c is 90.5%.

[0172] The thiamine composite antioxidant (A9) synthesized in this example was analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry. The results are as follows: Figure 5 ,and Figure 6 As shown. Figure 5 It can be seen that the characterization data of thiamine antioxidant (A9) are: 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 thiamine complex antioxidant (A9).

[0173] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0174]

[0175] Thiamine complex antioxidant A9

[0176] Embodiment 13:

[0177] The preparation steps of the antioxidant intermediate and the thiamine composite antioxidant (A10) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 1, except that 2-iodonaphthalene in step c is replaced by 2-methyl-2-iodopropane, and the yield of step c is 92.7%.

[0178] The thiamine composite antioxidant (A10) synthesized in this example was analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry. The results are as follows: Figure 7 ,and Figure 8 As shown. Figure 7 It can be seen that the characterization data of thiamine antioxidant (A10) are: 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 thiamine complex antioxidant (A10).

[0179]

[0180] Thiamine complex antioxidant A10

[0181] In the granulation section of the poly 4-methyl-1-pentene material, 0.1% of the above-mentioned thiamine composite antioxidant is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene material resin are tested. The physical property test results of the poly 4-methyl-1-pentene material are shown in Table 1.

[0182] Embodiment 14:

[0183] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheology body (model FX5920A) were put into a high-speed mixer according to a mass ratio of 1:0.15:0.15:0.05, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to 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 composite additive is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 250° C. and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0185] Embodiment 15:

[0186] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheology body (model FX5920A) were put into a high-speed mixer according to a mass ratio of 1:0.15:0.15:0.05, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to 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 composite additive is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 270°C and an extrusion rate of 10 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0188] Embodiment 16:

[0189] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheology body (model FX5920A) were put into a high-speed mixer according to a mass ratio of 1:0.15:0.15:0.05, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to 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 composite additive is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 5 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0191] Embodiment 17:

[0192] The thiamine composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate, zinc stearate and fluorine rheology body (model FX5920A) were put into a high-speed mixer according to a mass ratio of 1:0.15:0.15:0.05, stirred at room temperature, mixed for 5 to 20 minutes, and then sent to 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 composite additive is added, and the extruder is melt-extruded, drawn and granulated, with an extrusion temperature of 260° C. and an extrusion rate of 15 r / min. Then, the mechanical properties and oxidation induction period of the poly 4-methyl-1-pentene resin are tested. The physical property test results of the poly 4-methyl-1-pentene resin are shown in Table 1.

[0194] Embodiment 18:

[0195] The preparation steps of the antioxidant intermediate and thiamine composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant recorded in Example 1, except that the amount of the methanol solution of 1,14-tetradecanediamine added in step a is 25 ml, and the yield of step a is 87.6%; the amount of the toluene solution of p-phenylenediamine added in step b is 150 ml, and the yield of step b is 79.9%; the amount of the toluene solution of 2-iodonaphthalene added in step c is 100 ml, and the yield of step c is 76.1%. The hydrogen spectrum and mass spectrum of the obtained product are respectively the same as those of Figure 1 and Figure 2 same.

[0196] Embodiment 19:

[0197] The preparation steps of the antioxidant intermediate and thiamine composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant recorded in Example 1, except that the amount of the methanol solution of 1,14-tetradecanediamine added in step a is 40 ml, and the yield of step a is 91.6%; the amount of the toluene solution of p-phenylenediamine added in step b is 300 ml, and the yield of step b is 85.0%; the amount of the toluene solution of 2-iodonaphthalene added in step c is 170 ml, and the yield of step c is 83.6%. The hydrogen spectrum and mass spectrum of the obtained product are respectively the same as those of Figure 1 and Figure 2 same.

[0198] Embodiment 20:

[0199] The preparation steps of the antioxidant intermediate and thiamine composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant recorded in Example 1, except that the amount of the catalyst hexahydropyridine added in step a is 0.00015 mol, and the yield of step a is 67.4%; the amount of the catalyst pyridine added in step b is 0.00006 mol, and the yield of step b is 71.8%; the amount of the toluene solution of 2-iodonaphthalene added in step c is 200 ml, and the yield of step c is 83.7%. The hydrogen spectrum and mass spectrum of the obtained product are respectively the same as those of Figure 1 and Figure 2 same.

[0200] Embodiment 21:

[0201] The preparation steps of the antioxidant intermediate and thiamine composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant recorded in Example 1, except that the amount of the catalyst hexahydropyridine added in step a is 0.0006 mol, and the yield of step a is 91.5%; the amount of the catalyst pyridine added in step b is 0.0006 mol, and the yield of step b is 85.1%; the amount of the catalyst bistriphenylphosphine palladium dichloride added in step c is 0.0005 mol, and the yield of step c is 74.5%. The hydrogen spectrum and mass spectrum of the obtained product are respectively the same as those of Figure 1 and Figure 2 same.

[0202] Embodiment 22:

[0203] The preparation steps of the antioxidant intermediate and thiamine composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant recorded in Example 1, except that the catalyst in step a is diazabicyclic, and the yield of step a is 52.8%; the amount of pyridine added as catalyst in step b is 0.0012 mol, and the yield of step b is 85.4%; the amount of bistriphenylphosphine palladium dichloride added as catalyst in step c is 0.0007 mol, and the yield of step c is 83.7%. The hydrogen spectrum and mass spectrum of the obtained product are respectively Figure 1 and Figure 2 same.

[0204] Embodiment 23:

[0205] The preparation steps of the antioxidant intermediate and thiamine composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant recorded in Example 1, except that the reaction temperature of step a is 40°C, and the yield of step a is 89.4%; the reaction temperature of step b is 80°C, and the yield of step b is 71.3%; the amount of the catalyst bistriphenylphosphine palladium dichloride added in step c is 0.0012 mol, and the yield of step c is 83.8%. The hydrogen spectrum and mass spectrum of the obtained product are respectively Figure 1 and Figure 2 same.

[0206] Embodiment 24:

[0207] The preparation steps of the antioxidant intermediate and thiamine composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant recorded in Example 1, except that the reaction temperature of step a is 50°C, and the yield of step a is 47.2%; the reaction temperature of step b is 140°C, and the yield of step b is 79.9%; the amount of the accelerator N,N-diisopropylethylamine added in step c is 0.0001 mol, and the yield of step c is 64.8%. The hydrogen spectrum and mass spectrum of the obtained product are respectively Figure 1 and Figure 2 same.

[0208] Embodiment 25:

[0209] The preparation steps of the antioxidant intermediate and thiamine composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant recorded in Example 1, except that the reaction time of step a is 6 hours, and the yield of step a is 79.4%; the reaction time of step b is 4 hours, and the yield of step b is 67.2%; the amount of the accelerator N,N-diisopropylethylamine added in step c is 0.0003 mol, and the yield of step c is 77.5%. The hydrogen spectrum and mass spectrum of the obtained product are respectively Figure 1 and Figure 2 same.

[0210] Embodiment 26:

[0211] The preparation steps of the antioxidant intermediate and thiamine composite antioxidant (A1) of this embodiment are basically the same as the preparation steps of the thiamine composite antioxidant recorded in Example 1, except that the reaction time of step a is 11 hours, and the yield of step a is 91.3%; the reaction time of step b is 12 hours, and the yield of step b is 85.3%; the amount of the accelerator N,N-diisopropylethylamine added in step c is 0.0007 mol, and the yield of step c is 83.3%. The hydrogen spectrum and mass spectrum of the obtained product are respectively Figure 1 and Figure 2 same.

[0212] Embodiment 27:

[0213] The preparation steps of the antioxidant intermediate and thiamine composite antioxidant (A1) in this example are basically the same as those of the thiamine composite antioxidant in Example 1, except that the reaction time of step a is 14 h, 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 hydrogen spectrum and mass spectrum of the obtained product are respectively Figure 1 and Figure 2 same.

[0214] Embodiment 28:

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

[0216] Embodiment 29:

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

[0218] Embodiment 30:

[0219] The preparation steps of the antioxidant intermediate and thiamine composite antioxidant (A8) in this example are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 11, except that the reaction time of step c is 2 hours and the yield of step c is 72.6%. The hydrogen spectrum and mass spectrum of the obtained product are respectively Figure 3 and Figure 4 same.

[0220] Embodiment 31:

[0221] The preparation steps of the antioxidant intermediate and thiamine composite antioxidant (A10) in this example are basically the same as the preparation steps of the thiamine composite antioxidant described in Example 13, except that the reaction time of step c is 6 hours and the yield of step c is 92.9%. The hydrogen spectrum and mass spectrum of the obtained product are respectively Figure 7 and Figure 8 same.

[0222] Comparative Example 1:

[0223] In the poly-4-methyl-1-pentene granulation section, 0.1% (based on the total mass of poly-4-methyl-1-pentene as 100%, the same below) of antioxidant DNP is added thereto to replace the composite antioxidant of the present invention, and according to the extrusion granulation process of Example 1, wire drawing and granulation are performed by a twin-screw extruder, the extrusion temperature is 260° C., and the extrusion rate is 10 r / min. Then the oxidation induction period and mechanical properties of poly-4-methyl-1-pentene are tested. The test results of the poly-4-methyl-1-pentene are shown in Table 1.

[0224]

[0225] Antioxidant DNP

[0226] Comparative Example 2:

[0227] In the poly-4-methyl-1-pentene granulation section, 0.1% antioxidant D is added thereto to replace the composite antioxidant of the present invention, and according to the extrusion granulation process of Example 1, the twin-screw extruder is used for extrusion drawing and granulation, the extrusion temperature is 260°C, and the extrusion rate is 10r / min. Then, the oxidation induction period and mechanical properties of the poly-4-methyl-1-pentene are tested. The test results of the poly-4-methyl-1-pentene are shown in Table 1.

[0228]

[0229] Antioxidant D

[0230] Comparative Example 3:

[0231] In the poly-4-methyl-1-pentene granulation section, 0.1% of didodecanol thiodipropionate was added thereto to replace the composite antioxidant of the present invention, and the extrusion granulation process of Example 1 was followed by extrusion, drawing and granulation by a twin-screw extruder, with an extrusion temperature of 260° C. and an extrusion rate of 10 r / min. Then, the oxidation induction period and mechanical properties of the poly-4-methyl-1-pentene were tested. The test results of the poly-4-methyl-1-pentene are shown in Table 1.

[0232] Test Case

[0233] OIT analysis was carried out in accordance with GB / T 2951.1-1994 in a nitrogen atmosphere, with the temperature rising to 200°C at 20°C / min, held constant for 5 min, and then the nitrogen was replaced by oxygen and dropped to 25°C at -20°C / min.

[0234] Mechanical properties test was carried out in accordance with GB / T 1040-2006. Poly-4-methyl-1-pentene pellets were made into 5A dumbbell-shaped specimens by compression molding and placed at a temperature of (23±2)°C and a relative humidity of (50±5)% for 24 hours. The tensile rate was 50 mm / min.

[0235] The above OIT analysis results and mechanical properties test results are shown in Table 1:

[0236] Table 1 Analysis and test results of poly 4-methyl-1-pentene

[0237]

[0238]

[0239] It can be seen from the data in Table 1 that the thiamine composite antioxidants A1-A10 prepared by the present invention can effectively improve the mechanical properties and oxidation induction period of poly-4-methyl-1-pentene materials, and antioxidants A1 and A10 have the best antioxidant effects. At the same time, the antioxidant effect of the synthesized thiamine composite antioxidant is significantly better than that of commercial amine and thioether antioxidants when compared with commercial antioxidants.

[0240] The present invention provides a thiamine composite antioxidant, which contains both the naphthylamine group of the main antioxidant and the thioether group of the auxiliary antioxidant, and can realize the synergistic effect of the main and auxiliary antioxidants in the molecule, that is, the free radical chain reaction can be quickly terminated, and the hydroperoxide produced by the chain reaction can be decomposed, and there is a very excellent antioxidant effect. At the same time, the thiamine composite antioxidant has a large molecular weight, is not easy to precipitate during processing and use, has good extraction resistance, has multiple rigid benzene ring structures in the molecular structure, and a linking group that is not easy to hydrolyze, is not easy to hydrolyze and thermally decompose into small molecules during processing and use, and the stability of the antioxidant is better. It is applied to high-end resins such as polybutene-1 and poly-4-methyl-1-pentene, and the antioxidant properties of the material can be effectively improved, which has important guiding significance for the development and use of high-end resin additives.

Claims

1. A method for preparing a thiamine compound represented by formula (I), wherein: The method comprises the steps of: 15 X is a raw material for preparing a thiamine compound represented by formula (I), R6 is an 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; R 15 Selected from C6-C 20 Aryl or C1-C 10 A branched or straight chain alkyl group; X is selected from F, Cl, Br or I.

2. The preparation method according to claim 1, wherein The compound of formula (III) and R 15 Formula X undergoes a substitution reaction in the presence of a catalyst to prepare a thiamine compound represented by formula (I), wherein the catalyst is bistriphenylphosphine palladium dichloride and / or palladium acetate.

3. The preparation method according to claim 2, 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 a thiamine compound represented by formula (I), wherein the promoter is N,N-diisopropylethylamine.

4. The preparation method according to any one of claims 1 to 3, wherein The compound of formula (III) and R 15 In the step of preparing the thiamine compound represented by formula (I) using X as a raw material, the reaction temperature is 50-100°C.

5. The preparation method according to any one of claims 1 to 4, wherein The compound of formula (III) and R 15 In the step of preparing the thiamine compound represented by formula (I), 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 a thiamine compound represented by formula (I), wherein the molar amount of the promoter is 0.01-0.07 times the molar amount of the compound represented by formula (III), the molar amount of the catalyst is 0.05-0.12 times the molar amount of the compound represented by formula (III), and R 15 The molar amount of X is 5-10 times the molar amount of the compound of formula (III), and the reaction time is 2-6 hours.

6. The preparation method according to any one of claims 1 to 5, wherein: The method also includes preparing a compound represented by formula (III) using compounds represented by formula (IV) and formula (V) as raw materials:

7. The preparation method according to claim 6, wherein: The compound of formula (IV) and the compound of formula (V) are prepared in the presence of a basic catalyst to obtain the compound of formula (III), wherein the basic catalyst is pyridine.

8. The preparation method according to claim 5 or 6, wherein: In the step of preparing the compound represented by formula (III) using the compound represented by formula (IV) and the compound represented by formula (V) as raw materials, the reaction temperature is 80-140°C.

9. The preparation method according to any one of claims 6 to 8, wherein: The compound of formula (IV) and the compound of formula (V) are prepared in a non-polar solvent in the presence of an alkaline catalyst to obtain a compound of formula (III), the molar amount of the alkaline catalyst is 0.02-0.4 times the molar amount of the compound of formula (IV), the molar amount of the compound of formula (V) is 5-10 times the molar amount of the compound of formula (IV), and the reaction time is 4-12 hours.

10. The preparation method according to any one of claims 6 to 9, wherein: The method also includes preparing a compound represented by formula (IV) using a compound represented by formula (VI) and a compound represented by formula (VII) as raw materials: R 16 It is a bond or an alkylene group having 2 carbon atoms less than R6.

11. The preparation method according to claim 10, wherein: The compound of formula (VI) and the compound of formula (VII) are reacted in the presence of a catalyst to obtain the compound of formula (IV), wherein the catalyst is diazabicycle or hexahydropyridine.

12. The preparation method according to claim 10 or 11, wherein: In the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials, the molar amount of the compound represented by formula (VII) is 2-4 times the molar amount of the compound represented by formula (VI).

13. The preparation method according to any one of claims 10 to 12, wherein: The reaction temperature of the step of preparing the compound represented by formula (IV) using the compound represented by formula (VI) and the compound represented by formula (VII) as raw materials is room temperature to 50°C.

14. The preparation method according to any one of claims 10 to 13, wherein: The compound of formula (VI) and the compound of formula (VII) are reacted in a non-polar solvent in the presence of a catalyst to obtain a compound of formula (IV), the molar amount of the catalyst is 0.05-0.2 times the molar amount of the compound of formula (VI), and the reaction time is 6-14 hours.

15. The preparation method according to any one of claims 1 to 14, wherein: R1 is C2-C 14 of alkylene; 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-C4 alkyl; preferably hydrogen; R 15 Selected from C6-C 14 or a C1-C6 branched or straight chain alkyl group.

16. The preparation method according to any one of claims 1 to 15, 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.

17. The preparation method according to any one of claims 1 to 16, wherein: The thiamine compound is selected from the following compounds:

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