Highly active hydroxylamine antioxidants and methods for their preparation

Abstract

The application belongs to the field of synthetic materials, and particularly relates to a high-activity hydroxylamine antioxidant and a preparation method thereof. The high-activity hydroxylamine antioxidant has simple production process, mild reaction condition, and fast reaction speed; compared with traditional single active center straight-chain hydroxylamine antioxidants, the high-activity hydroxylamine antioxidant has higher decomposition temperature, smaller addition amount, and longer antioxidation effect time.

Description

Technical Field

[0001] This invention belongs to the field of synthetic materials, specifically relating to a highly active hydroxylamine antioxidant and its preparation method. Background Technology

[0002] Hydroxylamine antioxidants, by avoiding the presence of phenolic substances, give products excellent resistance to yellowing caused by fumes and good color stability, making them more effective than traditional hindered phenolic antioxidants. The most representative hydroxylamine antioxidant on the market is BASF's Lrgastab FS042, a novel, high-temperature resistant, highly efficient, multifunctional, phenol-free antioxidant. Its CAS number is 143925-92-2, and its chemical formula is C2. 36 H 75 NO, with a molecular weight of 538. Currently, the use of hydroxylamine antioxidant bis(octadecyl)hydroxylamine mainly relies on imports, and there are few related research reports both domestically and internationally. Patent CN113651730A discloses a method for synthesizing bis(octadecyl)hydroxylamine using hydroxylamine hydrochloride, an acid-binding agent, and halooctadecane. However, in practical applications, there is a problem that triethylamine hydrochloride cannot be completely removed, resulting in low yield, low product purity, and poor antioxidant effect. Patent CN102952308B discloses a method for preparing bis(octadecyl)hydroxylamine using N,N-dialkylamine and hydrogen peroxide under heating. Due to the extreme instability of hydrogen peroxide under heating, there is a risk of explosion during large-scale preparation. The hydroxylamine antioxidant disclosed in this invention has a significantly different structure from bis(octadecyl)hydroxylamine, with a decomposition temperature exceeding 300 degrees Celsius, and superior antioxidant effect. Summary of the Invention

[0003] The main content of this invention is to provide a highly active hydroxylamine antioxidant and its preparation method, based on the shortcomings of the prior art, including a multi-active-center hydroxylamine antioxidant and a single-active-center cyclic hydroxylamine antioxidant.

[0004] The purpose of this invention is to provide a highly active hydroxylamine antioxidant and its preparation method, in order to improve the problem of high dosage of existing bis(octadecyl)hydroxylamine.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A highly active hydroxylamine antioxidant, comprising multi-active-center hydroxylamine antioxidants and single-active-center cyclic hydroxylamine antioxidants, wherein the multi-active-center hydroxylamine antioxidant has the following structure: Where X = Cl, Br, I, m = 0-30, n = 1-100;

[0007] The structure of a single-active-center cyclic hydroxylamine antioxidant is as follows: Where y = 4 - 30.

[0008] Furthermore, the preparation method of the highly active hydroxylamine antioxidant includes the following steps:

[0009] Weigh out hydroxylamine hydrochloride, alkali, haloalkanes and solvent in proportion, mix and react for a certain period of time, filter, wash with water and dry to obtain the highly active hydroxylamine antioxidant.

[0010] Furthermore, the base is one or more of sodium hydroxide, potassium hydroxide, pyridine, 1,8-diazobisspirocyclic [5.4.0]undecyl-7-ene, 4-dimethylaminopyridine, N,N-dimethylethylamine, N,N-diethylmethylamine, N,N-dimethylaniline, triethylamine, and triethylenediamine.

[0011] Furthermore, the amount of alkali used is 10%-300% of the total mass of hydroxylamine hydrochloride.

[0012] Furthermore, the haloalkane is Where X = one of Cl, Br, and I, and m = 0-30.

[0013] Alternatively, the haloalkane is Where X = one of Cl, Br, and I, a = 0-30, b = 1-6.

[0014] Furthermore, the solvent is one or more of benzene, toluene, xylene, trimethylbenzene, trifluorotoluene, diethyl ether, acetonitrile, dichloromethane, dichloroethane, chloroform, ethyl acetate, tetrahydrofuran, 1,4-dioxane, methyldioxane, 1,3-dioxane, and propylene oxide.

[0015] Furthermore, the reaction temperature is 10-300℃.

[0016] Furthermore, the reaction time is 1 second to 48 hours.

[0017] Application: The use of highly active antioxidants in improving the antioxidant effect of polyolefins.

[0018] The beneficial effects of this invention are:

[0019] This invention provides a multi-active-center hydroxylamine antioxidant and a single-active-center cyclic hydroxylamine antioxidant, as well as their preparation methods. The production process is simple, the reaction conditions are mild, and the reaction rate is fast. Compared with single-active-center chain hydroxylamine antioxidants, the amount added is less, the decomposition temperature is higher, and the antioxidant effect lasts longer. Attached Figure Description

[0020] Figure 1 The image shows the 1H NMR spectrum of antioxidant A obtained in Example 1.

[0021] Figure 2 The thermogravimetric spectrum of antioxidant A obtained in Example 1 is shown. Detailed Implementation

[0022] The technical solution of the present invention will be further described below through embodiments.

[0023] Unless otherwise stated, the terms used in this invention generally have the meanings commonly understood by those skilled in the art.

[0024] In the following embodiments, the various processes and methods not described in detail are conventional methods known in the art. Furthermore, due to the large variety of bases and the diverse structural proportions of haloalkanes, not all preparation methods are described in detail; instead, typical examples are used to illustrate the specific process steps of the present invention.

[0025] Example 1

[0026] In a 500 mL flask, 2.08 g of hydroxylamine hydrochloride, 25 mL of N,N-dimethylethylamine, and 90 mL of tetrahydrofuran were added. The mixture was premixed at 30 °C for 30 min, then the temperature was raised to 60 °C and 20 g of 1,18-dibromooctadecane was added dropwise. After the addition was complete, the temperature was raised to 85 °C and the reaction was maintained for 7 h. After the reaction was complete, the reaction solution was cooled and filtered. The filter cake was washed with water and dried to obtain 2.5 g of white powdered antioxidant A1, with a yield of 66%. The results were analyzed by HPLC and... 1 The structural formula of white powdery antioxidant A, determined by H NMR analysis, is: (5% of the weight) and (95% by mass), where n is 1-10.

[0027] Example 2

[0028] In a 500 mL flask, 2.08 g of hydroxylamine hydrochloride, 25 mL of N,N-dimethylethylamine, and 90 mL of dichloroethane were added. The mixture was premixed at 30 °C for 30 min, then the temperature was raised to 60 °C and 20 g of 1,18-dibromooctadecane was added dropwise. After the addition was complete, the temperature was raised to 85 °C and the reaction was maintained for 7 h. After the reaction was complete, the reaction solution was cooled and filtered. The filter cake was washed with water and dried to obtain 1.8 g of white powdered antioxidant A1, with a yield of 62%. The results were analyzed by HPLC and... 1 The structural formula of white powdery antioxidant A, determined by H NMR analysis, is: (5% of the weight) and (95% by mass), where n is 1-10.

[0029] Example 3

[0030] In a 500 mL flask, 2.08 g of hydroxylamine hydrochloride, 25 mL of N,N-dimethylethylamine, and 90 mL of toluene were added. The mixture was premixed at 30 °C for 30 min, then the temperature was raised to 60 °C and 20 g of 1,18-dibromooctadecane was added dropwise. After the addition was complete, the temperature was raised to 85 °C and the reaction was maintained for 7 h. After the reaction was complete, the reaction solution was cooled and filtered. The filter cake was washed with water and dried to obtain 3.1 g of white powdered antioxidant A1, with a yield of 69%. The results were analyzed by HPLC and... 1 The structural formula of white powdery antioxidant A, determined by H NMR analysis, is: (4% of quality) and (96% by quality), where n is 1-10.

[0031] Example 4

[0032] In a 500 mL flask, 2.08 g of hydroxylamine hydrochloride, 25 mL of pyridine, and 90 mL of trimethylbenzene were added. The mixture was premixed at 30 °C for 30 min, then the temperature was raised to 60 °C and 20 g of 1,18-dibromooctadecane was added dropwise. After the addition was complete, the temperature was raised to 100 °C and the reaction was maintained for 7 h. After the reaction was complete, the reaction solution was cooled and filtered. The filter cake was washed with water and dried to obtain 3.6 g of white powdered antioxidant A1, with a yield of 72%. The results were analyzed by HPLC and... 1 The structural formula of white powdery antioxidant A, determined by H NMR analysis, is: (3% of the weight) and (97% by quality), where n is 1-10.

[0033] Example 5

[0034] In a 500 mL flask, 2.08 g of hydroxylamine hydrochloride, 17 mL of DBU, and 90 mL of ethyl acetate were added. The mixture was premixed at 30 °C for 30 min, then the temperature was raised to 60 °C and 20 g of 1,18-dibromooctadecane was added dropwise. After the addition was complete, the temperature was raised to 85 °C and the reaction was maintained for 7 h. After the reaction was complete, the reaction solution was cooled and filtered. The filter cake was washed with water and dried to obtain 1.7 g of white powdered antioxidant A1, with a yield of 62%. The results were analyzed by HPLC and... 1 The structural formula of white powdery antioxidant A, determined by H NMR analysis, is: (5% of the weight) and (95% by mass), where n is 1-10.

[0035] Example 6

[0036] The reaction procedure and operation were the same as in Example 1, except that the solvent was acetonitrile. The reaction was stopped, and after post-treatment, 2.4 g of white powdered antioxidant A1 was obtained, with a yield of 65%. The results were analyzed by HPLC and... 1The structural formula of white powdery antioxidant A, determined by H NMR analysis, is: (5% of the weight) and (95% by mass), where n is 1-10.

[0037] Example 7

[0038] The reaction steps and operations were the same as in Example 1, except that the solvent was toluene and the reaction temperature was maintained at 100°C. The reaction was stopped, and after post-treatment, 0.9 g of white powdered antioxidant A1 was obtained, with a yield of 57%. HPLC analysis and... 1 The structural formula of white powdery antioxidant A, determined by H NMR analysis, is: (4% of quality) and (96% by quality), where n is 1-10.

[0039] Example 8

[0040] The reaction steps and operations were the same as in Example 1, except that 1,18-dibromooctadecane was replaced with 1,20-dibromoeicosane. After post-treatment, 0.9 g of a white powdery antioxidant B1 was obtained, with a yield of 57%. HPLC analysis and... 1 The structural formula of the white powdery antioxidant B, determined by H NMR analysis, is: (5% of the weight) and

[0041]

[0042] (95% by mass), where n is 1-10.

[0043] Example 9

[0044] The reaction steps and operations were the same as in Example 1, except that 1,18-dibromooctadecane was replaced with 1,12-dibromododecane. After post-treatment, 5.2 g of a white powdery antioxidant F was obtained, with a yield of 27%. HPLC analysis and... 1 The structural formula of the white powdery antioxidant F, determined by H NMR analysis, is: (37% of the quality) and (63% by mass), where n is 1-10.

[0045] Example 10

[0046] The reaction steps and operations were the same as in Example 12, except that the amount of 1,12-dibromododecane added was changed to 10 g. After post-treatment, 5.2 g of white powdered antioxidant F was obtained, with a yield of 57%. HPLC analysis and... 1 The structural formula of the white powdery antioxidant F, determined by H NMR analysis, is: (100% of the quality).

[0047] Application Example 1

[0048] The process of modifying HDPE with antioxidant A

[0049] HDPE (HS5820, Sinochem Quanzhou Petrochemical), antioxidant A from Example 1, auxiliary antioxidant 168, calcium stearate, zinc stearate, and PPA additive were mixed in a mass ratio of 10000:1:1:3:1:2. After the mixture was thoroughly mixed in a high-speed mixer, it was fed into a twin-screw extruder through the main feed port. The set temperatures of the extruder from the feed zone to the die head were 60℃, 90℃, 130℃, 180℃, 200℃, 220℃, 220℃, 210℃, 190℃, and 180℃, and the screw speed was 200 r / min. Modified HDPE granules were prepared by extrusion granulation.

[0050] Application Example 2

[0051] The process of modifying HDPE with antioxidant B

[0052] HDPE (HS5820, Sinochem Quanzhou Petrochemical), antioxidant B from Example 8, auxiliary antioxidant 168, calcium stearate, zinc stearate, and PPA additive were mixed in a mass ratio of 10000:1:1:3:1:2. After the mixture was thoroughly mixed in a high-speed mixer, it was fed into a twin-screw extruder through the main feed port. The set temperatures of the extruder from the feed zone to the die head were 60℃, 90℃, 130℃, 180℃, 200℃, 220℃, 220℃, 210℃, 190℃, and 180℃, and the screw speed was 200 r / min. Modified HDPE granules were prepared by extrusion granulation.

[0053] Application Comparative Example 1

[0054] The process of modifying HDPE with bis(octadecyl)hydroxylamine

[0055] HDPE (HS5820, Sinochem Quanzhou Petrochemical), bis(octadecyl)hydroxylamine, auxiliary antioxidant 168, calcium stearate, zinc stearate, and PPA additive were mixed in a mass ratio of 10000:1:1:3:1:2. After the mixture was homogenized by a high-speed mixer, it was fed into a twin-screw extruder through the main feed port. The set temperatures of the extruder from the feed zone to the die head were 60℃, 90℃, 130℃, 180℃, 200℃, 220℃, 220℃, 210℃, 190℃, and 180℃, and the screw speed was 200 r / min. Modified HDPE granules were prepared by extrusion granulation.

[0056] The modified HDPE prepared in Example 1-2 was repeatedly extruded using a twin-screw extruder. The change in the yellow index of the HDPE after multiple extrusions was measured to test the persistence of the antioxidant. The comparative data of bis(octadecyl)hydroxylamine with each application example are listed in the table below.

[0057] sample Decomposition temperature First time squeezing out the yellow index Fourth squeeze out yellow index bis(octadecyl)hydroxylamine 143℃ -1.54 2.03 Antioxidant A 348℃ -2.57 1.25 Antioxidant B 323℃ -2.96 1.07

[0058] Compared to bis(octadecyl)hydroxylamine, antioxidants A and B exhibit significantly increased decomposition temperatures, indicating a substantial improvement in their stability. Furthermore, the yellow index of polyolefin materials produced by antioxidants A and B remained low in both first and multiple extrusion processes, suggesting that these hydroxylamine antioxidants possess higher activity compared to traditional bis(octadecyl)hydroxylamine.

[0059] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. A highly active hydroxylamine antioxidant characterized in that, The high activity hydroxylamine antioxidant includes a multi-active center hydroxylamine antioxidant and a single-active center cyclic hydroxylamine antioxidant, wherein the multi-active center hydroxylamine antioxidant has a structure of wherein X = Cl, Br, I, m = 0-30, n = 1-100; The structure of the single-site cyclic hydroxylamine antioxidant is wherein y = 4-30.

2. The process for the preparation of high activity hydroxylamine antioxidant according to claim 1, characterized in that, The method comprises the following steps: The hydroxylamine hydrochloride, the base, the halogenated alkane and the solvent are weighed in proportion, mixed for a certain time, filtered, washed with water and dried to obtain the high-activity hydroxylamine antioxidant.

3. The production method according to claim 2, characterized by, The base is one or more of sodium hydroxide, potassium hydroxide, pyridine, 1,8-diazobis-spiro[5.4.0]undec-7-ene, 4-dimethylaminopyridine, N,N-dimethylethylamine, N,N-diethylmethylamine, N,N-dimethylaniline, triethylamine and triethylenediamine.

4. The preparation method according to claim 2, characterized in that, The amount of the base is 10%-300% of the total mass of the hydroxylamine hydrochloride.

5. The production method according to claim 2, characterized by, The halogenated alkane is where X = one of Cl, Br, I, and m = 0-30.

6. The preparation method according to claim 2, characterized in that, The solvent is one or more of benzene, toluene, xylene, trimethylbenzene, trifluorotoluene, diethyl ether, acetonitrile, dichloromethane, dichloroethane, trichloromethane, ethyl acetate, tetrahydrofuran, 1,4-dioxane, methyl dioxane, 1,3-dioxane and propylene oxide.

7. The production method according to claim 2, characterized by, The reaction temperature is 10-300 o C.

8. The production method according to claim 2, characterized by, The reaction time is 1 s-48 h.

9. Application of the high-activity hydroxylamine antioxidant of claim 1 to improving the antioxidant effect of polyolefins.

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