CN114736190A - Preparation method of high molecular weight hindered amine light stabilizer - Google Patents

Preparation method of high molecular weight hindered amine light stabilizer Download PDF

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CN114736190A
CN114736190A CN202210334676.9A CN202210334676A CN114736190A CN 114736190 A CN114736190 A CN 114736190A CN 202210334676 A CN202210334676 A CN 202210334676A CN 114736190 A CN114736190 A CN 114736190A
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catalyst
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hindered amine
light stabilizer
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韩炎
项瞻波
蔡裕伟
胡方洲
王�章
胡新利
李兆亮
项然
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Suqian Liansheng Auxiliaries Co ltd
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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Abstract

The preparation method of the high molecular weight hindered amine light stabilizer comprises the following steps: s1: introducing hydrogen, and carrying out hydrogenation reaction on the tert-octylamine and triacetonamine under the action of a catalyst I; s2: carrying out substitution reaction on the product obtained in the step S1 and cyanuric chloride under the action of a catalyst II; s3: carrying out methylation reaction on the product of the step S2 and formaldehyde under the action of a catalyst III; s4: carrying out substitution reaction on the product obtained in the step S3 and N, N' -bis (3-aminopropyl) -ethylene diamine under the action of a catalyst IV to obtain a high molecular weight hindered amine light stabilizer product; the raw material triacetonamine adopted by the invention is a basic raw material of the company, so that the resources are rich and the quality is excellent; the prepared high molecular weight hindered amine light stabilizer product has excellent antioxidant effect; the preparation method is simple, the atom utilization rate is high, and the method is green and environment-friendly.

Description

Preparation method of high molecular weight hindered amine light stabilizer
Technical Field
The invention belongs to the technical field of light stabilizers, and particularly relates to a preparation method of a high molecular weight hindered amine light stabilizer.
Background
Through the rapid development of recent decades, hindered amine light stabilizers have become the most widely used type in the field of light stabilizers, and have the largest market share. At present, how to better improve the light stability effect of hindered amine light stabilizers, better match the hindered amine light stabilizers with high polymer materials and better adapt the hindered amine light stabilizers to application environments is the development trend and development direction of the hindered amine light stabilizers.
Although the traditional hindered amine light stabilizer developed in the early stage has good light stabilizing effect, the molecular weight of the traditional hindered amine light stabilizer is generally small, the extraction resistance is poor, and particularly, for polymer materials with small thickness such as agricultural films, the traditional hindered amine light stabilizer is easy to escape from the polymer materials in the processing process, so that the actual addition amount of the traditional hindered amine light stabilizer is continuously reduced, and the light stabilizing effect is influenced.
It has been found that high molecular weight can improve the extraction resistance and migration resistance of the hindered amine light stabilizer, but if the molecular weight is too high, the development of light stability is hindered. Proper migration capability is necessary in the practical application of polymer materials, especially thicker products, and the light stabilizer which is consumed and dissipated is timely migrated to the surface of the material to be supplemented, so that the aging process from the outside to the inside can be effectively prevented, and the migration capability of the hindered amine light stabilizer is reduced due to the overhigh molecular weight, and the use effect of the hindered amine light stabilizer is influenced. At present, it is considered that the relative molecular mass of 2000-3000 is a suitable distribution range.
Because the traditional hindered amine light stabilizer is developed on the basis of the structure of triacetonamine, the N-H group in the structure of the traditional hindered amine light stabilizer enables the traditional hindered amine light stabilizer to have higher alkalinity, and the hindered amine light stabilizer with overhigh alkalinity easily causes the hindered amine light stabilizer to form salt when meeting acidic environment, acidic resin or acidic compound agent, influences the generation quantity and the generation rate of nitroxide radicals, damages the actual content of the nitroxide radicals and reduces the action effect. The light stabilizer can not be used in the acidic environment such as polyvinyl chloride or paint, and can not be used together with other acidic auxiliary agents in polymer materials, so that the application range of the traditional light stabilizer is limited, and the efficacy of the traditional light stabilizer cannot be maximized.
Therefore, on the basis of ensuring the light stability, the development of hindered amine light stabilizers with higher molecular weight is imperative, and the hindered amine light stabilizers have better adaptability, better environmental adaptability, higher efficiency and lower production cost.
Ciba corporation in Switzerland started the earliest in this regard, and in 1978 they introduced Tinuvin 622, a polymeric hindered amine Chimassbor944 and a monomeric hindered amine Chimassbor 119 with a molecular weight of about 2136 were developed. Meanwhile, other light stabilizer production companies also put forward polymeric products with high relative molecular mass, such as Cyasorb UV3346 and the like. These products all show excellent application properties.
Although the common polymeric hindered amine light stabilizer on the market has excellent performance, the steps in the synthesis process are complex, and the molecular weight is difficult to control. Therefore, the invention carries out comparative research on synthesis processes of several widely used hindered amine light stabilizers such as Chimassorb-944 and Chimassbor 119 in the market, and discloses a preparation method of a high molecular weight hindered amine light stabilizer by improving the synthesis processes, so that the synthesis process is more efficient, and the molecular weight control is easier. The molecular weight of the hindered amine light stabilizer disclosed by the invention is 2734.54, and the hindered amine light stabilizer has the advantages of appropriate molecular weight, simple and convenient synthesis process and the like.
Disclosure of Invention
In order to solve the problems, the invention discloses a preparation method of a high molecular weight hindered amine light stabilizer.
In order to achieve the purpose, the technical scheme of the invention is as follows:
it is an object of the present invention to provide a high molecular weight hindered amine light stabilizer having the structural formula shown in formula (I):
Figure BDA0003576288430000021
another object of the present invention is to provide a process for the preparation of a high molecular weight hindered amine light stabilizer comprising the steps of:
s1: introducing hydrogen, and carrying out hydrogenation reaction on the tert-octylamine and triacetonamine under the action of a catalyst I to generate 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine;
Figure BDA0003576288430000022
s2: carrying out substitution reaction on 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine and cyanuric chloride under the action of a catalyst II to obtain 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentane-2-yl) -1,3, 5-triazine-2, 4-diamine reaction solution;
Figure BDA0003576288430000031
s3: carrying out methylation reaction on organic reaction liquid containing 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine and formaldehyde under the action of a catalyst III to obtain 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine reaction solution;
Figure BDA0003576288430000032
s4: carrying out substitution reaction on an organic reaction solution containing 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine and N, N' -bis (3-aminopropyl) -ethylenediamine under the action of a catalyst IV to obtain a high molecular weight hindered amine light stabilizer product;
Figure BDA0003576288430000033
further, in step S1, the molar ratio of triacetonamine to tert-octylamine to catalyst I and hydrogen is 1: 0.5-1.5: 0.1-0.9: 0.1-1.5.
Further, in step S1, the catalyst I is one or more of framework copper, framework nickel, and framework cobalt, the temperature of the hydrogenation reaction is 85 to 120 ℃, and the time of the hydrogenation reaction is 8 to 30 hours.
Further, in step S2, the molar ratio of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentan-2-yl) piperidin-4-amine to cyanuric chloride to catalyst ii is 1: 0.5-1.2: 1-8, wherein the mass ratio of the 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine to the solvent is 1: 1-5; the dropping flow rate of the 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine is 5-50 g/min.
Further, in step S2, the catalyst II is 32 wt% of liquid caustic soda, and the dropping flow rate of the liquid caustic soda is 5-50 g/min; the solvent for the substitution reaction is one or more of dimethylbenzene and methylbenzene; the temperature of the substitution reaction is 80-110 ℃, and the time of the substitution reaction is 24-60 h.
In the step S2, after the substitution reaction is completed, water is divided and washed, wherein the washing amount is 0.5-1.6 times of the weight of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine, the washing temperature is 60-90 ℃, and the washing time is 0.1-5 h.
Further, in step S3, the mass ratio of the 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine reaction solution to formaldehyde to the catalyst iii is 1: 0.01-1.1: 0.02-0.09.
Further, in step S3, the catalyst iii is one or more of formic acid, dimethyl sulfate, methyl iodide, and methyl bromide, the dropping flow rate of the catalyst iii is 5-20g/min, the temperature of the methylation reaction is 65-120 ℃, and the time of the methylation reaction is 12-26 h.
In the step S3, after the methylation reaction is completed, water is divided and washed, wherein the amount of the washed water is 0.1-2 times of the weight of the reaction solution of 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine, the washing temperature is 60-85 ℃, and the washing time is 0.1-5 h.
Further, in step S4, the mass ratio of the reaction solution containing 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine to N, N' -bis (3-aminopropyl) -ethylenediamine to catalyst iv is 1: 0.01-1.2: 0.02-0.8.
Further, in step S4, the catalyst IV is 32 wt% liquid caustic soda, the temperature of the substitution reaction is 155-255 ℃, and the time of the substitution reaction is 8-30 h.
In the step S4, after the substitution reaction is completed, water is divided and washed, wherein the amount of the water washing is 0.2 to 3 times of the weight of the reaction solution containing 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine, the washing temperature is 65 to 85 ℃, and the washing time is 1 to 10 hours.
The invention has the beneficial effects that:
1. the raw material triacetonamine adopted by the invention is a basic raw material of the company, so that the resources are rich and the quality is excellent;
2. the high molecular weight hindered amine light stabilizer prepared by the invention has excellent antioxidant effect;
3. the preparation method is simple, the atom utilization rate is high, and the method is green and environment-friendly.
Drawings
FIG. 1 is an infrared spectrum of a target product prepared in step S1 of example 1 of the present invention;
FIG. 2 is an infrared spectrum of a target product prepared in step S2 of example 1 of the present invention;
FIG. 3 is an infrared spectrum of a target product prepared in step S3 of example 1 of the present invention;
fig. 4 is an infrared spectrum of the objective product prepared in step S4 of example 1 of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Example 1
S1: 450g of tert-octylamine, 450g of triacetonamine, 80g of framework copper and nitrogen are put into a 3L hydrogenation kettle for replacement, stirring is started, the temperature is raised to 95 ℃, 5.5g of hydrogen is introduced, then the heat preservation reaction is carried out for 10 hours, and distillation and desolventization are carried out, so that 739.34g of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine are prepared.
The structural formula is as follows:
Figure BDA0003576288430000051
the infrared spectrum of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidin-4-amine is shown in figure 1 and is 2955cm-1、1455cm-1、1398cm-1Absorption peak, indicating the presence of-CH3、-CH2-a stretching, bending vibration vC-H. At 3260cm-1Has an absorption peak of vN-H at 1237cm-1The characteristic absorption peak of vC-N is shown, which indicates that secondary amine exists in the molecule.
S2: 600g of dimethylbenzene and 115g of cyanuric chloride are put into a 5L flask, 264g of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine is started to be stirred and dripped, the reaction temperature is controlled to be 85 ℃ when the dripping is carried out, the dripping flow rate is controlled to be 10g/min, 132g of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine is dripped, 584g of liquid alkali (the mass fraction is 32%) is started to be dripped simultaneously, and the liquid alkali dripping flow rate is controlled to be 15 g/min. Then heating to 90 ℃ for reaction for 30h, after the reaction is finished, dividing water, after the water dividing is finished, adding 200g of 75 ℃ hot water into the organic layer for stirring and washing for 0.5h, and after the water washing is finished, dividing water to obtain 955g of 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine dimethylbenzene solution.
The structural formula is as follows:
Figure BDA0003576288430000061
the infrared spectrum of 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine is shown in figure 2, and is at 2965cm-1、1483cm-1、1369cm-1Absorption peak, indicating the presence of-CH3、-CH2-a stretching, bending vibration vC-H. At 1400-1600 cm-1The peak is the characteristic peak of benzene ring, and is 1242cm-1The characteristic absorption peak of vC-N is 700-750 cm-1Is a characteristic absorption peak of vC-Cl.
S3: 80g of formaldehyde is added into a flask containing 955g of 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine in xylene, the reaction temperature is controlled to be 70 ℃, 60g of formic acid (the mass fraction is 94%) is added dropwise, the dropping flow of the formic acid is controlled to be 5g/min, and after the dropwise addition is finished, the temperature is raised to 95 ℃ to react for 15 hours. After the reaction is finished, water is separated. Then, 220g of hot water at 72 ℃ was added to the organic layer, and the mixture was stirred and washed with water for 1 hour, and after the washing with water was completed, water was separated to obtain 960g of a xylene solution of 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine.
The structural formula is as follows:
Figure BDA0003576288430000062
the infrared spectrum of 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine is shown in figure 3 and is at 2969cm-1、1485cm-1、1358cm-1Absorption peak, indicating the presence of-CH3、-CH2The stretching, bending vibration vC-H of (a), is a characteristic absorption peak of the hindered amine group. At 1400-1600 cm-1The peak is the characteristic peak of benzene ring and is 1291cm-1The characteristic absorption peak of vC-N is 700-750 cm-1Is a characteristic absorption peak of vC-Cl.
S4: 960g of 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine in xylene solution was transferred to a 5L autoclave, and 110g of liquid base (mass fraction: 32%) was added, 30g of N, N' -bis (3-aminopropyl) -ethylenediamine was added, nitrogen substitution was carried out, stirring was started and the temperature was raised to 185 ℃ and the reaction was maintained for 8 hours; after the reaction is finished, water is separated. And then adding 250g of 73 ℃ hot water into the organic layer, stirring and washing for 1h, after the washing is finished, dividing water, and desolventizing the organic layer to obtain 349.2g of finished product, wherein the yield is 96%.
The structural formula is as follows:
Figure BDA0003576288430000071
the infrared spectrum of the target product is shown in FIG. 4 and is at 2963cm-1、1472cm-1、1362cm-1Absorption peak, indicating the presence of-CH3、-CH2The expansion and bending vibration vC-H is the characteristic absorption peak of the hindered amine group and is 1400-1600 cm-1The peak is a characteristic peak of a benzene ring and is 1262cm-1And presents a characteristic absorption peak of vC-N.
Example 2
S1: 1380g of tert-octylamine, 1400g of triacetonamine, 120g of framework copper and nitrogen substitution are put into a 5L hydrogenation kettle, stirring is started, the temperature is raised to 90 ℃, 22.5g of hydrogen is introduced, then the reaction is carried out for 15h under the condition of heat preservation, and distillation and desolventization are carried out, so that 1938.12g of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine are prepared.
S2: 3200g of dimethylbenzene and 1430g of cyanuric chloride are put into a 10L glass reaction kettle, 1938.12g of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine is dropwise added under stirring, the reaction temperature is controlled to be 95 ℃ during dropwise addition, the dropwise addition flow rate is controlled to be 15g/min, 750g of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine is dropwise added, 1875g of liquid alkali (the mass fraction is 32%) is simultaneously dropwise added, and the liquid alkali dropwise addition flow rate is controlled to be 15 g/min. Then heating to 90 ℃ for reaction for 36h, after the reaction is finished, dividing water, after the water dividing is finished, adding 1800g of hot water at 85 ℃ into the organic layer for stirring and washing for 2h, and after the water washing is finished, dividing water to obtain 6945.8g of 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine xylene solution.
S3: 230g of formaldehyde are added into a flask containing 6945.8g of xylene solution of 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine, the reaction temperature is controlled to be 85 ℃, then 305g of dimethyl sulfate is dropwise added, the dropwise addition flow rate of the dimethyl sulfate is controlled to be 15g/min, after the dropwise addition is finished, the temperature is raised to 95 ℃, and the reaction is carried out for 12 hours. After the reaction is finished, water is separated. Then 2600g of hot water at 75 ℃ were added to the organic layer, and the mixture was washed with stirring water for 1.5h, after the washing with water was completed, water was separated to obtain 6782.7g of a xylene solution of 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine.
S4: 6782.7g of 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine in xylene are transferred into a 20L reaction kettle, 580g of liquid alkali (mass fraction is 32%) are added, 490g of N, N' -bis (3-aminopropyl) -ethylenediamine is added, nitrogen gas is replaced, stirring is started, the temperature is raised to 185 ℃ and the temperature is kept for reaction for 8 hours; after the reaction is finished, water is separated. And then adding 2050g of hot water with the temperature of 80 ℃ into the organic layer, stirring and washing for 1h, after the washing is finished, dividing water, and desolventizing the organic layer to obtain 3576.9g of finished product, wherein the yield is 98.8%.
Example 3
S1: 680g of tert-octylamine, 590g of triacetonamine and 40g of skeletal nickel are put into a 3L hydrogenation kettle, nitrogen is replaced, stirring is started, the temperature is raised to 90 ℃, 8.8g of hydrogen is introduced, then the reaction is kept for 12 hours, and distillation and desolventization are carried out, so that 939.6g of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine are prepared.
S2: adding 800g of dimethylbenzene and 635g of cyanuric chloride into a 10L glass reaction kettle, starting stirring, dropwise adding 939.6g of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine, controlling the reaction temperature at 95 ℃ during dropwise adding, controlling the dropwise adding flow at 15g/min, dropwise adding 450g of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine, and then simultaneously dropwise adding 600g of liquid alkali (the mass fraction is 32%) at the beginning, and controlling the liquid alkali dropwise adding flow at 15 g/min. Then heating to 90 ℃ for reaction for 30h, after the reaction is finished, dividing water, after the water dividing is finished, adding 690g of hot water at 85 ℃ into the organic layer, stirring and washing for 2h, and after the water washing is finished, dividing water to obtain 1805.8g of 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine xylene solution.
S3: a flask containing 1805.8g of a xylene solution of 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine was charged with 90g of formaldehyde, the reaction temperature was controlled at 82 ℃, 56g of methyl bromide was then added dropwise, the flow rate of methyl bromide was controlled at 12g/min, and after the addition, the temperature was raised to 90 ℃ to react for 16 hours. After the reaction is finished, water is separated. Then, 1000g of hot water at 75 ℃ was added to the organic layer, and the mixture was stirred and washed with water for 0.5 hour, and after the washing with water was completed, water was separated to obtain 1690.1g of a xylene solution of 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine.
S4: 1690.1 xylene solution of 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidine-4-yl) -N2, N4-bis (2,4, 4-trimethylpentane-2-yl) -1,3, 5-triazine-2, 4-diamine is transferred into a 5L reaction kettle, 320g liquid alkali (the mass fraction is 32 percent) is added, 60g N, N' -bis (3-aminopropyl) -ethylenediamine is added for nitrogen replacement, stirring is started, the temperature is raised to 185 ℃ and the temperature is kept for reaction for 12 hours; after the reaction is finished, water is separated. And then 600g of hot water with the temperature of 80 ℃ is added into the organic layer to be stirred and washed for 1 hour, after the washing, the water is separated, and 852.2g of finished product is obtained after the organic layer is desolventized, wherein the yield is 94.76%.
Example 4
S1: 450g of tert-octylamine, 450g of triacetonamine, 80g of skeleton nickel and nitrogen are put into a 5L hydrogenation kettle for replacement, stirring is started, the temperature is raised to 95 ℃, 5.5g of hydrogen is introduced, then the heat preservation reaction is carried out for 10 hours, and distillation and desolventization are carried out, so as to obtain 696.5g of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine.
S2: 600g of toluene and 115g of cyanuric chloride are put into a 5L flask, 264g of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidin-4-amine are added dropwise with stirring, the reaction temperature is controlled to be 85 ℃ when the 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidin-4-amine is added dropwise, the dropping flow is controlled to be 10g/min, 132g of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidin-4-amine is added dropwise, 187g of liquid alkali (the mass fraction is 32%) is added dropwise at the same time, and the liquid alkali dropping flow is controlled to be 15 g/min. Then heating to 90 ℃ for reaction for 30h, after the reaction is finished, dividing water, after the water dividing is finished, adding 200g of 75 ℃ hot water into the organic layer for stirring and washing for 0.5h, and after the water washing is finished, dividing water to obtain 925.8g of 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine toluene solution.
S3: 80g of formaldehyde is added into a flask containing 925.8g of toluene solution of 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine, the reaction temperature is controlled to be 70 ℃, 60g of formic acid (the mass fraction is 94%) is added dropwise, the dropping flow of the formic acid is controlled to be 5g/min, after the dropwise addition is finished, the temperature is raised to 95 ℃, and the reaction is carried out for 15 hours. After the reaction is finished, water is separated. Then, 220g of hot water at 72 ℃ was added to the organic layer, and the mixture was stirred and washed with water for 1 hour, and after the washing with water was completed, water was separated to obtain 926.4g of a toluene solution of 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine.
S4: 926.4g of 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine in toluene are transferred into a 5L autoclave, 110g of liquid alkali (mass fraction: 32%) are added, 30g of N, N' -bis (3-aminopropyl) -ethylenediamine are added, nitrogen is replaced, stirring is started, the temperature is raised to 185 ℃ and the temperature is kept for reaction for 8 hours; after the reaction is finished, water is separated. And then adding 250g of 73 ℃ hot water into the organic layer, stirring and washing for 1h, after the washing is finished, dividing water, and desolventizing the organic layer to obtain 318.9g of finished product with the yield of 96.7%.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.

Claims (10)

1. A high molecular weight hindered amine light stabilizer characterized by the structural formula (I):
Figure FDA0003576288420000011
2. a preparation method of a high molecular weight hindered amine light stabilizer is characterized by comprising the following steps:
s1: introducing hydrogen, and carrying out hydrogenation reaction on the tert-octylamine and triacetonamine under the action of a catalyst I to generate 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine;
Figure FDA0003576288420000012
s2: carrying out substitution reaction on 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidine-4-amine and cyanuric chloride under the action of a catalyst II to obtain 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentane-2-yl) -1,3, 5-triazine-2, 4-diamine reaction solution;
Figure FDA0003576288420000013
s3: methylating the 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine reaction solution with formaldehyde under the action of a catalyst III to obtain a 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine reaction solution;
Figure FDA0003576288420000021
s4: carrying out substitution reaction on 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentane-2-yl) -1,3, 5-triazine-2, 4-diamine reaction solution and N, N' -bis (3-aminopropyl) -ethylenediamine under the action of a catalyst IV to obtain a high molecular weight hindered amine light stabilizer product;
Figure FDA0003576288420000022
3. the method for preparing a high molecular weight hindered amine light stabilizer according to claim 2, wherein in step S1, the molar ratio of triacetonamine to tert-octylamine to catalyst I to hydrogen is 1: 0.5-1.5: 0.1-0.9: 0.1-1.5.
4. The method for preparing a high molecular weight hindered amine light stabilizer according to claim 2, wherein in step S1, the catalyst I is one or more of framework copper, framework nickel and framework cobalt, the hydrogenation reaction temperature is 85-120 ℃, and the hydrogenation reaction time is 8-30 h.
5. The method of claim 2, wherein in step S2, the molar ratio of 2,2,6, 6-tetramethyl-N- (2,4, 4-trimethylpentane-2-yl) piperidin-4-amine to cyanuric chloride to catalyst ii is 1: 0.5-1.2: 1-8.
6. The method for preparing a high molecular weight hindered amine light stabilizer according to claim 2, wherein in step S2, the catalyst ii is 32 wt% liquid alkali, and the solvent for the substitution reaction is one or more of xylene and toluene; the temperature of the substitution reaction is 80-110 ℃, and the time of the substitution reaction is 24-60 h.
7. The method of claim 2, wherein in step S3 and step S3, the mass ratio of the 6-chloro-N2, N4-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine reaction solution to formaldehyde to the catalyst iii is 1: 0.01-1.1: 0.02-0.09.
8. The method of claim 2, wherein in step S3, the catalyst iii is one or more selected from formic acid, dimethyl sulfate, methyl iodide, and methyl bromide, the temperature of the methylation reaction is 65-120 ℃, and the time of the methylation reaction is 12-26 h.
9. The method for preparing a high molecular weight hindered amine light stabilizer according to claim 2, wherein in step S4 and step S4, the mass ratio of the reaction solution containing 6-chloro-N2, N4-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N2, N4-bis (2,4, 4-trimethylpentan-2-yl) -1,3, 5-triazine-2, 4-diamine to N, N' -bis (3-aminopropyl) -ethylenediamine to catalyst IV is 1: 0.01-1.2: 0.02-0.8.
10. The method as claimed in claim 2, wherein in step S4, the catalyst IV is 32 wt% liquid alkali, the temperature of the substitution reaction is 155-255 ℃, and the time of the substitution reaction is 8-30 h.
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CN115975189A (en) * 2022-12-26 2023-04-18 江苏富比亚化学品有限公司 Synthesis method of hindered amine light stabilizer 944

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EP0835873A1 (en) * 1996-10-14 1998-04-15 Ciba Speciality Chemicals Holding Inc. Mixtures of trisubstituted and tetrasubstituted polyalkylpiperidinylaminotriazine tetraamine compounds
CN110922389A (en) * 2019-10-14 2020-03-27 天津利安隆新材料股份有限公司 Preparation method of hindered amine light stabilizer
CN113307795A (en) * 2021-06-03 2021-08-27 宿迁市振兴化工有限公司 Preparation method of hindered amine light stabilizer 119

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EP0835873A1 (en) * 1996-10-14 1998-04-15 Ciba Speciality Chemicals Holding Inc. Mixtures of trisubstituted and tetrasubstituted polyalkylpiperidinylaminotriazine tetraamine compounds
CN110922389A (en) * 2019-10-14 2020-03-27 天津利安隆新材料股份有限公司 Preparation method of hindered amine light stabilizer
CN113307795A (en) * 2021-06-03 2021-08-27 宿迁市振兴化工有限公司 Preparation method of hindered amine light stabilizer 119

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115975189A (en) * 2022-12-26 2023-04-18 江苏富比亚化学品有限公司 Synthesis method of hindered amine light stabilizer 944
CN115975189B (en) * 2022-12-26 2024-06-11 江苏富比亚化学品有限公司 Synthesis method of hindered amine light stabilizer 944

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