CN112661695B - Method for preparing hindered amine light stabilizer by solvent method - Google Patents
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Abstract
The invention provides a method for preparing a hindered amine light stabilizer by adopting a solvent method. The method for preparing the hindered amine light stabilizer by adopting the solvent method comprises the following steps: under the action of a catalyst, in an organic solvent, carrying out transesterification on a 2, 6-tetramethyl piperidinyl matrix and dimethyl sebacate to obtain a transesterification product; and (3) sequentially carrying out water washing, filtering and desolventizing treatment on the transesterification product to obtain the hindered amine light stabilizer and wastewater. The preparation method of the hindered amine light stabilizer is beneficial to reducing the process cost and improving the purity, recovery rate and light transmittance of the hindered amine light stabilizer.
Description
Technical Field
The invention relates to the field of synthesis of hindered amine light stabilizers, in particular to a method for preparing a hindered amine light stabilizer by a solvent method.
Background
The hindered amine light stabilizer (Hindered Amine Light Stabilizer, HALS for short) is an efficient auxiliary agent for inhibiting photooxidative degradation of high polymer materials, and the stabilizing effect is 2-4 times that of the traditional absorption type light stabilizer. The light stabilizer has good synergistic effect with ultraviolet absorber and antioxidant, and has good compatibility with various polymer materials.
Bis (2, 6-tetramethyl-4-piperidinyl) sebacate, UV-770, has long been industrialized and is a representative species of low molecular weight HALS. To improve the properties of hindered amine light stabilizers, many industries developed novel hindered amine light stabilizers, such as UV-292, a mixture of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate and mono (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, which have better ability to absorb ultraviolet light. At present, research on domestic non-polymeric low molecular weight HALS has been rapidly developed.
The prior preparation of the non-polymeric low molecular HALS adopts a transesterification method. As patent application CN200910036230.2, there is provided a light stabilizer bis (2, 6-tetramethylpiperidinyl) sebacate and a process for producing the same, dimethyl sebacate, 2, 6-tetramethyl piperidine and dimethylbenzene are used as raw materials, dibutyl tin oxide is used as a catalyst, and bis (2, 6-tetramethyl piperidinyl) sebacate is synthesized. The dimethylbenzene adopted in the synthesis process has pungent smell and low toxicity, and belongs to substances capable of being carcinogenic.
In addition, the prior art has the problems of low esterification rate, poor light transmittance of products, unstable quality and the like. In view of the above problems, there is a need to develop a novel process for preparing non-polymeric light stabilizers which is energy-efficient, gives high yields and is stable in product properties.
Disclosure of Invention
The invention mainly aims to provide a method for preparing a hindered amine light stabilizer by adopting a solvent method, so as to solve the problems of low production efficiency, high energy consumption, high cost and poor light transmittance of products in the existing preparation method of the hindered amine light stabilizer.
In order to achieve the above object, the present invention provides a method for preparing a hindered amine light stabilizer by a solvent method, the method for preparing the hindered amine light stabilizer by the solvent method comprising: under the action of a catalyst, in an organic solvent, carrying out transesterification on a 2, 6-tetramethyl piperidinyl matrix and dimethyl sebacate to obtain a transesterification product; sequentially performing water washing, filtering and desolventizing treatment on the transesterification product to obtain a hindered amine light stabilizer and wastewater, wherein a 2, 6-tetramethylpiperidinyl matrix has the following structure:
r is H, methyl, ethyl, isopropyl,N-propyl, n-butyl or C 1 -C 10 Alkoxy, A is H or hydroxy; the organic solvent is selected from solvent oil, petroleum ether and C 5 ～C 12 At least one of an alkane or a cycloalkane.
Further, the method for preparing the hindered amine light stabilizer by adopting the solvent method further comprises the following steps: acid washing the transesterification product prior to the water washing step; and/or adding liquid alkali and solvent to the wastewater for extraction to recover unreacted 2, 6-tetramethylpiperidinyl precursors.
Further, C 5 ～C 12 The alkane or cycloalkane is selected from one or more of heptane, n-hexane, cyclohexane, n-octane and nonane; the solvent oil is at least one selected from solvent oil D30 and solvent oil D20.
Further, when the 2, 6-tetramethyl piperidinyl matrix A is hydroxy, R is H, methyl, ethyl, isopropyl, n-propyl or n-butyl.
Further, the weight ratio of the 2, 6-tetramethyl piperidinyl parent and the organic solvent is 1 (1.2-1.8).
Further, the weight ratio of the 2, 6-tetramethyl piperidinyl matrix, the dimethyl sebacate and the catalyst is 1 (0.4-0.9) to 0.004-0.02.
Further, the catalyst is selected from one or more of n-butyl titanate, tetraisopropyl titanate, sodium methoxide, aluminum isopropoxide, lithium amide and dibutyltin oxide.
Further, the temperature of the transesterification reaction is 110-160 ℃, and the reaction time is 4-24 h.
Further, the acid adopted in the acid washing step is one or more selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid and p-toluenesulfonic acid, and the addition amount of the acid is 1-20wt% of the 2, 6-tetramethylpiperidinyl matrix.
Further, when the method for preparing the hindered amine light stabilizer by adopting the solvent method comprises an acid washing step and an extraction step, the molar ratio of the addition amount of liquid alkali to the addition amount of acid in the acid washing step is 1-2:1; preferably, the extraction solvent is selected from the group consisting of mineral spirits, petroleum ether and C 5 ～C 12 At least one of an alkane or a cycloalkane.
By applying the technical scheme of the invention, when the hindered amine light stabilizer is synthesized in the presence of the solvent, the product quality is easy to control, the process is simple, the large-scale production is convenient, and the light transmittance of the product is improved.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As described in the background art, the existing preparation method of the hindered amine light stabilizer has the problems of low production efficiency, high energy consumption, high cost and poor light transmittance of the product. In order to solve the technical problems, the application provides a method for preparing a hindered amine light stabilizer by adopting a solvent method, which comprises the following steps: under the action of a catalyst, in an organic solvent, carrying out transesterification on a 2, 6-tetramethyl piperidinyl matrix and dimethyl sebacate to obtain a transesterification product; sequentially performing water washing, filtering and desolventizing treatment on the transesterification product to obtain a hindered amine light stabilizer and wastewater, wherein a 2, 6-tetramethylpiperidinyl matrix has the following structure:
r is H, methyl, ethyl, isopropyl, n-propyl, n-butyl or C 1 -C 8 Alkoxy, A is H or hydroxy; the organic solvent is selected from solvent oil, petroleum ether and C 5 ～C 12 At least one of an alkane or a cycloalkane.
Researches show that when the hindered amine light stabilizer is synthesized in the presence of a solvent, the product quality is easy to control, the process is simple, the large-scale production is convenient, and the light transmittance of the product is improved. Especially, when the organic hydrocarbon solvent is selected, the reaction can be carried out at a lower reaction temperature, which is beneficial to ensuring the light transmittance of the product; further found that the solvent oil and C 5 ～C 12 The yield of the product can be further improved when alkane or cycloalkane is used; in the research process, the inventor has experimented with various solvents including benzene solvents (such as toluene, xylene and the like) and high-boiling solvents (such as undecane and dodecane), and found that the benzene solvents are not beneficial for improving the light transmittance; high boiling point solvents are also unfavorable for improving the light transmittance of the product and affecting the quality of the product.
Since the waste water also contains a certain amount of unreacted raw materials, in order to improve the utilization rate of the raw materials and the environmental protection of the waste water, the method for preparing the hindered amine light stabilizer by adopting the solvent method preferably further comprises the following steps: acid washing the transesterification product before the water washing step; and/or adding liquid alkali and solvent to the wastewater for extraction to recover unreacted 2, 6-tetramethylpiperidinyl precursors.
In the specific application process, the substituent in the 2, 6-tetramethyl piperidinyl matrix can be optimized according to the requirement, preferably, when R in the 2, 6-tetramethyl piperidinyl matrix is alkoxy, C 1 -C 10 Alkoxy groups include, but are not limited to, methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, or octoxy.
In a specific application process, the substituent groups in the 2, 6-tetramethyl piperidinyl matrix can be optimized according to the needs, and preferably, when the A is hydroxyl, R is H, methyl, ethyl, isopropyl, n-propyl and n-butyl.
In a preferred embodiment, the solvent oil includes, but is not limited to, at least one of solvent oil D30 and solvent oil D20; c (C) 5 ～C 12 The alkane or cycloalkane is selected from one or more of heptane, n-hexane, cyclohexane, n-octane and nonane, and the adoption of the solvents is more beneficial to improving the light transmittance and the yield of the product.
In a preferred embodiment, the weight ratio of 2, 6-tetramethylpiperidinyl precursor to organic solvent is 1 (1.2-1.8), e.g., in the specific example, 1:1.5.
In a preferred embodiment, the weight ratio of 2, 6-tetramethylpiperidinyl precursor, dimethyl sebacate and catalyst is 1 (0.4-0.9): 0.004-0.02. The weight ratio of the 2, 6-tetramethylpiperidinyl precursor, dimethyl sebacate and the catalyst includes, but is not limited to, the above ranges, and limiting it to the above ranges is advantageous for further improving the yield of the hindered amine light stabilizer.
In a preferred embodiment, the catalyst includes, but is not limited to, one or more of the group consisting of n-butyl titanate, tetraisopropyl titanate, sodium methoxide, aluminum isopropoxide, lithium amide, and dibutyltin oxide.
In a preferred embodiment, the transesterification reaction is carried out at a temperature of from 110 to 160℃and for a reaction time of from 4 to 24 hours. The reaction at the temperature is favorable for further improving the catalytic activity of the catalyst and the selectivity of the reaction, thereby being favorable for further improving the reaction rate of the transesterification reaction and also being favorable for improving the yield of the hindered amine light stabilizer. Preferably, the temperature of the transesterification reaction is 120-150 ℃, e.g. 120 ℃,130 ℃,140 ℃,150 ℃.
In order to further increase the solubility of the 2, 6-tetramethylpiperidinyl precursor in water, it is preferred that the acid employed in the pickling process include, but are not limited to, one or more of sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, p-toluenesulfonic acid, the acid being added in an amount of 1 to 20wt%, preferably 0.05 to 0.1% of the 2, 6-tetramethylpiperidinyl precursor, said acid being generally added in an amount of 100% pure acid.
In the process of recovering 2, 6-tetramethylpiperidinyl precursors:
the extraction solvent is the same as the organic solvent of transesterification, i.e. the organic solvent is selected from the group consisting of mineral spirits, petroleum ether and C 5 ～C 12 The solvent used for extraction is 10-20 times (volume weight ratio) of the theoretical recovered 2, 6-tetramethylpiperidinyl precursor. The extraction solvent and the transesterification adopt the same organic solvent, which is more beneficial to improving the purity and quality of the recovered 2, 6-tetramethyl piperidinyl matrix, and the recovered 2, 6-tetramethyl piperidinyl matrix can be directly fed for the next batch of reaction without influencing the yield, purity and light transmittance of the productThe rate.
In order to improve the recovery rate of the 2, 6-tetramethyl piperidinyl matrix, the method for preparing the hindered amine light stabilizer by adopting the solvent method comprises an acid washing step and an extraction step, and the molar ratio of the addition amount of liquid alkali to the addition amount of acid is 1-2:1. In a preferred embodiment, the liquid alkali can be sodium hydroxide solvent, potassium hydroxide solution or other liquid alkali known in the art, and especially 10-30% sodium hydroxide solution or potassium hydroxide solution is selected to be more beneficial to improving the recovery rate of the 2, 6-tetramethyl piperidinyl matrix, facilitating the treatment and protecting the environment.
In the reaction system, the organic solvent is adopted to promote the transesterification reaction, so that the light transmittance of the product can be improved, meanwhile, the solvent can dissolve unreacted 2, 6-tetramethyl piperidinyl parent raw materials, and the same solvent can be used for the reaction solvent to realize the efficient recovery of the 2, 6-tetramethyl piperidinyl parent through the treatment of wastewater, thereby saving the production cost and reducing the raw material consumption.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
Into a four-necked flask, 120.15g (0.7653 mol) of 2, 6-tetramethylpiperidinol, 80.06g (0.3476 mol) of dimethyl sebacate and 175.47g of solvent oil D20 (Yue Yangjia Xin) were sequentially added, and N was introduced 2 Fully protecting, installing a condenser, starting magnetic stirring, heating to 120 ℃, refluxing and dehydrating until no water drops exist, dropwise adding 1.74g of tetraisopropyl titanate, dropwise adding for 10-15 min, heating to 150 ℃, carrying out heat preservation reaction, continuously steaming out methanol in the reaction process, adding 24g of 80% acetic acid after the reaction is finished, carrying out pickling and washing, filtering and desolventizing to obtain white crystalline powder bis (2, 6-tetramethylpiperidinyl) sebacate, wherein the product yield is 99.62wt%, the GC content is 99.41%, and the light transmittance at 425nm is 99.25%. 50g of liquid alkali (containing 20% of sodium hydroxide) and 175.47g of solvent oil D are added into the generated wastewater to extract, and about 10g of 2, 6-tetramethylpiperidinol is recovered, so that the recovery rate is 90%.
Example 2
Four-way openingThe flask was charged with 120.09g (0.7022 mol) of 1,2, 6-pentamethyl-4-piperidinol, 85.38g (0.3707 mol) of dimethyl sebacate, 200.65g of solvent oil D30 (Yue Yangjia Xin) and N was introduced 2 Fully protecting, installing a condenser, starting magnetic stirring, heating to 125 ℃, refluxing and dehydrating until no water drops exist, dropwise adding 0.75g of tetraisopropyl titanate, dropwise adding 10-15 min, heating to 150 ℃, preserving heat for reaction, continuously steaming out methanol in the reaction process, adding 12g of 80% acetic acid after the reaction is finished, and carrying out acid washing, water washing, filtering and desolventizing to obtain light yellow liquid, namely a mixture of bis (1, 2, 6-pentamethylpiperidine alcohol) sebacate and mono (1, 2, 6-pentamethylpiperidine alcohol) sebacate, wherein the product yield is 99.09wt%, the GC content is 99.76%, and the light transmittance is 425nm 99.9%. 22g of liquid alkali (containing 20% of sodium hydroxide) and 200.65g of solvent oil D are added into the generated wastewater to extract, and about 8g of 1,2, 6-pentamethyl-4-piperidinol is recovered, so that the recovery rate is 88%.
Example 3
The differences from example 1 are: the solvent is petroleum ether.
The yield of bis (2, 6-tetramethylpiperidinyl) sebacate was 97.2% by weight, the GC content was 99.6%, and the light transmittance at 425nm was 99.8%.
Example 4
The differences from example 1 are: the solvent was heptane.
The yield of bis (2, 6-tetramethylpiperidinyl) sebacate was 99.5% by weight, the GC content was 99.5%, and the light transmittance at 425nm was 99.5%.
Example 5
The differences from example 1 are: the raw materials are as follows: 110.15g of 2, 6-tetramethylpiperidinyl parent, 10g of 2, 6-tetramethylpiperidinyl parent recovered in the examples, together with 120.15g.
The yield of bis (2, 6-tetramethylpiperidinyl) sebacate was 99.6wt%, the GC content was 99.3%, and the light transmittance at 425nm was 99.4%.
Comparative example 1
The differences from example 1 are: no organic solvent is added during the transesterification reaction.
The yield of bis (2, 6-tetramethylpiperidinyl) sebacate was 98.7% by weight, the GC content was 98.1%, and the 425nm light transmittance was 97.1%.
Comparative example 2
The differences from example 1 are: the transesterification process is not followed by acid washing but only water washing. The resulting wastewater was directly extracted with solvent oil D20. 20 175.47g to recover 2, 6-tetramethylpiperidinol.
The yield of bis (2, 6-tetramethylpiperidinyl) sebacate was 98.9% by weight, the GC content was 99.4%, and the 425nm transmittance was 98.0%. The recovery rate of 2, 6-tetramethyl piperidinol was 30%.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the preparation method of the hindered amine light stabilizer is beneficial to reducing the process cost and improving the purity, recovery rate and light transmittance of the hindered amine light stabilizer.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described herein.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The method for preparing the hindered amine light stabilizer by adopting the solvent method is characterized by comprising the following steps of:
under the action of a catalyst, in an organic solvent, carrying out transesterification on a 2, 6-tetramethyl piperidinyl matrix and dimethyl sebacate to obtain a transesterification product;
sequentially performing water washing, filtering and desolventizing treatment on the transesterification product to obtain the hindered amine light stabilizer and wastewater, wherein the 2, 6-tetramethylpiperidinyl matrix has the following structure:
r is H, methyl, ethyl, isopropyl, n-propyl, n-butyl or C 1 -C 10 Alkoxy, A is H or hydroxy;
the organic solvent is selected from solvent oil, petroleum ether and C 5 ～C 12 At least one of an alkane or a cycloalkane;
the C5-C12 alkane or cycloalkane is selected from one or more of heptane, n-hexane, cyclohexane, n-octane and nonane; the solvent oil is at least one selected from solvent oil D30 and solvent oil D20;
the weight ratio of the 2, 6-tetramethyl piperidinyl matrix to the organic solvent is 1 (1.2-1.8);
the temperature of the transesterification reaction is 130-160 ℃; the catalyst is selected from n-butyl titanate and tetraisopropyl titanate;
acid washing the transesterification product prior to the washing step; and/or the number of the groups of groups,
adding liquid alkali and solvent into the wastewater for extraction to recover unreacted 2, 6-tetramethyl piperidinyl matrix.
2. The method for preparing a hindered amine light stabilizer by a solvent method according to claim 1, wherein when a is hydroxyl, R is H, methyl, ethyl, isopropyl, n-propyl, n-butyl.
3. The method for preparing a hindered amine light stabilizer by a solvent method according to claim 1 or 2, wherein the weight ratio of the 2, 6-tetramethylpiperidinyl matrix, the dimethyl sebacate and the catalyst is 1:
(0.4～0.9):(0.004～0.02)。
4. a method for preparing a hindered amine light stabilizer by a solvent method according to claim 3, wherein the reaction time is 4 to 24 hours.
5. The method for preparing the hindered amine light stabilizer by adopting the solvent method according to claim 1, wherein the acid adopted in the acid washing process is one or more selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid and p-toluenesulfonic acid, and the addition amount of the acid is 1-20wt% of the 2, 6-tetramethyl piperidinyl matrix.
6. The method for preparing the hindered amine light stabilizer by adopting the solvent method according to claim 1, wherein the molar ratio of the addition amount of the liquid alkali to the addition amount of the acid is 1-2:1.
7. The method for preparing a hindered amine light stabilizer according to claim 6, wherein the extraction solvent is selected from the group consisting of mineral spirits, petroleum ether and C 5 ～C 12 At least one of an alkane or a cycloalkane.
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| CN116143685A (en) * | 2022-11-23 | 2023-05-23 | 江苏富比亚化学品有限公司 | Synthesis method of hindered amine light stabilizer 292 |
| CN115819325A (en) * | 2022-12-29 | 2023-03-21 | 江苏富比亚化学品有限公司 | Method for synthesizing light stabilizer 770 by solvent-free method |
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Address after: 053400 No.9, Jiheng Road, Hengshui industrial new area, Hebei Province Applicant after: Lian longkaiya (Hebei) new material Co.,Ltd. Applicant after: RIANLON Corp. Address before: 053400 9 Jiheng Road, Hengshui industrial new area, Hebei Province Applicant before: Lian longkaiya (Hebei) new material Co.,Ltd. Applicant before: RIANLON Corp. |
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