CN103319398A - Preparation method of hindered amine light stabilizer - Google Patents
Preparation method of hindered amine light stabilizer Download PDFInfo
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- CN103319398A CN103319398A CN2013101859484A CN201310185948A CN103319398A CN 103319398 A CN103319398 A CN 103319398A CN 2013101859484 A CN2013101859484 A CN 2013101859484A CN 201310185948 A CN201310185948 A CN 201310185948A CN 103319398 A CN103319398 A CN 103319398A
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Abstract
The invention relates to a light stabilizer, and especially relates to a preparation method of a hindered amine light stabilizer. The method is mainly used for solving the technical problems of high cost, non-mild reaction process, complicated operation, high cost, and low yield of prior art adopting dicarboxylate as a raw material. According to the invention, alkyl-substituted-4-hydroxyl piperidine and dicarboxylic acid are added into solvent oil; nitrogen is delivered for protection; heating and dissolving are carried out, and temperature maintaining is carried out; and a reflux reaction is carried out, wherein a molar ratio of alkyl-substituted-4-hydroxyl piperidine to dicarboxylic acid is 2.0:1 to 2.6:1; cooling precipitation is carried out after the reaction is completed; the solvent is separated, and water washing is carried out, such that a crude product is obtained. The crude product is added into fresh solvent oil, and active carbon is added for discoloring; and re-crystallization is carried out, such that a pure hindered amine light stabilizer is obtained.
Description
Technical field
The present invention relates to a kind of photostabilizer, especially relate to a kind of preparation method of hindered amine as light stabilizer.
Background technology
Hindered amine light stabilizer (HALS) becomes the main flow of photostabilizer consumption market in the synthetic material auxiliary agent, dominate in world's photostabilizer market comsupton structure owing to its superior performance.Along with the fundamental research of photostabilizer and deepening continuously of applied research, the range of application of HALS constantly enlarges.At present, the application of HALS has been contained in the various fields such as plastic sheeting for farm use, engineering plastics, fiber, high-molecular coating, artificial carpet and outdoor various plastics.
People have known and two (piperidines of the replacement) esters of the preparation that can in all sorts of ways, domestic and foreign literature is reported in the existing synthetic method, mainly contain the reaction of (1) chloride thing and alkyl replacement-4-hydroxy piperidine and get (2) employing dicarboxylic ester and the reaction of alkyl replacement-4-hydroxy piperidine, in catalyzer (sodium alkoxide class for example, Lithamide class etc.) under the condition of Cun Zaiing, not or have under the condition that inert solvent (for example toluene) exists, utilize transesterification reaction, generate dibasic acid esters and the byproduct methyl alcohol of used piperidines alcohol.
For example at United States Patent (USP) 4,021, sebacic acid chloride thing has been described with 1 in 432,2,2,6, photostabilizer Tinuvin 292 is produced in the reaction of 6-pentamethyl-piperidines alcohol, and this reaction yield is 71%, but this reaction has used expensive chloride thing to be raw material, 1,2,2,6,6-pentamethyl-piperidines alcohol is excessive 40%, aftertreatment trouble, cost height.
At United States Patent (USP) 4,4461, in 898, with alkyl replacement-4-hydroxy piperidine and dimethyl sebacate under the catalysis of lithium amide, 100-145 ℃ of reaction.Reaction generates the mixture of the various esters of many alkylpiperidine derivatives under the condition of fusion, and yield is about 91%; The technology that adopts in Zhang Zepeng [" Hebei chemical industry ", the 2nd phase P43-45 in 1998] reaction: 2,2,6,6-tetramethylpiperidinol and dimethyl sebacate are catalyzer with the sodium methylate, and toluene is that solvent is produced two 2,2, the 6-tetramethyl-s of sebacic acid-4-piperidines ester.Yield is about 97%.But this type of catalyst for reaction poor stability is preserved difficulty, and the quality of catalyzer is difficult to detect, but reaction to catalyzer require highly, bring unsettled hidden danger to reaction.(sodium methylate is poisonous, and easy firing is met water and easily decomposed)
The technology that in Liu Junsheng [" Guangzhou chemical industry " 2009 37 volumes the 3rd phase P136-138] reaction, adopts: dimethyl sebacate and the reaction of 1,2,2,6,6-pentamethyl-piperidines alcohol.Be that catalyzer is produced photostabilizer Tinuvin 292 with the tetra isopropyl titanate.Temperature of reaction was reacted 8 hours at 160 ℃, and yield is 91%; Having described in 5,817,821 in United States Patent (USP) to adopt dicarboxylic ester and alkyl replacement-4-hydroxy piperidine to react, is the various esters that raw material is produced many alkylpiperidine derivatives with Dibutyltin oxide.This catalysts stable in properties, but catalyzer price comparison costliness, and contain the metallic tin ion in the reaction product.
Summary of the invention
The present invention need provide a kind of preparation method of hindered amine as light stabilizer, it mainly is to solve existing in prior technology to adopt dicarboxylic ester be that the price of raw material is higher, and the process of reaction is not gentleer, the operation more complicated, cost is higher, the low technical problem that waits of yield.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals:
The preparation method of a kind of hindered amine as light stabilizer of the present invention, it is characterized in that described method be with
(a) have the alkyl replacement-4-hydroxy piperidine of following general formula,
R wherein
1,R
2, R
3And R
4Be CH partly or entirely
3Or C
2H
5; R
5Be H or CH
3
(b) have the dicarboxylic acid of following molecular formula,
Wherein n is the integer of 2-20;
Join in the solvent oil; logical nitrogen protection; be incubated under the condition of rising temperature for dissolving; carry out back flow reaction then; wherein the mol ratio of alkyl replacement-4-hydroxy piperidine and dicarboxylic acid is 2.0:1 to 2.6:1, adopts cooling to separate out after reaction is finished, by separating solvent; washing obtains thick product, slightly adds the activated carbon decolorizing recrystallization in the solvent oil that the product input is fresh and namely gets pure product hindered amine as light stabilizer.
The concrete synthetic route of the present invention can be expressed as:
Under nitrogen protection, use solvent oil, the rising temperature for dissolving raw material, and constantly isolate water.
As preferably, described solvent oil, its boiling range is at 140-210 ℃.
As preferably, the temperature of described back flow reaction is 140-210 ℃, and the reaction times is 6-36 hour.
As preferably, cool to 10-30 ℃ after described reaction is finished and separate out product or steam solvent and obtain product.
As preferably, described dicarboxylic acid is sebacic acid.The sebacic acid molecular weight is little, and consumption is few, and unit price is more cheap.Dicarboxylic acid is that sebacic acid is that photostabilizer 770 also has industrial prospect by the synthetic product of the technical process of above-mentioned patent.
Therefore; it is raw material that the present invention adopts dicarboxylic acid and alkyl replacement-4-hydroxy piperidine; the greenization of realization response technology (by-product is water); average yield is more than 92%, and dicarboxylic acid greatly reduces with respect to the price of dicarboxylic ester, and reaction has the solvent protective reaction gentle relatively; operate fairly simple; cost is low, and the yield height is fit to scale operation.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1: the preparation method of a kind of hindered amine as light stabilizer of this example, and the solvent oil of adding 200ml adds raw material sebacic acid (20.2g 0.1mol) and 2 again in the 500ml flask, 2,6,6-tetramethylpiperidinol (34.6g 0.22mol) and catalyzer are warming up to backflow.Finish through reaction in 10-15 hour.Cooling is separated out, the solvent reclaiming of separating.Washing, further refining fusing point is two (2,2,6,6-tetramethyl--4-piperidyl) sebates of pure product of 81-83 ℃, yield is 80.5%
Embodiment 2: the preparation method of a kind of hindered amine as light stabilizer of this example, the recovery solvent oil that in the 500ml flask, adds the embodiment 1 of 200ml, add raw material sebacic acid (20.2g 0.1mol) and 2 again, 2,6,6-tetramethylpiperidinol (0.22mol) and catalyzer are warming up to back flow reaction.Finish through reaction in 10-15 hour.Cooling is separated out, the solvent reclaiming of separating.Washing drops into crude product in the solvent oil and to add the activated carbon decolorizing recrystallization, obtains main content〉two (2,2,6,6-tetramethyl--4-piperidyl) sebates of 98%, yield is 94.0%.
Embodiment 3: the preparation method of a kind of hindered amine as light stabilizer of this example, and the solvent oil of adding 200ml adds raw material sebacic acid (20.2g 0.1mol) and 1 again in the 500ml flask, 2,2,6,6-pentamethyl-piperidines alcohol (0.22mol) and catalyzer are warming up to back flow reaction.After reaction in 10-15 hour finished, the washing decolouring steamed solvent reclaiming.Get two (1,2,2,6,6-pentamethyl--4-piperidyl) sebates, yield is 90.0%.
The above only is specific embodiments of the invention, but constitutional features of the present invention is not limited thereto, and any those skilled in the art is in the field of the invention, and the variation of doing or modify all is encompassed among the claim of the present invention.
Claims (6)
1. the preparation method of a hindered amine as light stabilizer, it is characterized in that described method be with
(a) have the alkyl replacement-4-hydroxy piperidine of following general formula,
R wherein
1,R
2, R
3And R
4Be CH partly or entirely
3Or C
2H
5; R
5Be H or CH
3
(b) have the dicarboxylic acid of following molecular formula,
Wherein n is the integer of 2-20;
Join in the solvent oil; logical nitrogen protection; be incubated under the condition of rising temperature for dissolving; carry out back flow reaction then, wherein the mol ratio of alkyl replacement-4-hydroxy piperidine and dicarboxylic acid is 2.0:1 to 2.6:1, adopts cooling to separate out after reaction is finished; by separating solvent; washing, thick product is further refining namely to be got pure product hindered amine as light stabilizer or by steaming solvent, directly obtains product.
2. the preparation method of a kind of hindered amine as light stabilizer according to claim 1 is characterized in that the boiling range of described solvent oil is at 140-210 ℃.
3. the preparation method of a kind of hindered amine as light stabilizer according to claim 1, the temperature that it is characterized in that described back flow reaction is 140-210 ℃, the reaction times is 6-36 hour.
4. the preparation method of a kind of hindered amine as light stabilizer according to claim 1 is characterized in that cooling to 10-30 ℃ after described reaction is finished separates out crude product.
5. the preparation method of a kind of hindered amine as light stabilizer according to claim 1 is characterized in that described dicarboxylic acid is preferably sebacic acid.
6. preparation method according to claim 1 adds catalyzer when it is characterized in that reacting.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906550A (en) * | 2016-05-23 | 2016-08-31 | 杭州欣阳三友精细化工有限公司 | Preparation method of UV770 |
| CN106008321A (en) * | 2016-05-23 | 2016-10-12 | 杭州欣阳三友精细化工有限公司 | UV292 preparing method |
| CN110387064A (en) * | 2019-07-12 | 2019-10-29 | 西安工业大学 | A kind of mixed type low alkalinity hindered amine light stabilizer and preparation method thereof |
| CN112661695A (en) * | 2020-12-22 | 2021-04-16 | 利安隆凯亚(河北)新材料有限公司 | Method for preparing hindered amine light stabilizer by adopting solvent method |
| CN114015114A (en) * | 2021-11-10 | 2022-02-08 | 湖南岳化化工股份有限公司 | Hindered amine light stabilizer and preparation method and application thereof |
| CN114230511A (en) * | 2021-12-31 | 2022-03-25 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021432A (en) * | 1971-11-30 | 1977-05-03 | Ciba-Geigy Corporation | Piperidine derivatives |
| US4049647A (en) * | 1971-11-30 | 1977-09-20 | Ciba-Geigy Corporation | Bis piperidyl carboxylates |
| CN1066064A (en) * | 1991-04-24 | 1992-11-11 | 黑蒙特股份公司 | The preparation method of hindered amine as light stabilizer |
| CN102382039A (en) * | 2011-08-08 | 2012-03-21 | 宿迁联盛化学有限公司 | Synthesizing technology of hindered amine light stabilizer Tinuvin-770 |
-
2013
- 2013-05-20 CN CN2013101859484A patent/CN103319398A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021432A (en) * | 1971-11-30 | 1977-05-03 | Ciba-Geigy Corporation | Piperidine derivatives |
| US4049647A (en) * | 1971-11-30 | 1977-09-20 | Ciba-Geigy Corporation | Bis piperidyl carboxylates |
| CN1066064A (en) * | 1991-04-24 | 1992-11-11 | 黑蒙特股份公司 | The preparation method of hindered amine as light stabilizer |
| CN102382039A (en) * | 2011-08-08 | 2012-03-21 | 宿迁联盛化学有限公司 | Synthesizing technology of hindered amine light stabilizer Tinuvin-770 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906550A (en) * | 2016-05-23 | 2016-08-31 | 杭州欣阳三友精细化工有限公司 | Preparation method of UV770 |
| CN106008321A (en) * | 2016-05-23 | 2016-10-12 | 杭州欣阳三友精细化工有限公司 | UV292 preparing method |
| CN105906550B (en) * | 2016-05-23 | 2018-06-12 | 杭州欣阳三友精细化工有限公司 | A kind of preparation method of UV770 |
| CN110387064A (en) * | 2019-07-12 | 2019-10-29 | 西安工业大学 | A kind of mixed type low alkalinity hindered amine light stabilizer and preparation method thereof |
| CN112661695A (en) * | 2020-12-22 | 2021-04-16 | 利安隆凯亚(河北)新材料有限公司 | Method for preparing hindered amine light stabilizer by adopting solvent method |
| CN112661695B (en) * | 2020-12-22 | 2024-03-05 | 利安隆凯亚(河北)新材料有限公司 | Method for preparing hindered amine light stabilizer by solvent method |
| CN114015114A (en) * | 2021-11-10 | 2022-02-08 | 湖南岳化化工股份有限公司 | Hindered amine light stabilizer and preparation method and application thereof |
| CN114230511A (en) * | 2021-12-31 | 2022-03-25 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate |
| CN114230511B (en) * | 2021-12-31 | 2024-01-26 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of bis (2, 6-tetramethyl-4-piperidinyl) sebacate |
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Application publication date: 20130925 |