CN105566204B - A kind of light stabilizer intermediate 2,2,6,6- tetramethyls -4- piperidine ester compounds and preparation method thereof - Google Patents
A kind of light stabilizer intermediate 2,2,6,6- tetramethyls -4- piperidine ester compounds and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of 2,2,6,6 tetramethyl of light stabilizer intermediate, 4 piperidine ester compounds (I), is chemically reacted and is obtained by the unsaturated organic dibasic acid of 2,2,6,6 tetramethylpiperidinols and formula (II)；Meet the 2 of logical formula (I) the present invention also provides a kind of, 2,6,6 tetramethyl, 4 piperidine ester light stabilizer, the light stabilizer is mainly used in other high molecular materials such as plastic film, coating, papermaking, engineering plastics, it can directly participate in chemically reacting, significantly improve the light aging resisting of product, extend the service life of product.The present invention uses (SO4)2‑/TiO2ZnO mixed crystal solid acid carrier complex catalysts have the advantages that can be easily separated with reaction system, not etching apparatus, environmental-friendly.
Description
Technical field
The present invention relates to a kind of light stabilizer intermediate 2,2,6,6- tetramethyl -4- piperidine ester compounds and its preparation sides
Method more particularly to a kind of intermediate for reacting preparation hindered amine light stabilizer with alkyl acid by 2,2,6,6- tetramethylpiperidinols
Method.
Background technology
Light stabilizer is a kind of rising industry and science and technology, and the light stabilizer overwhelming majority that the whole world uses is that recent decades are opened
The kind of hair, light stabilizer are related to multidisciplinary voluminous industry, it is of science to be related to photochemistry, polymer.Reasonable employment light stabilizer,
Number can be saved every year with ten million ton of material, saved the natural resources such as a large amount of oil for the mankind, can not only be protected ecosystem, also
Discharge can be reduced, there is important economy and social value.
At present, light stabilizer belongs to fine chemistry, and preparation process is complicated.EP0508940 discloses this kind of compound
Preparation method, using two-step method, be first dehydrated into imines, then loading type Pd, Pt catalyst or skeleton tweezer catalyst exist
Lower hydrogenating reduction is product.The preparation method is complicated and not easy to control, and the purity of first step reaction generation alkali intermediate is not high,
Second step hydrogenation process can generate side reaction, influence the selectivity and quality of product, more increase the complicated journey of production process
Degree.
On this basis, Chinese patent CN1159296C discloses a kind of three-step approach and prepares 2,2,6,6- tetramethyl of light stabilizer
Base -4- piperidinamines compounds, are that by-product is further reduced, and product yield and purity are high, however preparation method is still relatively more multiple
It is miscellaneous.
Invention content
What the present invention was proposed to solve the above problem of the prior art.
The present invention provides a kind of preparation sides of light stabilizer intermediate 2,2,6,6- tetramethyls -4- piperidine ester compounds
Method.
The present invention also provides a kind of 2,2,6,6- tetramethyl -4- piperidine ester compounds for light stabilizer.
To achieve the above object, the present invention uses following technical scheme：
The first aspect of the invention is to provide a kind of light stabilizer intermediate 2,2,6,6- tetramethyls -4- piperidine esters
The preparation method of object (I) is closed, it is anti-to carry out chemistry by 2,2,6,6- tetramethylpiperidinols and the unsaturated organic dibasic acid of formula (II)
It answers and obtains；
Wherein, R C4-20Alkyl, at least one conjugate moiety is contained in the alkyl.
Preferably, the unsaturated organic dibasic acid is 1,3-butadiene-Isosorbide-5-Nitrae-diacid, i.e. muconic acid.
The synthetic method of the muconic acid is according to Sun Changjun etc.《Organic compound synthesizes handbook》Page 399.
In a preferred embodiment of the present invention, the chemical reaction is in (SO4)2-/TiO2- ZnO mixed crystal solid acid carries
Body complex catalyst, potassium rhodanide, radium chloride sodium and 98% concentrated sulfuric acid catalysis under carry out.(the SO4)2-/TiO2- ZnO is mixed
Brilliant solid acid carrier complex catalyst is prepared by following steps：
Step 1：By TiCl4, zinc nitrate be dispersed in water, be warming up to 90 DEG C -100 DEG C, such as 95 DEG C, then add in 25%
Ammonium hydroxide, sodium tetraborate and basic nickel carbonate keep the temperature 2-4 hours, such as 3 hours, are then down to room temperature, stand at least 2 hour,
As after 3 hours, sediment is collected；
Step 2：The sediment is roasted 2-4 hours, such as 3 hours at 700 DEG C -900 DEG C, such as 850 DEG C；
Step 3：Step 2 gained product of roasting impregnates at least 2 hours in the sulfuric acid solution of 10% mass concentration, then
It is roasted at 500 DEG C -600 DEG C, such as 550 DEG C 3-5 hours, such as 4 hours；
Step 4：The product that triphenylphosphine closes cobalt, ferrocene mixes, step 3 obtains is dispersed in the molten of such as absolute ethyl alcohol
In agent, remove solvent at 70 DEG C -90 DEG C, such as 80 DEG C, then dry at 120 DEG C -150 DEG C, such as 135 DEG C 6-10 hours, such as 8
Hour, obtain (SO4)2-/TiO2- ZnO mixed crystal solid acid carrier complex catalysts.
In another of the invention preferred embodiment, described 2,2,6,6- tetramethylpiperidinols and unsaturated organic dibasic acid
It is reacted in the solvent of such as absolute ethyl alcohol.
Preferably, the chemical reaction temperature is 60 DEG C -70 DEG C, and the reaction time is 5-8 hours, is more preferably 5-6 hours.
Preferably, after the chemical reaction, at least 1 hour is stood, collects sediment.
Preferably, the weight proportion of catalyst used in the preparation method for：
Preferably, the parts by weight of chemical raw material used in the preparation method for：
Second method of the present invention is to provide a kind of 2,2,6,6- tetramethyl -4- piperidine esters for light stabilizer
Object is closed, which meets general formula (I)：
Wherein, R C4-20Alkyl, at least one conjugate moiety is contained in the alkyl.
Preferably, the compound is formula (III) compound.
2,2,6, the 6- tetramethyl -4- piperidine esters light stabilizers of the present invention have the light stabilizer of space steric effect,
It is also simultaneously reaction intermediate, is mainly used in other high molecular materials such as plastic film, coating, papermaking, engineering plastics, it can be straight
Participation chemical reaction is connect, significantly improves the light aging resisting of product, extends the service life of product.The present invention uses (SO4)2-/
TiO2- ZnO mixed crystal solid acid carrier complex catalysts, can be activated inactive at typical condition using catalyst acidity height
Saturated hydrocarbons can make saturated hydrocarbons that various chemical reactions occur, and the chemical reaction that some can also be made harsh is under normal conditions
It carries out, the shortcomings that overcoming liquid acid, has the advantages that can be easily separated with reaction system, not etching apparatus, environmental-friendly.
Specific embodiment
The present invention is described in more detail below by specific embodiment, for a better understanding of the present invention,
But following embodiments are not intended to limit the scope of the invention.
The present invention provides a kind of 2,2,6,6- tetramethyl -4- piperidine ester light stabilizers, which meets general formula
(I)：
Wherein, R C4-20Alkyl, at least one conjugate moiety is contained in the alkyl..
Preferably, the light stabilizer is formula (II) compound.
Embodiment 1：
The synthetic method of 2,2,6,6- tetramethyl -4- piperidine ester light stabilizers of formula (II), includes the following steps：Equipped with
The 100 parts of 2,2,6,6- tetramethylpiperidinols and 50 being dissolved in 300 parts of anhydrous ethanol solvents are added in the four-hole boiling flask of stirring
Part muconic acid, adds 1 part of potassium rhodanide, 0.1 part of radium chloride sodium, 1 part of 98% concentrated sulfuric acid, 5 parts of (SO4)2-/TiO2- ZnO mixed crystal
Solid acid carrier complex catalyst, under the conditions of 60 DEG C, back flow reaction 6 hours after reaction, stands 1 hour, detaches lower floor
Then sediment is evaporated under reduced pressure, until during pulpous state, then with 200 parts of mixings of redistilled water, stand 20 minutes, take
Layer segment；By top section again with 200 parts of mixings of redistilled water, 20 minutes are stood, then take top section；Pass through decompression
It is dry, obtain faint yellow solid muconic acid two (- 4 base of 2,2,6,6- tetramethyl -4- piperidines) ester.
Wherein, (SO4)2-/TiO2- ZnO mixed crystal solid acid carrier complex catalysts, are prepared by following steps：
Step 1：By 20 parts of TiCl4, 20 parts of zinc nitrates be dispersed in 100 parts of deionized waters, be warming up to 95 DEG C, immediately after
50 part of 25% ammonium hydroxide, 5 parts of sodium tetraborates and 3 parts of basic nickel carbonates are added in, keep the temperature 3 hours, are then down to room temperature, stand 3 hours
Afterwards, filtering precipitate is cleaned 3 times every time with 100 parts of deionized waters, dry to moisture all evaporations at 120 DEG C with decompression method；
Step 2：The product that step 1 obtains is roasted 3 hours at 850 DEG C；
Step 3：Step 2 products therefrom is impregnated 2 hours in 10% sulfuric acid solution, then roasting 4 is small at 550 DEG C
When；
Step 4：1 part of triphenylphosphine is closed into cobalt and 3 parts of ferrocene mix, after being dissolved with 20 parts of absolute ethyl alcohols, is added to step 3
In obtained product, ethyl alcohol is removed at 80 DEG C, then dry 8 hours at 135 DEG C, obtain (SO4)2-/TiO2- ZnO mixed crystal solid acids
Carrier complex catalyst.
Embodiment 2：
The synthetic method of 2,2,6,6- tetramethyl -4- piperidine ester light stabilizers of formula (II), includes the following steps：Equipped with
The 200 parts of 2,2,6,6- tetramethylpiperidinols and 100 being dissolved in 300 parts of anhydrous ethanol solvents are added in the four-hole boiling flask of stirring
Part muconic acid, adds 3 parts of potassium rhodanides, 0.3 part of radium chloride sodium, 3 part of 98% concentrated sulfuric acid, 10 parts of (SO4)2-/TiO2- ZnO is mixed
Brilliant solid acid carrier complex catalyst, under the conditions of 70 DEG C, back flow reaction 5 hours after reaction, stands 1 hour, under separation
Layer sediment, is then evaporated under reduced pressure, until during pulpous state, then with 200 parts of mixings of redistilled water, stand 20 minutes, take
Top section；By top section again with 200 parts of mixings of redistilled water, 20 minutes are stood, then take top section；By subtracting
It press dry dry, obtains faint yellow solid muconic acid two (- 4 base of 2,2,6,6- tetramethyl -4- piperidines) ester.
Wherein, (SO4)2-/TiO2The preparation method is the same as that of Example 1 for-ZnO mixed crystal solid acid carriers complex catalyst.
Embodiment 3：
The synthetic method of 2,2,6,6- tetramethyl -4- piperidine ester light stabilizers of formula (II), includes the following steps：Equipped with
The 150 parts of 2,2,6,6- tetramethylpiperidinols and 75 being dissolved in 300 parts of anhydrous ethanol solvents are added in the four-hole boiling flask of stirring
Part muconic acid, adds 2 parts of potassium rhodanides, 0.2 part of radium chloride sodium, 2 part of 98% concentrated sulfuric acid, 8 parts of (SO4)2-/TiO2- ZnO mixed crystal
Solid acid carrier complex catalyst, under the conditions of 65 DEG C, back flow reaction 5.5 hours after reaction, stands 1 hour, under separation
Layer sediment, is then evaporated under reduced pressure, until during pulpous state, then with 200 parts of mixings of redistilled water, stand 20 minutes, take
Top section；By top section again with 200 parts of mixings of redistilled water, 20 minutes are stood, then take top section；By subtracting
It press dry dry, obtains faint yellow solid muconic acid two (- 4 base of 2,2,6,6- tetramethyl -4- piperidines) ester.
Wherein, (SO4)2-/TiO2The preparation method is the same as that of Example 1 for-ZnO mixed crystal solid acid carriers complex catalyst.
Embodiment 4：
With muconic acid two (- 4 base of 2,2,6,6- tetramethyl -4- piperidines) ester of the present invention, using additive amount as 1%, production
The agricultural fruit trees protection stone paper of 0.04mm thickness, the agricultural fruit trees protection with being not added with light stabilizer production 0.04mm thickness of the present invention
With stone paper, the performance data that every month was measured by 5 months after sunshine natural aging is compared, and comparison result is see table 1.
Table 1
In table, tensile strength is with KY8000 universal tensile testing machines, the long 4.0cm of test sample, width 2.5cm.
By table 1 it is found that the stone paper after adding in light stabilizer of the present invention is after natural aging in 5 months, tensile strength is also
There is more than 50% retention rate, illustrate the function admirable of the light stabilizer of the present invention.
Specific embodiments of the present invention are described in detail above, but it is intended only as example, it is of the invention and unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
It substitutes also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (5)
1. a kind of preparation method of light stabilizer intermediate, which is characterized in that by 2,2,6,6- tetramethylpiperidinols and 1,3- fourth
Diene -1,4- dicarboxylic acids carries out esterification and obtains；Wherein, the structure formula (I) of the light stabilizer intermediate is as follows：
Wherein, the esterification is in (SO4)2-/
TiO2- ZnO mixed crystal solid acid carriers complex catalyst, potassium rhodanide, radium chloride sodium and 98% concentrated sulfuric acid catalysis under carry out.
2. the preparation method according to claim 1, which is characterized in that (SO4)2-/TiO2- ZnO mixed crystal solid acid carriers
Complex catalyst is prepared by following steps：
Step 1：By TiCl4, zinc nitrate be dispersed in water, be warming up to 90 DEG C -100 DEG C, then add in ammonium hydroxide, sodium tetraborate and alkali
Formula nickelous carbonate keeps the temperature 2-4 hours, after being then cooled to 40 DEG C hereinafter, standing at least 2 hours, collects sediment；
Step 2：The sediment is roasted 2-4 hours at 700 DEG C -900 DEG C；
Step 3：Step 2 gained product of roasting is impregnated at least 2 hours in the sulfuric acid solution of 10% mass concentration, Ran Hou
It is roasted 3-5 hours at 500 DEG C -600 DEG C；
Step 4：The product that triphenylphosphine closes cobalt, ferrocene mixes, step 3 obtains is disperseed in a solvent, after removing solvent, then
It is dried 6-10 hours at 120 DEG C -150 DEG C, obtains (SO4)2-/TiO2- ZnO mixed crystal solid acid carrier complex catalysts.
3. preparation method according to claim 1 or 2, which is characterized in that described 2,2,6,6- tetramethylpiperidinols and 1,
3- butadiene -1,4- dicarboxylic acids carries out the esterification in a solvent.
4. preparation method according to claim 1 or 2, which is characterized in that the temperature of the esterification is 60 DEG C -70
DEG C, the reaction time is 5-8 hours.
5. preparation method according to claim 1 or 2, which is characterized in that the catalyst used in the preparation method
Weight proportion is：
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|---|---|---|---|---|
| US4487870A (en) * | 1982-12-27 | 1984-12-11 | Exxon Research & Engineering Co. | UV Stabilizer system and UV stabilized polyolefins |
| US4921962A (en) * | 1988-10-19 | 1990-05-01 | Ciba-Geigy Corporation | Process for preparing N-hydrocarbyloxy derivatives of sterically hindered amines |
| 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 |
| CN103657732A (en) * | 2013-10-16 | 2014-03-26 | 上海东升新材料有限公司 | Preparation method of SO4<2->/TiO2-ZnO mixed crystal solid acid carrier coordination catalyst |
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- 2014-10-17 CN CN201410554593.6A patent/CN105566204B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487870A (en) * | 1982-12-27 | 1984-12-11 | Exxon Research & Engineering Co. | UV Stabilizer system and UV stabilized polyolefins |
| US4921962A (en) * | 1988-10-19 | 1990-05-01 | Ciba-Geigy Corporation | Process for preparing N-hydrocarbyloxy derivatives of sterically hindered amines |
| 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 |
| CN103657732A (en) * | 2013-10-16 | 2014-03-26 | 上海东升新材料有限公司 | Preparation method of SO4<2->/TiO2-ZnO mixed crystal solid acid carrier coordination catalyst |
Non-Patent Citations (1)
| Title |
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| Thermal stability and thermal decomposition study of hindered amine light stabilizers;A.I.Balabanovich et al.;《thermochimica acta》;20070324;第459卷;第1-8页 * |
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Denomination of invention: A light stabilizer intermediate 2,2,6,6-tetramethyl-4-piperidine ester compound and its preparation method Effective date of registration: 20210125 Granted publication date: 20180619 Pledgee: Bank of Hangzhou Limited by Share Ltd. Shanghai branch Pledgor: SHANGHAI DONGSHENG NEW MATERIALS Co.,Ltd. Registration number: Y2021310000003 |
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Date of cancellation: 20230308 Granted publication date: 20180619 Pledgee: Bank of Hangzhou Limited by Share Ltd. Shanghai branch Pledgor: SHANGHAI DONGSHENG NEW MATERIALS Co.,Ltd. Registration number: Y2021310000003 |