CN108623566A - A kind of synthesis technology of hindered amine light stabilizer 944 - Google Patents
A kind of synthesis technology of hindered amine light stabilizer 944 Download PDFInfo
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- CN108623566A CN108623566A CN201810401814.4A CN201810401814A CN108623566A CN 108623566 A CN108623566 A CN 108623566A CN 201810401814 A CN201810401814 A CN 201810401814A CN 108623566 A CN108623566 A CN 108623566A
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- light stabilizer
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
Abstract
The present invention relates to a kind of synthesis technologies of hindered amine light stabilizer 944, are as follows：Cyanuric Chloride is added into solvent after stirring and dissolving, t-octanylamine solution ＆ stir is added dropwise, is kept the temperature after being added dropwise, sodium hydroxide solution is added dropwise, is kept the temperature after being added dropwise, washing filtering, obtains 1 solution of intermediate；It is kept the temperature after 1 solution of intermediate is mixed with water, then cooling filtering precipitation, obtains intermediate 2；Sodium hydroxide solution and hexamethylene diamine piperidines are sequentially added into 1 solution of intermediate, then heats to 90 120 DEG C, after keeping the temperature 0.5 2h, continue to heat up, often heat up 5 15 DEG C, keeps the temperature 0.5 2h, it waits for that solution is heated to 130 160 DEG C, then keeps the temperature 5 15h, obtain 3 solution of intermediate；Reaction solution is washed, is filtered by heat preservation after being stirred in the addition to 3 solution of intermediate of intermediate 2, precipitation obtains hindered amine light stabilizer 944；The present patent application invention disclosed method, reduces the generation of small molecule product, reduces by-product, improves product quality, yield.
Description
Technical field
The present invention relates to a kind of synthesis technologies of hindered amine light stabilizer 944, belong to the preparation field of light stabilizer.
Background technology
Hindered amine light stabilizer 944 is one of the kind that application performance is best in current light stabilizer in the world.It has
Low volatility, thermal stability is high, and anti-extracting property is good, good without easy to migrate with resin compatible, and plastics are easily molded and using stingless
Swash the hot spots such as property.
In 944 synthetic method of presently disclosed hindered amine light stabilizer, there are mainly two types of：Two-step method, three-step approach.Wherein two
Footwork is to be obtained by the reaction intermediate 2- t-octanylamines base -4,6- bis- chloro- 1 with Cyanuric Chloride and t-octanylamine, 3,5 triazines, that is, intermediate 1,
Then high pressure polymerisation is carried out with hexamethylene diamine piperidines, temperature programming obtains hindered amine light stabilizer 944.Three-step approach is then first with trimerization
Chlorine cyanogen and t-octanylamine generate intermediate 1, then add to intermediate 1 on hexamethylene diamine piperidines, finally again with a small amount of hexamethylene diamine
Piperidines polymerize to obtain hindered amine light stabilizer 944.Both methods is required for that excessive hexamethylene diamine piperazine is added in the polymerization
Pyridine polymerize to terminate, therefore will produce a large amount of cyclic annular insoluble matter and small molecule product, increases the difficulty of post-processing, product matter
Amount reduces, cost increase.
Invention content
The present invention is directed to the deficiencies in the prior art, provides a kind of synthesis technology of hindered amine light stabilizer 944,
To solve problems of the prior art.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of synthesis technology of hindered amine light stabilizer 944, is as follows：
（1）Cyanuric Chloride is added into solvent after stirring and dissolving, t-octanylamine solution ＆ stir is added dropwise, is kept the temperature after being added dropwise,
Dropwise addition mass fraction is 20-40% sodium hydroxide solutions, is kept the temperature after being added dropwise, washing filtering, obtains 1 solution of intermediate；
（2）It is kept the temperature after 1 solution of intermediate is mixed with water, then cooling filtering precipitation, obtains intermediate 2；
（3）The sodium hydroxide solution and hexamethylene diamine piperidines that mass fraction is 5%-40% are sequentially added into 1 solution of intermediate, so
After be warming up to 90-120 DEG C, after keeping the temperature 0.5-2h, continue to heat up, often heat up 5-15 DEG C, keep the temperature 0.5-2h, wait for that solution is heated to
130-160 DEG C, then 5-15h is kept the temperature, obtain 3 solution of intermediate；
（4）Will intermediate 2 be added to after stirring in 3 solution of intermediate heat preservation reaction solution is washed, is filtered, precipitation obtain by
Hinder amine light stabilizer 944.
As an improvement of the present invention, the step（1）, step（2）Middle solvent is toluene, dimethylbenzene, C7-C10 alkane
Hydrocarbon any one.
As an improvement of the present invention, the step（1）The temperature that middle t-octanylamine solution is added dropwise is 10-50 DEG C, is added dropwise
Time 6-15h, soaking time 1-5h.
As an improvement of the present invention, the step（1）The temperature that middle sodium hydroxide solution is added dropwise be at 10-50 DEG C,
Time for adding is 2-8h, soaking time 2-6h.
As an improvement of the present invention, the step（2）The temperature of middle reaction is 40-80 DEG C, soaking time 2-6h.
As an improvement of the present invention, the step（1）The weight ratio of middle solvent and Cyanuric Chloride is（2-6）：1；Institute
State step（1）The molar ratio of middle t-octanylamine and Cyanuric Chloride is（1.0-1.1）:1；The step（1）Middle sodium hydroxide and trimerization
The molar ratio of chlorine cyanogen is（1-3）:1.
As an improvement of the present invention, the step（2）The weight of middle water is 1 weight of intermediate in 1 solution of intermediate
0.1-5 times.
As an improvement of the present invention, the step（3）Middle sodium hydroxide solution and intermediate 1 in 1 solution of intermediate
Weight ratio be（1-5）：1, the step（3）The molar ratio of middle hexamethylene diamine piperidines and intermediate 1 in 1 solution of intermediate is（1-
2）:1.
As an improvement of the present invention, the step（4）Mole of middle intermediate 2 and intermediate 3 in 3 solution of intermediate
Than for（1-3）：1.
As an improvement of the present invention, the step（4）The temperature of middle stirring is 100-180 DEG C, soaking time 2-
15h。
The present invention removes hydrolyzing intermediate during preparing intermediate 2, using water, of low cost, and post-processing is easy,
Can be not required to post-processing can directly be transferred to participation reaction in polymeric kettle.
During preparing intermediate 3, by accurately controlling the degree of polymerization of intermediate 1 and hexamethylene diamine piperidines, reduce small
The possibility of the generation of molecular product and intermediate 1 and hexamethylene diamine piperidines cyclization improves product quality, and post-processing is easy, even
Next step reaction can directly be carried out.
Intermediate 2 is prepared using three different reaction conditions of chlorine on Cyanuric Chloride molecule.Using intermediate 2 as polymerization
Sealing end so that we control the degree of polymerization of reaction under conditions of not introducing other substances, reduce hindered amine light stabilizer
944 molecular weight widths.The last one chlorine atom on Cyanuric Chloride is eliminated, using hydroxyl and t-octanylamine as end-capping group, is then carried
The high compatibility of light stabilizer 944 and downstream product, enhances product performance
Reactive chemistry equation involved in the present invention is as follows：
Following reaction equation indicates the end capping reaction of hindered amine light stabilizer 944：
As a result of the above technology, the present invention compared with the prior art, has the advantage that as follows：
The invention discloses a kind of synthesis technology of hindered amine light stabilizer 944, step is：T-octanylamine adds with Cyanuric Chloride
At then hydrolyzing, then by itself and hexamethylene diamine piperidines addition synthetic intermediate, it is anti-that polymerization participated in using this intermediate as terminal
It answers.The present patent application invention disclosed method, reduces the generation of small molecule product, reduces by-product, and it is difficult to reduce post-processing
Degree improves product quality, yield.
Specific implementation mode
With reference to embodiment, the present invention is furture elucidated.
Embodiment 1：
A kind of synthesis technology of hindered amine light stabilizer 944 is as follows：
（1）92.3g Cyanuric Chlorides are poured into flask, 185g dimethylbenzene is added, 64.5g t-octanylamine solution is added dropwise at 10 DEG C,
Time for adding is 6h, after keeping the temperature 5h, the sodium hydroxide solution of 100g a concentration of 20% is slowly added dropwise, control temperature is on 10 DEG C of left sides
The right side, 2h are added dropwise, and then keep the temperature 6h.After reaction, through cooling down, washing and obtaining 1 solution of 322g intermediates（Wherein contain in 137g
Mesosome 1）.
（2）Take 1 solution of 129g intermediates（Intermediate containing 54.8g 1）It pours into flask, 5.5g water is added, it is anti-at 40 DEG C
6h is answered, cools down, water, filtering, precipitation is divided to obtain 50g intermediates 2.
（3）Take 1 solution of 193g intermediates（Intermediate containing 82.2g 1）It pours into autoclave, it is dense to sequentially add 82.2g
Degree is 40% sodium hydroxide solution, 152g hexamethylene diamine piperidines.100 DEG C are warming up to, 0.5h is kept the temperature, is then often heated up 10 DEG C, heat preservation
2h, until 130 DEG C, then 6h is kept the temperature, obtain 3 solution of intermediate（Intermediate containing 210g 3）；
（4）24.7g intermediates 2 are added into 3 solution of above-mentioned intermediate, react 5h at 100 DEG C.It is obtained through washing, filtering, precipitation
Hindered amine light stabilizer 944.It is 2100-2400 between molecular weight area, light transmittance 98.5%, yield is 95% or more.
Embodiment 2：
A kind of synthesis technology of hindered amine light stabilizer 944 is as follows：
（1）92.3g Cyanuric Chlorides are poured into flask, 370 toluene are added, 68g t-octanylamine solution are added dropwise at 30 DEG C, when dropwise addition
Between be 11h, after keep the temperature 2.5h, be slowly added dropwise the sodium hydroxide solution of 120g a concentration of 32%, control temperature at 30 DEG C or so,
6h is added dropwise, and then keeps the temperature 4h.After reaction, through cooling down, washing and obtaining 1 solution of intermediate.
（2）Take 1 solution of 200g intermediates（Intermediate containing 55.2g 1）It pours into flask, the water of 50g is added, it is anti-at 60 DEG C
4h is answered, cools down, water, filtering, precipitation is divided to obtain 50.3g intermediates 2.
（3）Take 1 solution of intermediate of 300g（Intermediate containing 82.8g 1）It pours into autoclave, it is dense to sequentially add 200g
Degree is 15% sodium hydroxide solution, and 158g hexamethylene diamine piperidines is warming up to 110 DEG C, keeps the temperature 1.5h, then often heats up 15 DEG C, heat preservation
1.5h, until 150 DEG C, then keep the temperature 10h.Obtain 3 solution of intermediate（Intermediate containing 217g 3）；
（4）50.3g intermediates 2 are added into 3 solution of above-mentioned intermediate, react 8h at 170 DEG C.It is obtained through washing, filtering, precipitation
Hindered amine light stabilizer 944.It is 2500-2630 between molecular weight area, light transmittance 98.5%, yield is 98% or more.
Embodiment 3：
A kind of synthesis technology of hindered amine light stabilizer 944 is as follows：
（1）The Cyanuric Chloride of 92.3g is poured into flask, the toluene of 554g is added, the t-octanylamine that 71g is added dropwise at 50 DEG C is molten
After keeping the temperature 1h the sodium hydroxide solution of 150g a concentration of 40% is slowly added dropwise, control temperature is 50 in liquid, time for adding 15h
DEG C or so, 8h is added dropwise, and then keeps the temperature 2h.After reaction, through cooling down, washing and obtaining 1 solution of intermediate.
（2）Take 1 solution of 276.5g intermediates（Intermediate containing 54.2g 1）It pours into flask, the water of 271g is added, at 80 DEG C
Lower reaction 2h cools down, water, filtering, precipitation is divided to obtain 50g intermediates 2.
（3）Take 1 solution of intermediate of 417.7g（Intermediate containing 83g 1）It pours into autoclave, it is dense to sequentially add 415g
Degree is 5% sodium hydroxide solution, and 212.7g hexamethylene diamine piperidines is warming up to 120 DEG C, keeps the temperature 2h, then often heats up 5 DEG C, heat preservation
0.5h, until 160 DEG C, then keep the temperature 15h.Obtain 3 solution of intermediate (intermediate containing 217g 3)；
（4）76.7g intermediates 2 are added into 3 solution of above-mentioned intermediate, react 15h at 180 DEG C.Through washing, filtering, precipitation
Obtain hindered amine light stabilizer 944.It is 2300-2600 between molecular weight area, light transmittance 98.5%, yield is 95% or more.
Above-described embodiment is only the preferred technical solution of the present invention, and is not construed as the limitation for the present invention, the present invention
Protection domain should with claim record technical solution, including claim record technical solution in technical characteristic etc.
It is protection domain with alternative, i.e., equivalent replacement within this range is improved, also within protection scope of the present invention.
Claims (10)
1. a kind of synthesis technology of hindered amine light stabilizer 944, which is characterized in that be as follows：
（1）Cyanuric Chloride is added into solvent after stirring and dissolving, t-octanylamine solution ＆ stir is added dropwise, is kept the temperature after being added dropwise,
Dropwise addition mass fraction is 20-40% sodium hydroxide solutions, is kept the temperature after being added dropwise, washing filtering, obtains 1 solution of intermediate；
（2）It is kept the temperature after 1 solution of intermediate is mixed with water, then cooling filtering precipitation, obtains intermediate 2；
（3）The sodium hydroxide solution and hexamethylene diamine piperidines that mass fraction is 5%-40% are sequentially added into 1 solution of intermediate, so
After be warming up to 90-120 DEG C, after keeping the temperature 0.5-2h, continue to heat up, often heat up 5-15 DEG C, keep the temperature 0.5-2h, wait for that solution is heated to
130-160 DEG C, then 5-15h is kept the temperature, obtain 3 solution of intermediate；
（4）Will intermediate 2 be added to after stirring in 3 solution of intermediate heat preservation reaction solution is washed, is filtered, precipitation obtain by
Hinder amine light stabilizer 944.
2. a kind of synthesis technology of hindered amine light stabilizer 944 according to claim 1, it is characterised in that：The step
（1）, step（2）Middle solvent be toluene, dimethylbenzene, C7-C10 alkane any one.
3. a kind of synthesis technology of hindered amine light stabilizer 944 according to claim 1, it is characterised in that：The step
（1）The temperature that middle t-octanylamine solution is added dropwise is 10-50 DEG C, time for adding 6-15h, soaking time 1-5h.
4. a kind of synthesis technology of hindered amine light stabilizer 944 according to claim 1, it is characterised in that：The step
（1）The temperature that middle sodium hydroxide solution is added dropwise is at 10-50 DEG C, time for adding 2-8h, soaking time 2-6h.
5. a kind of synthesis technology of hindered amine light stabilizer 944 according to claim 1, it is characterised in that：The step
（2）The temperature of middle reaction is 40-80 DEG C, soaking time 2-6h.
6. a kind of synthesis technology of hindered amine light stabilizer 944 according to claim 1, it is characterised in that：The step
（1）The weight ratio of middle solvent and Cyanuric Chloride is（2-6）：1；The step（1）The molar ratio of middle t-octanylamine and Cyanuric Chloride is
（1.0-1.1）:1；The step（1）The molar ratio of middle sodium hydroxide and Cyanuric Chloride is（1-3）:1.
7. a kind of synthesis technology of hindered amine light stabilizer 944 according to claim 1, it is characterised in that：The step
（2）The weight of middle water is 0.1-5 times of 1 weight of intermediate in 1 solution of intermediate.
8. a kind of synthesis technology of hindered amine light stabilizer 944 according to claim 1, it is characterised in that：The step
（3）The weight ratio of middle sodium hydroxide solution and intermediate 1 in 1 solution of intermediate is（1-5）：1, the step（3）Middle hexamethylene diamine
The molar ratio of piperidines and intermediate 1 in 1 solution of intermediate is（1-2）:1.
9. a kind of synthesis technology of hindered amine light stabilizer 944 according to claim 1, it is characterised in that：The step
（4）Middle intermediate 2 and the molar ratio of intermediate 3 in 3 solution of intermediate are（1-3）：1.
10. a kind of synthesis technology of hindered amine light stabilizer 944 according to claim 1, it is characterised in that：The step
（4）The temperature of middle stirring is 100-180 DEG C, soaking time 2-15h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678842A (en) * | 2019-01-31 | 2019-04-26 | 宿迁联盛科技股份有限公司 | A kind of production technology of 944 intermediate of continuous production light stabilizer |
| CN113861168A (en) * | 2021-09-16 | 2021-12-31 | 宿迁联盛科技股份有限公司 | Polymeric hindered amine light stabilizer and preparation method thereof |
| CN114507216A (en) * | 2022-03-08 | 2022-05-17 | 河南省化工研究所有限责任公司 | Preparation method of hindered amine light stabilizer 944 |
| WO2022184399A1 (en) | 2021-03-05 | 2022-09-09 | Basf Se | Process for preparing n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine |
| 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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| US4492791A (en) * | 1982-05-04 | 1985-01-08 | Ciba-Geigy Corporation | Process for the preparation of polyaminotriazines |
| CN1165138A (en) * | 1995-12-04 | 1997-11-19 | 希巴特殊化学控股公司 | Block oligomers containing 2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic material |
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| US4492791A (en) * | 1982-05-04 | 1985-01-08 | Ciba-Geigy Corporation | Process for the preparation of polyaminotriazines |
| CN1165138A (en) * | 1995-12-04 | 1997-11-19 | 希巴特殊化学控股公司 | Block oligomers containing 2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678842A (en) * | 2019-01-31 | 2019-04-26 | 宿迁联盛科技股份有限公司 | A kind of production technology of 944 intermediate of continuous production light stabilizer |
| WO2022184399A1 (en) | 2021-03-05 | 2022-09-09 | Basf Se | Process for preparing n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine |
| CN113861168A (en) * | 2021-09-16 | 2021-12-31 | 宿迁联盛科技股份有限公司 | Polymeric hindered amine light stabilizer and preparation method thereof |
| CN113861168B (en) * | 2021-09-16 | 2022-08-05 | 宿迁联盛科技股份有限公司 | Polymeric hindered amine light stabilizer and preparation method thereof |
| CN114507216A (en) * | 2022-03-08 | 2022-05-17 | 河南省化工研究所有限责任公司 | Preparation method of hindered amine light stabilizer 944 |
| 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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