CN103193698B - Preparation method of N-triacetic acid (1,2,2,6,6-pentamethyl-4-piperidyl) ester as hindered amine light stabilizer - Google Patents
Preparation method of N-triacetic acid (1,2,2,6,6-pentamethyl-4-piperidyl) ester as hindered amine light stabilizer Download PDFInfo
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- CN103193698B CN103193698B CN201310119226.9A CN201310119226A CN103193698B CN 103193698 B CN103193698 B CN 103193698B CN 201310119226 A CN201310119226 A CN 201310119226A CN 103193698 B CN103193698 B CN 103193698B
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- pentamethyl
- piperidyl
- ester
- catalyzer
- sodium nitride
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- -1 1,2,2,6,6-pentamethyl-4-piperidyl Chemical group 0.000 title claims abstract description 46
- 150000002148 esters Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000001412 amines Chemical class 0.000 title claims abstract description 10
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 20
- LPLDYOPZXOOCRT-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-4-yl) 2-chloroacetate Chemical compound CN1C(CC(CC1(C)C)OC(CCl)=O)(C)C LPLDYOPZXOOCRT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000035484 reaction time Effects 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000012044 organic layer Substances 0.000 claims description 9
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical group I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- 229960001701 chloroform Drugs 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Hydrogenated Pyridines (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of N-triacetic acid (1,2,2,6,6-pentamethyl-4-piperidyl) ester as a hindered amine light stabilizer. The method comprises the following steps: by taking sodium nitride and chloroacetic acid (1,2,2,6,6-pentamethyl-4-piperidyl) ester as raw materials, reacting at a definite temperature under the condition of the existence of a solvent and a catalyst, thereby preparing the N-triacetic acid (1,2,2,6,6-pentamethyl-4-piperidyl) ester. According to the method, the N-triacetic acid (1,2,2,6,6-pentamethyl-4-piperidyl) ester is synthesized by taking the sodium nitride and the chloroacetic acid (1,2,2,6,6-pentamethyl-4-piperidyl) ester as the raw materials, so that the method is simple in separation and purification process, short in reaction time and high in product yield, wherein the product yield reaches more than 94%. The N-triacetic acid (1,2,2,6,6-pentamethyl-4-piperidyl) ester is high in purity, low in energy consumption, less in environment pollution and low in cost. Therefore, the method disclosed by the invention is an ideal process for realizing the industrialization preparation.
Description
Technical field
The present invention relates to the preparation method of a kind of hindered amine light stabilizer N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester.
Background technology
N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester is the efficient hindered amine light stabilizer of a kind of macromolecular material.The duration of service that various plastic cement and coating irradiate out of doors can be extended.In use, the course of processing, smell can not be produced with polymer, also can not affect the original color of material.During high temperature process, product is not volatile.Good with most industry solvent phase dissolubility, there is superior polymer intermiscibility, be applicable to polyethylene, polypropylene, polystyrene and ABS resin.Its chemical name is: N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester; Molecular formula: C
36h
66n
4o
9; Molecular weight: 650.9.
Molecular structural formula:
Physico-chemical property: outward appearance is solid, powdery thing, thermotolerance 290 DEG C.
At present, the domestic disclosed research report of synthetic method about hindered amine light stabilizer N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester is few.According to pertinent literature content, existing with Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester, sodium nitride be raw material, synthesized N-nitrilotriacetic (1,2 under catalysts and solvents existent condition, 2,6,6-pentamethyl--4-piperidyl) ester.It is short that this method has the reaction times, and temperature of reaction is low, and aftertreatment is simple, the feature that product yield is higher.
Summary of the invention
The preparation method of hindered amine light stabilizer N-nitrilotriacetic (1,2,2,6, the 6-pentamethyl--4-piperidyl) ester that the object of the present invention is to provide a kind of product yield high.
Technical solution of the present invention is:
A kind of hindered amine light stabilizer N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) preparation method of ester is with Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester, sodium nitride be raw material, under solvent and catalyzer existent condition, solvent is methylene dichloride or trichloromethane or tetracol phenixin, preferred trichloromethane, be heated to certain temperature, the obtained N-nitrilotriacetic (1,2 of reaction, 2,6,6-pentamethyl--4-piperidyl) ester; Described catalyzer is that 4-propyl bromide or tetra isopropyl brometo de amonio or Tetrabutyl amonium bromide or cetyl trimethylammonium bromide and zinc chloride or zinc bromide or zinc iodide form, the mixture that preferred tetra isopropyl brometo de amonio and zinc iodide form.
Sodium nitride, Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester, catalyzer, solvent, gac usage ratio be by mass: sodium nitride: Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester: catalyzer: solvent: gac=1:9.25 ~ 11.95:0.06 ~ 0.18:2.41 ~ 5.23:0.003-0.005.
With sodium nitride, Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester is raw material, under solvent and catalyzer existent condition, carry out transesterification reaction, after reaction terminates, carry out filtering, washing, separate organic layer, separate that organic phase solution carries out dewatering, activated carbon decolorizing, the organic layer obtained carries out cooling down, crystallization, filters to obtain N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester.The temperature of described reaction is 40 ~ 55 DEG C, and the reaction times is 10-15h.
The present invention's sodium nitride, Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester is Material synthesis N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester, adopt the mixture catalyzer that tetra isopropyl brometo de amonio and zinc iodide form, separating-purifying process is simple, and the reaction times is short, and product yield is high, product yield can reach more than 94%, and product purity is high, and energy consumption reduces, environmental pollution is little, and cost is low, is the comparatively ideal technique realizing preparation of industrialization.
embodiment:
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and this embodiment only for explaining the present invention, does not form limiting the scope of the present invention.
A kind of hindered amine light stabilizer N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) preparation method of ester, with sodium nitride, Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester pyridine is raw material, under solvent and catalyzer existent condition, carries out transesterification reaction at a certain temperature and obtains N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester.Sodium nitride, Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester, catalyzer, solvent, gac usage ratio be by mass: sodium nitride: Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester: catalyzer: solvent: gac=1:9.25 ~ 11.95:0.06 ~ 0.18:2.41 ~ 5.23:0.003-0.005.Described catalyzer is that 4-propyl bromide or tetra isopropyl brometo de amonio or Tetrabutyl amonium bromide or cetyl trimethylammonium bromide and zinc chloride or zinc bromide or zinc iodide form, the mixture that preferred tetra isopropyl brometo de amonio and zinc iodide form, described solvent is methylene dichloride or trichloromethane or tetracol phenixin, preferred trichloromethane.。
Embodiment 1:
In the four-hole boiling flask of 250mL that thermometer is housed, add solvent 30g, sodium nitride 8.3g, Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester 29.3g, catalyzer 0.5g, loads onto prolong, starts agitator, when being warming up to 40-55 DEG C, reaction times 10-15h (with gas-chromatography monitoring reaction).After reaction terminates, carry out filtering, washing, collect organic phase, separate that organic phase solution carries out dewatering, activated carbon decolorizing, the organic layer obtained carries out cooling down, crystallization, filters to obtain N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester, product yield is 94.08%.
Embodiment 2:
In the four-hole boiling flask of 250mL that thermometer is housed, add solvent 30g, sodium nitride 8.3g, Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester 33.1g, catalyzer 0.6g, loads onto prolong, start agitator, when being warming up to 40-55 DEG C, in reaction process, constantly steam the methyl alcohol of generation, reaction times 10-15h (with gas-chromatography monitoring reaction).After reaction terminates, carry out filtering, washing, collect organic phase, separate organic phase solution and carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filters to obtain N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester, product yield is 94.36%.
Embodiment 3:
In the four-hole boiling flask of 250mL that thermometer is housed, add solvent 30g, sodium nitride 8.3g, Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester 35.9g, catalyzer 0.8g, loads onto prolong, start agitator, when being warming up to 40-55 DEG C, in reaction process, constantly steam the methyl alcohol of generation, reaction times 10-15h (with gas-chromatography monitoring reaction).After reaction terminates, carry out filtering, washing, collect organic phase, separate organic phase solution and carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filters to obtain N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester, product yield is 94.75%.
Embodiment 4:
In the four-hole boiling flask of 250mL that thermometer is housed, add solvent 30g, sodium nitride 8.3g, Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester 37.8g, catalyzer 0.8g, loads onto prolong, start agitator, when being warming up to 40-55 DEG C, in reaction process, constantly steam the methyl alcohol of generation, reaction times 10-15h (with gas-chromatography monitoring reaction).After reaction terminates, carry out filtering, washing, collect organic phase, separate organic phase solution and carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filters to obtain N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester, product yield is 94.92%.
Embodiment 5:
In the four-hole boiling flask of 250mL that thermometer is housed, add solvent 30g, sodium nitride 8.3g, Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester 33.1g, catalyzer 1.5g, loads onto prolong, start agitator, when being warming up to 40-55 DEG C, in reaction process, constantly steam the methyl alcohol of generation, reaction times 10-15h (with gas-chromatography monitoring reaction).After reaction terminates, carry out filtering, washing, collect organic phase, separate organic phase solution and carry out dewatering, decolouring, the organic layer obtained carries out cooling down, crystallization, filters to obtain N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester, product yield is 95.18%.
The present invention's sodium nitride, Mono Chloro Acetic Acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester is Material synthesis N-nitrilotriacetic (1,2,2,6,6-pentamethyl--4-piperidyl) ester, adopt the mixture catalyzer that tetra isopropyl brometo de amonio and zinc iodide form, separating-purifying process is simple, and the reaction times is short, and product yield is high, product yield can reach more than 94%, and product purity is high, and energy consumption reduces, environmental pollution is little, and cost is low, is the comparatively ideal technique realizing preparation of industrialization.
Claims (1)
1. a hindered amine light stabilizer N-nitrilotriacetic (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) preparation method of ester, it is characterized in that: with sodium nitride, Mono Chloro Acetic Acid (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester is raw material, react under the certain temperature that catalysts and solvents exists, after reaction terminates, filter, washing, separate organic layer, separate organic phase solution to dewater, activated carbon decolorizing, the organic layer obtained carries out cooling down, crystallization, filter to obtain N-nitrilotriacetic (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester, sodium nitride, Mono Chloro Acetic Acid (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester, catalyzer, solvent, the usage ratio of gac is by mass: sodium nitride: Mono Chloro Acetic Acid (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester: catalyzer: solvent: gac=1:9.25 ~ 11.95:0.06 ~ 0.18:2.41 ~ 5.23:0.003-0.005, described solvent is trichloromethane, described catalyzer is the mixture that tetra isopropyl brometo de amonio and zinc iodide form, its mass ratio is tetra isopropyl brometo de amonio: zinc iodide=1:0.5-1, the temperature of described reaction is 40 ~ 55 DEG C, reaction times is 10-15h.
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| CN201310119226.9A CN103193698B (en) | 2013-04-08 | 2013-04-08 | Preparation method of N-triacetic acid (1,2,2,6,6-pentamethyl-4-piperidyl) ester as hindered amine light stabilizer |
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| CN201310119226.9A CN103193698B (en) | 2013-04-08 | 2013-04-08 | Preparation method of N-triacetic acid (1,2,2,6,6-pentamethyl-4-piperidyl) ester as hindered amine light stabilizer |
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| CN103193698B true CN103193698B (en) | 2015-02-04 |
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| CN110283116B (en) * | 2019-06-27 | 2022-09-09 | 绍兴瑞康生物科技有限公司 | Hindered amine light stabilizer, preparation and application thereof |
| CN115557935A (en) * | 2022-10-17 | 2023-01-03 | 南通大学 | Preparation method of hindered amine light stabilizer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4110306A (en) * | 1975-12-01 | 1978-08-29 | Argus Chemical Corporation | Stabilizers for synthetic polymers comprising 2,2,6,6-tetramethyl-4-piperidyl carboxylic acid ester, a triphosphite, and an acid phosphite or salt thereof |
| US4619958A (en) * | 1982-10-02 | 1986-10-28 | Adeka Argus Chemical Co., Ltd. | Mixed 2,2,6,6-tetramethyl piperidinyl carboxylic acid ester and amide light stabilizers and stabilized synthetic polymers |
| JP3229748B2 (en) * | 1994-05-18 | 2001-11-19 | 三洋電機株式会社 | Electronic component automatic mounting device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2926185B2 (en) * | 1990-02-05 | 1999-07-28 | 旭電化工業株式会社 | Heat resistant ABS resin composition with improved light stability |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4110306A (en) * | 1975-12-01 | 1978-08-29 | Argus Chemical Corporation | Stabilizers for synthetic polymers comprising 2,2,6,6-tetramethyl-4-piperidyl carboxylic acid ester, a triphosphite, and an acid phosphite or salt thereof |
| US4619958A (en) * | 1982-10-02 | 1986-10-28 | Adeka Argus Chemical Co., Ltd. | Mixed 2,2,6,6-tetramethyl piperidinyl carboxylic acid ester and amide light stabilizers and stabilized synthetic polymers |
| JP3229748B2 (en) * | 1994-05-18 | 2001-11-19 | 三洋電機株式会社 | Electronic component automatic mounting device |
Non-Patent Citations (3)
| Title |
|---|
| Thermal oxidation of polypropylene containing hindered piperidine compounds;Ye Yongcheng;《Polymer Degradation and Stability》;19921231;第37卷;11-17，第12页右栏第1-2段 * |
| Tris-Nitrilotriacetic Acids of Subnanomolar Affinity Toward Hexahistidine Tagged Molecules;ZhaohuaHuang等;《Bioconjugate Chem.》;20091231;第20卷;1667-1672 * |
| 叶永成,张涛,陈忠汉.四 甲基和五甲基崛咤对聚合物的稳定作用(二).《塑料工业》.1986,(第二期),45-48. * |
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