CN106905225A - A kind of preparation method of multi-functional Polvamide stabilisers - Google Patents
A kind of preparation method of multi-functional Polvamide stabilisers Download PDFInfo
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- CN106905225A CN106905225A CN201710111609.XA CN201710111609A CN106905225A CN 106905225 A CN106905225 A CN 106905225A CN 201710111609 A CN201710111609 A CN 201710111609A CN 106905225 A CN106905225 A CN 106905225A
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- tetramethyl
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- piperidyls
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- benzenedicarboxamides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/56—Nitrogen atoms
- C07D211/58—Nitrogen atoms attached in position 4
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- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
The present invention relates to N, N' double (2,2, the piperidyl of 6,6 tetramethyl 4) 1,3 benzenedicarboxamides preparation method, with DMIP or dimethyl isophthalate and 2,2,6, the amino piperidine of 6 tetramethyl 4 is raw material, solvent and catalyst are not used, is first reacted 12 hours at 190 DEG C, then heat to 220 240 DEG C and react 36 hours, direct amine solution, prepares target product.
Description
Technical field
The present invention relates to Polvamide stabilisers N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'-
（I）Preparation method.
（I）.
Background technology
Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N, N'-（I）It is a kind of excellent polyamide light
Stabilizer and processing aid；It passes through " molecular recognition " and interlinkage amidatioon and polyamide compatible, makes its stability to nylon
The limit of beyond tradition light stabilizer, can be applied in combination with UV- absorbents, significantly improve light stablizing effect；Polyamides can also be improved
The process of amine melt, stable polyamides melt pressure, steady process, fracture of wire when reducing Fypro spinning；Its
Molecular structure neutral and alkali group and its secondary action, can strengthen the affinity of metal dye and acid dyes, enable polyamide steady
Fixed, economic, compatible and Inner dyeing.
Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N, N'-（I）Preparation, main side at present
Method is to use 1,3- phthalyl chlorides (IPC) and 2,2,6,6- tetramethyl -4- amino piperidines（II）Reaction.Technology is updated,
There is following patent report：EP 1556350 (equivalent CN 1671664 A, CN 1279024 C, WO 2004016591A1,
US 7632949), CN 105481759 A, CN 103554009 A, CN 103554009B, CN 103508938 A, CN
The A of 103508938B, CN 103030588.These methods use 1,3- phthalyl chlorides（IPC）, because acyl chlorides is easily hydrolyzed, and
The hydrogen chloride in acid binding agent with generation need to be used.And double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzene of the N of generation, N'-
Diformamide（I）Insoluble in atent solvent（Such as aromatic hydrocarbons, chloralkane etc.）, cause reaction controlling difficult, purification process trouble is dirty
Water is more.
（I）
The application that the A of CN 104974075 are proposed relate to without 1,3- phthalyl chlorides（IPC）New design：Use isophthalic diformazan
Acid diesters（III）With 2,2,6,6- tetramethyl -4- amino piperidines（II）Through alkyl aluminum be catalyzed normal pressure amine solution, wherein specifically mention with
Trimethyl aluminium（Embodiment 1-4,7,8, right 6）Or diethyl aluminum（Embodiment 5,6, right 6）, or tri-propyl aluminum, triisopropyl
Aluminium, tri-butyl aluminum（Right 6）It is catalyst, toluene（Embodiment 1-5, right 7）, methyl alcohol（Embodiment 7, right 7）Or ethanol（It is real
Apply example 6, right 7）Be solvent, DMIP or dimethyl isophthalate or M-phthalic acid diisopropyl ester with
Then 2,2,6,6- tetramethyl -4- amino piperidines, azeotropic distillation lowers the temperature, washes, filters, is dried to obtain target product.
（I）
But catalyst trialkylaluminium is inflammable and explosive.Trimethyl aluminium is at normal temperatures and pressures colourless transparent liquid, in atmosphere certainly
Combustion, moment can just catch fire, alcohol type, acids intense reaction with active hydrogen；React fierce with water, even if in cold water
Explosive decomposition can be produced to react, and generate methane, can also be under fire sometimes.The A of CN 104974075 mention diethyl aluminum material name
Claim incorrect imperfect, and the A of CN 104974075 mention azeotropic distillation and go out methyl alcohol（Active hydrogen）, therefore this application has
The principles of science problem and severe safety problem, it is impossible to implement.
The content of the invention
The present invention is to solve the problems, such as above prior art, there is provided one kind without acyl chlorides, and safe and feasible N,
Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamide preparation methods of N'-.
Technical scheme is as follows:
With di 2 ethylhexyl isophthalate（III）With 2,2,6,6- tetramethyl -4- amino piperidines（II）It is raw material, solvent is not used and is urged
Agent, directly implements aminolysis reaction, and N, double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- benzenedicarboxamides of N'- is obtained（I）.
Di 2 ethylhexyl isophthalate（III）It is DMIP or dimethyl isophthalate.
（I）
Di 2 ethylhexyl isophthalate is 1.0 with the mass ratio of 2,2,6,6- tetramethyl -4- amino piperidines:2.0-1.0:7.0, preferably
Mass ratio 1.0:3.5.
First reacted 1-2 hours at 190 DEG C, then heat to 220-240 DEG C and react 3-6 hours.
Less than 180 DEG C are cooled to, 2,2,6,6- excessive tetramethyl -4- amino piperidines are reclaimed in vacuum distillation.
Then with water to the N that generates, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- are washed
Wash, filter, drying obtains crystal product.
In sum, the present invention successfully solves the problems, such as prior art, is adapted to industry actual production.
Specific embodiment
The present invention is described in further details with reference to embodiment；The following examples are explanation of the invention,
Protection scope of the present invention is not limited to by following examples.
Embodiment 1
By 6.0 kilograms of DMIPs, 21.0 kilogram 2,2,6,6- tetramethyl -4- amino piperidines add 50 liters of reactors
In, close reactor all materials gateway.First reacted 2 hours at 190 DEG C, then heat to 230 DEG C and react 5 hours.Drop
Temperature reclaims 2,2,6,6- excessive tetramethyl -4- amino piperidines to less than 180 DEG C with the vacuum distillation of circulating vacuum water pump.Then
With water to the N that generates, double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- benzenedicarboxamides of N'- are washed, filtered, dried
It is dry, obtain 12.8 kilograms of needle-like white crystals products, yield 93.5%.278-280 DEG C of fusing point.
Embodiment 2
By 6.8 kilograms of dimethyl isophthalates, 24.0 kilogram 2,2,6,6- tetramethyl -4- amino piperidines add 50 liters of reactors
In, close reactor all materials gateway.First reacted 2 hours at 190 DEG C, then heat to 230 DEG C and react 6 hours.Drop
Temperature reclaims 2,2,6,6- excessive tetramethyl -4- amino piperidines to less than 180 DEG C with the vacuum distillation of circulating vacuum water pump.Then
With water to the N that generates, double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- benzenedicarboxamides of N'- are washed, filtered, dried
It is dry, obtain 12.4 kilograms of needle-like white crystals products, yield 91.6%.278-280 DEG C of fusing point.
Embodiment 3
6.0 kilograms of DMIPs, 21.0 kilograms of 2 for reclaiming and purifying, 2,6,6- tetramethyl -4- amino piperidines are added
Enter in 50 liters of reactors, close reactor all materials gateway.First reacted 2 hours at 190 DEG C, then heat to 230 DEG C
Reaction 5 hours.Less than 180 DEG C are cooled to, 2,2,6,6- excessive tetramethyl -4- ammonia are reclaimed with the vacuum distillation of circulating vacuum water pump
Phenylpiperidines.Then with water to the N that generates, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- are washed
Wash, filter, drying obtains 12.6 kilograms of needle-like white crystals products, yield 92.1%.278-280 DEG C of fusing point.
With N obtained in the inventive method, double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- benzenedicarboxamides, product of N'-
Matter is good, has carried out differential thermal analysis, and infrared spectrum and hydrogen nuclear magnetic resonance are tested.
Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamide DSC differential thermal analyses of accompanying drawing 1 N, N'-.
Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamide infrared spectrums of accompanying drawing 2 N, N'-.
Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamide proton nmr spectras of accompanying drawing 3 N, N'-.
Claims (6)
1. preparation structure（I）Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- phenyl-diformyls of formula Polvamide stabilisers N, N'-
The method of amine
（I）,
It is characterized in that：With di 2 ethylhexyl isophthalate（III）With 2,2,6,6- tetramethyl -4- amino piperidines（II）It is raw material, no
Using solvent and catalyst, direct amine solution is obtained N, double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- benzenedicarboxamides of N'-
（I）.
2., according to claim 1, it is technically characterized in that：The di 2 ethylhexyl isophthalate is DMIP or isophthalic
Dicarboxylate.
3., according to claim 1, it is technically characterized in that：Di 2 ethylhexyl isophthalate and 2,2,6,6- tetramethyl -4- amino piperidines
Mass ratio be 1.0:2.0-1.0:7.0.
4., according to claim 1, it is technically characterized in that：First reacted 1-2 hours at 190 DEG C, then heat to 220-240 DEG C
Reaction 3-6 hours.
5., according to claim 1, it is technically characterized in that：Less than 180 DEG C are cooled to, excessive 2,2,6,6- are reclaimed in vacuum distillation
Tetramethyl -4- amino piperidines.
6., according to claim 1, it is technically characterized in that：Then with water to the N, the double (2,2,6,6- tetramethyls -4- of N'- that generate
Piperidyl) -1,3- benzenedicarboxamides are washed, and are filtered, and drying obtains crystal product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710111609.XA CN106905225A (en) | 2017-02-28 | 2017-02-28 | A kind of preparation method of multi-functional Polvamide stabilisers |
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| CN201710111609.XA CN106905225A (en) | 2017-02-28 | 2017-02-28 | A kind of preparation method of multi-functional Polvamide stabilisers |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382828A (en) * | 2017-08-02 | 2017-11-24 | 新秀化学（烟台）有限公司 | A kind of synthetic method of N, N ' two (piperidyl of 2,2,6,6 tetramethyl 4) 1,3 benzenedicarboxamides |
| US20180194727A1 (en) * | 2015-07-03 | 2018-07-12 | Clariant Plastics & Coatings Ltd | Polymer additive and a method for the production thereof |
| CN109651235A (en) * | 2018-12-13 | 2019-04-19 | 天津利安隆新材料股份有限公司 | A kind of preparation method of nylon auxiliary agent |
| CN111410628A (en) * | 2019-11-01 | 2020-07-14 | 湘潭大学 | Novel polyamide stabilizer with crystal structure |
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| CN1671664A (en) * | 2002-08-19 | 2005-09-21 | 科莱恩有限公司 | Process for the preparation of stabilizers for polymers |
| CN104974075A (en) * | 2015-08-07 | 2015-10-14 | 新秀化学（烟台）有限公司 | Preparation method of N, N-bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide |
| WO2017005413A1 (en) * | 2015-07-03 | 2017-01-12 | Clariant International Ltd | Polymer additive and a method for the production thereof |
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2017
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| CN1671664A (en) * | 2002-08-19 | 2005-09-21 | 科莱恩有限公司 | Process for the preparation of stabilizers for polymers |
| WO2017005413A1 (en) * | 2015-07-03 | 2017-01-12 | Clariant International Ltd | Polymer additive and a method for the production thereof |
| CN104974075A (en) * | 2015-08-07 | 2015-10-14 | 新秀化学（烟台）有限公司 | Preparation method of N, N-bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180194727A1 (en) * | 2015-07-03 | 2018-07-12 | Clariant Plastics & Coatings Ltd | Polymer additive and a method for the production thereof |
| US10745353B2 (en) * | 2015-07-03 | 2020-08-18 | Clariant Plastics & Coatings Ltd | Polymer additive and a method for the production thereof |
| CN107382828A (en) * | 2017-08-02 | 2017-11-24 | 新秀化学（烟台）有限公司 | A kind of synthetic method of N, N ' two (piperidyl of 2,2,6,6 tetramethyl 4) 1,3 benzenedicarboxamides |
| US10336699B2 (en) * | 2017-08-02 | 2019-07-02 | Sunshow (Yantai) Specialty Chemical Company Limited | Method for synthesizing N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,3-benzenedicarboxamide |
| CN107382828B (en) * | 2017-08-02 | 2020-05-12 | 烟台新秀化学科技股份有限公司 | Synthesis method of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide |
| CN109651235A (en) * | 2018-12-13 | 2019-04-19 | 天津利安隆新材料股份有限公司 | A kind of preparation method of nylon auxiliary agent |
| CN111410628A (en) * | 2019-11-01 | 2020-07-14 | 湘潭大学 | Novel polyamide stabilizer with crystal structure |
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Application publication date: 20170630 |