CN106831539B - The synthesis of polyamide stabilizer - Google Patents
The synthesis of polyamide stabilizer Download PDFInfo
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- CN106831539B CN106831539B CN201710116687.9A CN201710116687A CN106831539B CN 106831539 B CN106831539 B CN 106831539B CN 201710116687 A CN201710116687 A CN 201710116687A CN 106831539 B CN106831539 B CN 106831539B
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- tetramethyl
- bis
- synthetic method
- piperidyl
- terephthalate
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to Polvamide stabilisers N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1, the synthetic method of 4- benzenedicarboxamide, with dimethyl terephthalate (DMT) or diethyl terephthalate and 2,2,6,6- tetramethyl -4- amino piperidine is raw material, does not use solvent and catalyst, first reacts 1-2 hours at 190 DEG C, then heat to 220-240 DEG C of reaction 3-6 hours, N, N'- bis- (2 is made in direct aminolysis, 2,6,6- tetramethyl -4- piperidyls)-Isosorbide-5-Nitrae-benzenedicarboxamide.
Description
Technical field
The present invention relates to Polvamide stabilisers N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,4- benzenedicarboxamides of N'-
(I) synthetic method.
(I).
Background technique
Bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N, N'- are as a kind of polyamides amine light stabilizer
And the existing many reports of processing aid；Its synthetic method of following patent report: EP 1556350 (equivalent CN 1671664A,
CN 1279024C, WO 2004016591A1, US 7632949), CN 105481759A, CN 104974075A, CN
103554009A, CN 103554009B, CN 103508938A, CN 103508938B, CN 103030588A.
However the synthesis and materialization of bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,4- benzenedicarboxamides (I) of N, N'-
Matter is almost without document report, (the equivalent DE 102008026075, CN of JP 2015224286, WO 2009144044
102037080A, CN 102037080B, EP 2128198), (equivalent 1738002 US of EP of WO 2005103345
20050239927 CN 1942613A), JP 2000239924 is only referred to N, the bis- (2,2,6,6- tetramethyl -4- piperidines of N'-
Base) application of-Isosorbide-5-Nitrae-benzenedicarboxamide describes and claim, but illustrate without preparation, no synthetic example and Application Example.
Only JP 1970-2619 (equivalent DE 2040975, US3684765, GB 1318559), US3684765
The Table 3 of embodiment 3 lists N, the use of bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,4- benzenedicarboxamides (I) of N'-
In the good results data of the anti-aging experiment of polyamide nylon 6；However above is referred to N, the bis- (2,2,6,6- tetramethyl -4- of N'-
Piperidyl) -1,4- benzenedicarboxamide (I) patent without synthesis explanation and synthetic example；Even more has no the object of object test
Change property detailed literature report (Scifinder retrieval).
Summary of the invention
The invention proposes one kind to be used for Polvamide stabilisers N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,4- of N'-
The synthetic method of benzenedicarboxamide develops its industrial application value with benefit.This stabilizer molecular structure symmetry is high, amido bond
It can more preferably be combined with hydrogen bond formation with the amido bond in polyamide, give full play to its excellent results, as shown in (IV) formula.
(IV).
Technical scheme is as follows:
With 2,2,6,6- tetramethyl -4- amino piperidines (II) and bis- terephthalate (III) for raw material, solvent is not used
And N, bis- (2,2,6, the 6- tetramethyl -4- piperidyl)-Isosorbide-5-Nitrae-benzenedicarboxamides (I) of N'- are made in catalyst, direct aminolysis.
Bis- terephthalate (III) is dimethyl terephthalate (DMT) or diethyl terephthalate.
(I)。
The mass ratio of bis- terephthalate and 2,2,6,6- tetramethyl -4- amino piperidine is 1.0:2.0-1.0:7.0,
Preferred mass ratio 1.0:3.6.
It is first reacted 1-2 hours at 190 DEG C, then heats to 220-240 DEG C of reaction 3-6 hours.
Because of N, bis- (2,2,6,6- tetramethyl -4- piperidyl)-Isosorbide-5-Nitrae-benzenedicarboxamide (I) the molecular structure symmetry of N'- are good,
Cool down to obtain the high crystal of crystalline stacks density, and excessive 2,2,6,6- tetramethyl -4- amino piperidines (II) are recovered by filtration.
Then with water to the N of generation, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,4- benzenedicarboxamides (I) of N'- into
Row washing, is filtered, and drying obtains crystal product.
In conclusion the present invention is successfully realized N, bis- (2,2,6,6- tetramethyl -4- the piperidyl)-Isosorbide-5-Nitraes-benzene diformazan of N'-
The preparation of amide (I) is suitble to industry actual production.
Specific embodiment
The present invention is described in further details below with reference to embodiment；The following examples are explanation of the invention,
Protection scope of the present invention is not limited to by following embodiment.
Embodiment 1
By 6.0 kilograms of dimethyl terephthalate (DMT)s, 22.0 kilogram 2, reaction kettle is added in 2,6,6- tetramethyl -4- amino piperidines
In, close reaction kettle all materials entrance.It is first reacted 2 hours at 190 DEG C, then heats to 230 DEG C and react 5 hours.Drop
Temperature crystallization, is recovered by filtration excessive 2,2,6,6- tetramethyl -4- amino piperidines.Then with water to the N of generation, N'- it is bis- (2,2,6,
6- tetramethyl -4- piperidyl)-Isosorbide-5-Nitrae-benzenedicarboxamide washed, and is filtered, and drying obtains 12.3 kilograms of square piece shape white crystals
Product, yield 89.9%.
Embodiment 2
By 6.6 kilograms of diethyl terephthalates, 24.0 kilogram 2, reaction kettle is added in 2,6,6- tetramethyl -4- amino piperidines
In, close reaction kettle all materials entrance.It is first reacted 2 hours at 190 DEG C, then heats to 230 DEG C and react 6 hours.Drop
Temperature crystallization, is recovered by filtration excessive 2,2,6,6- tetramethyl -4- amino piperidines.Then with water to the N of generation, N'- it is bis- (2,2,6,
6- tetramethyl -4- piperidyl)-Isosorbide-5-Nitrae-benzenedicarboxamide washed, and is filtered, and drying obtains 11.5 kilograms of square piece shape white crystals
Product, yield 87.5%.
Embodiment 3
By 6.0 kilograms of dimethyl terephthalate (DMT)s, 22.0 kilograms of 2,2,6,6- tetramethyl -4- amino piperazines for recycling and purifying
Pyridine is added in reaction kettle, closes reaction kettle all materials entrance.It is first reacted 2 hours at 190 DEG C, then heats to 230 DEG C
Reaction 5 hours.Excessive 2,2,6,6- tetramethyl -4- amino piperidines are recovered by filtration in decrease temperature crystalline.Then with water to the N of generation,
Bis- (2,2,6, the 6- tetramethyl -4- piperidyl)-Isosorbide-5-Nitrae-benzenedicarboxamides of N'- are washed, and are filtered, and drying obtains 12.1 kilograms of sides
Sheet white crystal product, yield 88.4%.
Bis- (2,2,6, the 6- tetramethyl -4- piperidyl)-Isosorbide-5-Nitrae-benzenedicarboxamides of the N made from the method for the present invention, N'-, it is red
External spectrum and hydrogen nuclear magnetic resonance test result are shown in Figure of description 1-2.
Bis- (2,2,6,6- tetramethyl -4- the piperidyl)-Isosorbide-5-Nitraes-benzenedicarboxamide infrared spectroscopy of attached drawing 1 N, N'-,
Bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,4- benzenedicarboxamide hydrogen nuclear magnetic resonance spectrums of attached drawing 2 N, N'-.
Claims (5)
1. a kind of bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,4- phenyl-diformyls of structure (I) formula Polvamide stabilisers N, N'-
The synthetic method of amine,
(I)
It is characterized by: 2,6,6- tetramethyl -4- amino piperidines (II) are raw material, no with bis- terephthalate (III) and 2
Using solvent and catalyst, is first reacted 1-2 hours at 190 DEG C, then heat to 220-240 DEG C of reaction 3-6 hours, directly
N, bis- (2,2,6, the 6- tetramethyl -4- piperidyl)-Isosorbide-5-Nitrae-benzenedicarboxamides (I) of N'- are made in aminolysis.
2. synthetic method according to claim 1 is technically characterized in that the bis- terephthalate is to benzene two
Formic acid dimethyl ester or diethyl terephthalate.
3. synthetic method according to claim 1, it is technically characterized in that bis- terephthalate and 2,2,6,6- tetra-
The mass ratio of methyl -4- amino piperidine is 1.0:2.0-1.0:7.0.
4. synthetic method according to claim 1, is technically characterized in that decrease temperature crystalline, excessive 2,2 are recovered by filtration,
6,6- tetramethyl -4- amino piperidine (II).
5. synthetic method according to claim 1, be technically characterized in that the N then with water to generation, N'- it is bis- (2,
2,6,6- tetramethyl -4- piperidyls)-Isosorbide-5-Nitrae-benzenedicarboxamide (I) washed, and is filtered, and drying obtains crystal product.
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| CN201710116687.9A CN106831539B (en) | 2017-03-01 | 2017-03-01 | The synthesis of polyamide stabilizer |
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| CN106831539B true CN106831539B (en) | 2019-02-01 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1675300A (en) * | 2002-08-07 | 2005-09-28 | 西巴特殊化学品控股有限公司 | Beta-nucleating, light stabilizing agents for polypropylene |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015224286A (en) * | 2014-05-28 | 2015-12-14 | 東レ株式会社 | Polyamide resin composition |
| DE102015212508A1 (en) * | 2015-07-03 | 2017-01-05 | Clariant International Ltd. | Polymer additive and process for its preparation |
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- 2017-03-01 CN CN201710116687.9A patent/CN106831539B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1675300A (en) * | 2002-08-07 | 2005-09-28 | 西巴特殊化学品控股有限公司 | Beta-nucleating, light stabilizing agents for polypropylene |
| 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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