CN108948344A - Polycaprolactam auxiliary agent and preparation method thereof, polycaprolactam - Google Patents
Polycaprolactam auxiliary agent and preparation method thereof, polycaprolactam Download PDFInfo
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- CN108948344A CN108948344A CN201710356803.4A CN201710356803A CN108948344A CN 108948344 A CN108948344 A CN 108948344A CN 201710356803 A CN201710356803 A CN 201710356803A CN 108948344 A CN108948344 A CN 108948344A
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- Prior art keywords
- polycaprolactam
- benzylamine
- preparation
- tpa
- piperidyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
This application discloses a kind of polycaprolactam auxiliary agents and preparation method thereof, polycaprolactam, and wherein the preparation method of polycaprolactam includes: with caprolactam, water, terephthalic acid (TPA), benzylamine, N, N|--- two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides carry out polymerization reaction, caprolactam, water, terephthalic acid (TPA), benzylamine, N, N as raw material|--- the weight ratio of two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides are as follows: 1550-1580:25-27:5.3-5.5:0.9-1.1:1.5-1.7.The polycaprolactam that the present invention obtains has more stable viscosity and dyeability.
Description
Technical field
This application involves polycaprolactam fields, more particularly to a kind of polycaprolactam auxiliary agent and preparation method thereof, gather
Caprolactam.
Background technique
German Sxhlack in 1938, which has been invented, produces daiamid-6 fiber, nineteen forty-one this fibre using caprolactam polymerization
Dimension starts to industrialize.Due to daiamid-6 fiber function admirable, in addition to having the advantages of general synthetic fibers, also have intensity it is high,
Resilience is good, wearability and fatigue durability, is widely used in and takes fiber, commercially with fiber and decoration fiber.Meanwhile polyamide
6 exploitations are for manufacturing high performance thin film material, and big, good toughness, gas barrier property are excellent with intensity for film, in packaging industry
Increasingly it is taken seriously.
Usually there is year and the unstable technical problem of dyeability in existing polycaprolactam.
Summary of the invention
The purpose of the present invention is to provide a kind of polycaprolactam auxiliary agents and preparation method thereof, polycaprolactam, to overcome
Deficiency in the prior art.
To achieve the above object, the invention provides the following technical scheme:
The embodiment of the present application discloses a kind of preparation method of polycaprolactam, with caprolactam, water, terephthalic acid (TPA), benzylamine, N,
N|--- two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides as raw material carry out polymerization reaction, caprolactam,
Water, terephthalic acid (TPA), benzylamine, N, N|--- the weight ratio of two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides are as follows:
1550-1580:25-27:5.3-5.5:0.9-1.1:1.5-1.7 。
Preferably, in the preparation method of above-mentioned polycaprolactam, caprolactam, water, terephthalic acid (TPA), benzylamine, N, N|--- the weight ratio of two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides are as follows: 82:10:5.4:1:1.6.
Preferably, in the preparation method of above-mentioned polycaprolactam, the polymeric reaction condition meets: temperature: 250-
260 DEG C, pressure: 1.45-1.55bar.
Correspondingly, disclosed herein as well is a kind of polycaprolactam auxiliary agent, including terephthalic acid (TPA), benzylamine and N, N|---
Two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides, terephthalic acid (TPA), benzylamine and N, N|--- two (2,2,6,6-
Tetramethyl -4- piperidyl) -1,3- benzene diamides weight ratio be 5.3-5.5:0.9-1.1:1.5-1.7.
Preferably, in above-mentioned polycaprolactam auxiliary agent, terephthalic acid (TPA), benzylamine and N, N|--- two (2,2,6,6- tetra-
Methyl -4- piperidyl) -1,3- benzene diamides weight ratio be 5.4:1:1.6.
Correspondingly, disclosed herein as well is a kind of preparation methods of polycaprolactam auxiliary agent, comprising steps of
(1), preparing tank is provided；
(2), exhaust valve is opened, N, N is added in whipping process|--- two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene two
Amide, opens baiting valve after 1.5 ~ 2 hours, and with nitrogen blowing-out, closes exhaust hand-operated valve；
(3), step (2) are repeated and terephthalic acid (TPA) is added；
(4), benzylamine is added, and stirs 1-1.5 hours.
Preferably, in the preparation method of above-mentioned polycaprolactam auxiliary agent, in the step (1), preparing tank is adjusted
Temperature is at 93 ~ 95 DEG C.
Preferably, in the preparation method of above-mentioned polycaprolactam auxiliary agent, in the step (1), the preparing tank
Agitating device includes blender and pneumatic vibrator device.
Compared with the prior art, the advantages of the present invention are as follows: the polycaprolactam that the present invention obtains has more stable
Viscosity and dyeability.
Detailed description of the invention
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in application, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 show the viscograph of polycaprolactam in the prior art；
Fig. 2 show the viscograph of the polycaprolactam of specific embodiment of the invention preparation.
Specific embodiment
As previously mentioned, inventor study for a long period of time and a large amount of realities in view of many deficiencies of the existing technology
It tramples, to solve these problems.
The embodiment of the present application discloses a kind of preparation method of polycaprolactam, with caprolactam, water, terephthalic acid (TPA)
(PTA), benzylamine, N, N|--- two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides (seed) are carried out as raw material
Polymerization reaction (temperature: 250-260 DEG C, pressure: 1.45-1.55bar), caprolactam, water, terephthalic acid (TPA), benzylamine, N, N|--- the weight ratio of two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides are as follows: 1550-1580:25-27:5.3-
5.5:0.9-1.1:1.5-1.7。
The embodiment of the present application also discloses a kind of polycaprolactam auxiliary agent, including terephthalic acid (TPA), benzylamine and N, N|--- two
(2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides, terephthalic acid (TPA), benzylamine and N, N|--- two (2,2,6,6- tetra-
Methyl -4- piperidyl) -1,3- benzene diamides weight ratio be 5.3-5.5:0.9-1.1:1.5-1.7.
Correspondingly, the preparation method of polycaprolactam auxiliary agent, comprising steps of
(1), preparing tank is provided；
(2), exhaust valve is opened, N, N is added in whipping process|--- two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene two
Amide, opens baiting valve after 1.5 ~ 2 hours, and with nitrogen blowing-out, closes exhaust hand-operated valve；
(3), step (2) are repeated and terephthalic acid (TPA) is added；
(4), benzylamine is added, and stirs 1-1.5 hours.
In a preferred embodiment, in the step (1), the temperature of preparing tank is adjusted in 93 ~ 95 DEG C, preferably 95
℃。
In a preferred embodiment, in the step (1), the agitating device of the preparing tank includes blender and pneumatic
Vibrator.
The present invention is described further by the following example: according to following embodiments, the present invention may be better understood.
However, as it will be easily appreciated by one skilled in the art that specific material ratio, process conditions and its result described in embodiment are only used
In illustrating the present invention, without the present invention described in detail in claims should will not be limited.
Most preferred embodiment
The quality that compounding agent solution is prepared, there is important influence to caprolactam polymerization.According to the actual condition of production, preparation side
Method includes:
1. confirming the temperature in preparing tank at 95 DEG C.
2. starting blender, pneumatic vibrator device is opened.
3. additive personnel are controlled in contacting when adding every kind of material, nitrogen replenishment valve is closed, after adding every kind of material, is controlled in connection
Personnel open nitrogen replenishment valve
4. seed first checks feed opening before being added, whether there is or not blockings, re-record gravimetric tank total weight, are first blown with feeder pipe top nitrogen
It sweeps 5 minutes, opens live exhaust valve, open the corresponding hand-operated valve of this line, feed under automatic mode, recorded after the completion of charging total
Weight and whether calculate additional amount correct, opens baiting valve manually, and with nitrogen blowing-out, closes exhaust hand-operated valve.
5.1.5 add PTA after hour, step and the same seed of method is added.
6.1.5 before adding benzylamine material, benzylamine material to be added after hour the bottom valve of gravimetric tank is first opened into 1/3 circle manually, opens scene
Corresponding hand-operated valve, total weight before record is added, is added in automatic mode, this line of on-site manual is closed after the completion of addition
Hand-operated valve records and calculates addition weight, recycles and stirs 1 hour.
7. being sampled by drain valve before delivery pump.
It polymerize the high-quality polycaprolactam to form certain viscosity by above-mentioned compounding agent solution, wherein terephthalic acid (TPA) (PTA)
Mainly play sealing end with benzylamine, the Amino End Group and carboxyl end group in adjustment polyamide 6 are in target value.N,N|--- two (2,2,6,
6- tetramethyl -4- piperidyl) thermal stability and dyeability of melt can be improved in -1,3- benzene diamides (seed).
Three kinds of auxiliary agents and caprolactam water solution are formulated together, according to a certain percentage, enter with caprolactam
Polymer reactor carries out polymerization reaction, and reaction temperature: 250 DEG C, pressure: 1.5bar generates the polycaprolactam of certain viscosity.
In the preferred embodiment, configuration proportion (weight): caprolactam 82%, water 10%, PTA5.4%, benzylamine 1%, SEED1.6%.
Comparative example
Auxiliary agent uses caprolactam, water and terephthalic acid (TPA), wherein caprolactam: 85%, water 10%, and terephthalic acid (TPA) additional amount
It is 5%, polycaprolactam is generated using polymerizing condition identical with most preferred embodiment.
Fig. 1 and Fig. 2 is respectively the viscosity profile of the polycaprolactam obtained in comparative example and most preferred embodiment.Wherein,
Abscissa refers to that continuous sampling number, ordinate refer to range of viscosities.Comparison is it is found that the polycaprolactam that most preferred embodiment obtains from figure
The viscosity and dyeability of amine are more stable.
Here, it should also be noted that, in order to avoid having obscured the present invention because of unnecessary details, in the accompanying drawings only
Show with closely related structure and/or processing step according to the solution of the present invention, and be omitted little with relationship of the present invention
Other details.
Finally, it is to be noted that, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive
Property include so that include a series of elements process, method, article or equipment not only include those elements, but also
Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic
Element.
Claims (8)
1. a kind of preparation method of polycaprolactam, it is characterised in that: with caprolactam, water, terephthalic acid (TPA), benzylamine, N, N|--- two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides as raw material carry out polymerization reaction, caprolactam, water,
Terephthalic acid (TPA), benzylamine, N, N|--- the weight ratio of two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides are as follows:
1550-1580:25-27:5.3-5.5:0.9-1.1:1.5-1.7 。
2. the preparation method of polycaprolactam according to claim 1, it is characterised in that: caprolactam, water, terephthaldehyde
Acid, benzylamine, N, N|--- the weight ratio of two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides are as follows: 82:10:5.4:
1:1.6。
3. the preparation method of polycaprolactam according to claim 1, it is characterised in that: the polymeric reaction condition is full
Foot: temperature: 250-260 DEG C, pressure: 1.45-1.55bar.
4. a kind of polycaprolactam auxiliary agent, which is characterized in that including terephthalic acid (TPA), benzylamine and N, N|--- two (2,2,6,6- tetra-
Methyl -4- piperidyl) -1,3- benzene diamides, terephthalic acid (TPA), benzylamine and N, N|--- two (2,2,6,6- tetramethyl -4- piperidines
Base) -1,3- benzene diamides weight ratio be 5.3-5.5:0.9-1.1:1.5-1.7.
5. polycaprolactam auxiliary agent according to claim 4, it is characterised in that: terephthalic acid (TPA), benzylamine and N, N|--- two
The weight ratio of (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides is 5.4:1:1.6.
6. the preparation method of polycaprolactam auxiliary agent described in claim 4 or 5, which is characterized in that comprising steps of
(1), preparing tank is provided；
(2), exhaust valve is opened, N, N is added in whipping process|--- two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene, two acyl
Amine, opens baiting valve after 1.5 ~ 2 hours, and with nitrogen blowing-out, closes exhaust hand-operated valve；
(3), step (2) are repeated and terephthalic acid (TPA) is added；
(4), benzylamine is added, and stirs 1-1.5 hours.
7. the preparation method of polycaprolactam auxiliary agent according to claim 6, it is characterised in that: in the step (1), adjust
The temperature of whole preparing tank is at 93 ~ 95 DEG C.
8. the preparation method of polycaprolactam auxiliary agent according to claim 6, it is characterised in that: in the step (1), institute
The agitating device for stating preparing tank includes blender and pneumatic vibrator device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710356803.4A CN108948344A (en) | 2017-05-19 | 2017-05-19 | Polycaprolactam auxiliary agent and preparation method thereof, polycaprolactam |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710356803.4A CN108948344A (en) | 2017-05-19 | 2017-05-19 | Polycaprolactam auxiliary agent and preparation method thereof, polycaprolactam |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812554A (en) * | 2021-02-20 | 2021-05-18 | 长乐力恒锦纶科技有限公司 | anti-UV, antibacterial and delustering polyamide chip and preparation method thereof |
| CN113956469A (en) * | 2021-11-10 | 2022-01-21 | 湖南岳化化工股份有限公司 | Nylon 6 and two-stage polymerization preparation method thereof |
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| CN112812554A (en) * | 2021-02-20 | 2021-05-18 | 长乐力恒锦纶科技有限公司 | anti-UV, antibacterial and delustering polyamide chip and preparation method thereof |
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