CN105753718A - Method for removing impurity 2,3,4,5-tetrahydropyridine in nylon salt and purified nylon salt - Google Patents
Method for removing impurity 2,3,4,5-tetrahydropyridine in nylon salt and purified nylon salt Download PDFInfo
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- CN105753718A CN105753718A CN201410790776.8A CN201410790776A CN105753718A CN 105753718 A CN105753718 A CN 105753718A CN 201410790776 A CN201410790776 A CN 201410790776A CN 105753718 A CN105753718 A CN 105753718A
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Abstract
The present invention provides a purified nylon salt formed from diamines and dicarboxylic acids, the diamines at least comprise 1,5-Diaminopentane, the content of impurity 2,3,4,5-tetrahydropyridine in the nylon salt is less than 0.1wt%, and the content is calculated on the basis of the weight of the 1,5-Diaminopentane. The present invention further provides a method for removing the impurity 2,3,4,5-tetrahydropyridine in the nylon salt. Compared with conventional nylon salts, the purified nylon salt has the characteristics of less impurities in particular low content of the impurity 2,3,4,5-tetrahydropyridine, and the yellowing problem of nylon obtained by subsequent polymerization can be effectively solved.
Description
Technical field
The present invention relates to a kind of method of 2,3,4,5-tetrahydropyridine impurity in removal nylon salt, be specially one
The content of impurity 2,3,4,5-tetrahydropyridine in nylon salt can be controlled the method in relatively low scope and gained
The nylon salt of purification.
Background technology
Polyamide is the important textile material of a class and engineering plastics.With pentanediamine (i.e. 1,5-pentanediamine, or
1,5-1,5-DAP) it is the polyamide series of products such as polyamide 56 prepared of monomer, polyamide 510, poly-
It is raw that amide 512 etc. can apply to the daily productions such as weaving, electronic apparatus, plant equipment, automobile component
The many aspects lived.
Nylon can be made up of diamine and binary acid direct polycondensation, it is possible to is first produced nylon by polymerization monomer
Salt, then nylon salt is polymerized.This polyreaction typically requires at a temperature of more than up to 200 DEG C
Carry out, therefore the impurity of trace in nylon salt, especially with unsaturated functional group and oxidizable chemical combination
, during high temperature polymerization, easily there is chemical reaction and xanthochromia in thing, and then to the color of nylon and product
Matter impacts.Additionally, comprise the compound of single amino, carboxyl functional group, in the polymerization,
Can stop carrying out further of polymerization as chain terminating agent, reduce the molecular weight of nylon, and then to Buddhist nun
Production and the performance of dragon impact.Therefore producing high-quality nylon salt is to produce high-quality nylon polymerization
The premise of thing.
The quality of nylon salt is affected by many factors, such as production technology, raw material type and the mode of production etc..
And determine and to control the content of critical impurities in nylon salt the most direct to the qualified production ensureing nylon product
With important.
2,3,4,5-tetrahydropyridines can be the impurity that pentanediamine can produce in preparation process, and patent
JP2012106935 has pointed out finished product 1,5-pentanediamine also can produce 2,3,4,5-tetrahydropyridine during storing
Deng impurity.It is colourless liquid under 2,3,4,5-tetrahydropyridine room temperature, is present in pentanediamine or its aqueous solution not
The color etc. of pentanediamine can be had a significant effect.On molecular structure, 2,3,4,5-tetrahydropyridines and pentanediamine
It is all organic amine compound, belongs to the monoamine containing a double bond, in nylon polymerization process, make
Tetrahydropyridine for monoamine can play the effect of stopping of chain agent, stops the carrying out of polyreaction, and impact is poly-
The molecular weight of compound, thus affect the mechanical performance of polyamide.On the other hand, the double bond in tetrahydropyridine
It is easily oxidised, polyamide its colour changed into yellow can be made so that the exterior quality of nylon product is defective.
Therefore, in order to improve the quality of polymer, it is necessary to containing of control wherein 2,3,4,5-tetrahydropyridine impurity
Amount.On the one hand, when using commercially available or the most individually purification pentanediamine to prepare nylon salt as raw material,
2 in raw material can be removed by this pentanediamine of direct purification, 3,4,5-tetrahydropyridine impurity, but follow-up
After being formed in the step of nylon salt or forming nylon salt, still have 2,3,4,5-tetrahydropyridine impurity shapes
Become so that remove 2,3,4,5-tetrahydropyridine impurity above by direct purification pentanediamine and realize nylon salt
Control with nylon quality is the most highly effective.On the other hand, individually pentanediamine raw material is purified also
Add step and the complexity of technique, need equipment and the technique of the most individually exploitation purification pentanediamine
Route, thus extremely it is unfavorable for the control of nylon salt production cost in technique.
In sum, from nylon salt, the most directly remove the impurity such as 2,3,4,5-tetrahydropyridines and become nylon
A key issue in production.Though prior art JP2012106935 pointed out minimizing 1,5-pentanediamine and
The store method of 2,3,4,5-tetrahydropyridine impurity in its salt, but do not provide the method removing this impurity.Cause
This, for guaranteeing the quality of nylon product, need 2,3,4,5-tetrahydropyridine impurity in a kind of removable nylon salt badly
Method.
Summary of the invention
In order to solve above-mentioned technical problem, it is provided that disclosure satisfy that the raw material needed for polymerization, the invention provides
A kind of method removing impurity 2,3,4,5-tetrahydropyridine in nylon salt and the nylon salt of purification.
The nylon salt of a kind of purification, the salt formed with dicarboxylic acids including diamine, described diamine is at least
Including 1,5-pentanediamine, wherein, impurity 2 in described nylon salt, the content of 3,4,5-tetrahydropyridines is less than
0.1wt%, described content is with described 1, on the basis of the weight of 5-pentanediamine.
According to an embodiment of the present invention, wherein said diamine includes C4～C18Binary aliphatic
One or more in amine and aromatic diamine.
According to another embodiment of the present invention, wherein said dicarboxylic acids includes C4～C18Aliphatic
One or more in diacid, aromatic diacid and heterocycle diacid.
According to another embodiment of the present invention, wherein said dicarboxylic acids selected from succinic acid, adipic acid,
One or more in decanedioic acid, dodecanedioic acid, p-phthalic acid, furan dicarboxylic acid.
According to another embodiment of the present invention, the content of wherein said impurity 2,3,4,5-tetrahydropyridine is less than
0.05wt%.
According to another embodiment of the present invention, the content of wherein said impurity 2,3,4,5-tetrahydropyridine is less than
0.03wt%.
Present invention also offers a kind of method of impurity 2,3,4,5-tetrahydropyridine in removal nylon salt, including,
One nylon salt to be purified is provided；By described nylon salt to be purified through sorbent treatment, obtain the nylon of purification
Salt, wherein, the diamidogen constituting described nylon salt at least includes 1,5-pentanediamine.
According to an embodiment of the present invention, in the nylon salt of wherein said purification, impurity 2,3,4,5-tetrahydrochysenes
The content of pyridine is less than 0.1wt%.
According to another embodiment of the present invention, wherein said absorbing agent treatment step includes, stirring
Lower by described adsorbent add described nylon salt to be purified aqueous solution in, keep solution temperature be 20 DEG C～
100 DEG C, separate described adsorbent, obtain the nylon salt of described purification.
According to another embodiment of the present invention, wherein said absorbing agent treatment step includes, treats described
The aqueous solution of purification nylon salt, by being filled with the adsorption column of described adsorbent, collects containing of described adsorption column
The effluent of nylon salt, obtains the nylon salt of described purification.
According to another embodiment of the present invention, wherein said adsorbent is selected from macroporous adsorbent resin or activity
Charcoal, described adsorbent is preferably nonpolar macroporous adsorption resin or wooden big mesoporous activated carbon.
According to another embodiment of the present invention, the consumption of wherein said adsorbent is 1～20wt%, excellent
Elect 1～12wt% as, with described 1, on the basis of the weight of 5-pentanediamine.
According to another embodiment of the present invention, the step wherein preparing described nylon salt to be purified includes:
Dicarboxylic acids is joined containing 1, in the diamine aqueous solution of 5-pentanediamine, and regulate the pH value of solution
It is 5.0～9.5.
The nylon salt that the present invention provides, compared with existing nylon salt, has impure few, particularly
The feature that 2,3,4,5-tetrahydropyridine content are low, effectively solves the nylon xanthochromia that follow-up polymerization obtains and asks
Topic.
Detailed description of the invention
Embodiment feature of present invention will describe the most in detail with the exemplary embodiments of advantage.Ying Li
Solve is that the present invention can have various changes in different embodiments, and it is all without departing from the present invention's
Scope, and explanation therein is inherently illustrated as being used, and be not used to limit the present invention.
The invention provides a kind of method of impurity 2,3,4,5-tetrahydropyridine in removal nylon salt, pass through the party
Method can be by impurity 2 in nylon salt, and the content of 3,4,5-tetrahydropyridines controls within 0.1wt%, for obtaining
Qualified nylon product is had laid a good foundation.
Offer one nylon salt to be purified is provided；By this nylon salt to be purified through adsorbent
After process, obtain the nylon salt of purification.
The nylon salt of the purification of prepared in accordance with the method for the present invention, the content of 2,3,4,5-tetrahydropyridines is the most not
Higher than 0.05wt%, more preferably not above 0.03wt%.2,3,4,5-tetrahydrochysene pyrrole involved in the present invention
The content of pyridine detects with gas chromatogram normalization method, and with relative to the weight of pentanediamine raw material in nylon salt
Percentage composition meter.Additionally, the pentanediamine in the present invention refers both to 1,5-pentanediamine.
In the present invention, nylon salt to be purified includes the salt that diamine is formed, described diamine with dicarboxylic acids
At least include 1,5-pentanediamine.
Except 1, beyond 5-pentanediamine, this diamine can also include aliphatic diamine, such as butanediamine,
Hexamethylene diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine；Aromatic diamine can also be included, such as
P-phenylenediamine, o-phenylenediamine, m-diaminobenzene. etc..
The dicarboxylic acids being used for preparing nylon salt to be purified in the present invention can be Straight chain diatomic acid, such as
C4～C18Binary acid, include but not limited to succinic acid, adipic acid, Azelaic Acid, decanedioic acid, 12 carbon
Binary acid, it is also possible to be aromatic acid, such as p-phthalic acid, phthalic acid, M-phthalic acid,
Can also is that heterocycle binary acid, such as furan dicarboxylic acid.
The present invention being also possible that, other monomers participate in into salt, such as 6-aminocaprolc acid (No. CAS:
60-32-2), 11-amino undecanoic acid (No. CAS: 2432-99-7), 12 amino dodecanoic acid (No. CAS:
The aminoacid such as 693-57-2).
The preparation method of the pentanediamine raw material for preparing nylon salt to be purified is limited by the present invention the most especially
Fixed, it can be prepared by the bioanalysis of fermentation or enzymatic conversion, as Japan Patent JP2008193898A is public
Open and obtained pentanediamine using lysine carbonate aqueous solution as substrate to carry out enzyme catalysis；Patent
CN102782146A discloses the method with enzymatic conversion and lysine hydrochloride is converted into the side of pentanediamine
Method；Patent CN102844440A discloses the method utilizing corynebacterium fermentation to prepare pentanediamine.Penta 2
Amine raw material can also act on lysine reaction by E.C. 4.1.1.18 and obtain enzymatic conversion liquid, and then extracts
Go out pentanediamine (referring to JP200400114A)；Gene technology can also be passed through, bad ammonia can generated
The bacterial strain of acid raises the expression of E.C. 4.1.1.18, or recombinant expressed E.C. 4.1.1.18, can send out
The lysine making generation during ferment synchronizes to be converted into pentanediamine, and direct fermentation obtains pentanediamine fermentation liquid (can
With reference to One-step production 1, the structure of 5-pentanediamine Corynebacterium glutamicum gene engineering bacteria, Niu Tao etc., China
Biological engineering magazine, 2010,30 (8): 93-99).
The pentanediamine of the present invention can also be prepared by chemical method, such as must mountain just et al. (lysine de-
Carboxylic method (fourth edition), pharmaceutical journal (ア ミ ノ acid takes off charcoal acid (the 4th)),
Vol.85 (6), P531-533,1965) disclose with lysine at the hexamethylene containing tetrahydronaphthalene peroxide
Through boiling prepared pentanediamine in alcohol.The clear 60-23328 of open patent discloses with the ethylene of 2-cyclic ethylene esters
Ketone compounds is catalyst, lysine the method manufacturing pentanediamine as raw material.
The nylon salt of the purification in the present invention can only comprise a kind of nylon salt, a kind of lipid structure
Nylon salt (-OOC(CH2)nCOOH3N(CH2)5NH3 +, n=0～18), it is specifically as follows succinic acid penta 2
Amine salt, adipic acid pentanediamine salt, decanedioic acid pentanediamine salt or 12 carbon dicarboxylic acids pentanediamine salt；Such as one
Plant the nylon salt containing aromatic structure, be specifically as follows p-phthalic acid pentanediamine salt.Two kinds can also be comprised
Or two or more different pentanediamine nylon salt.The nylon salt of above-mentioned purification may also include and is added on pentanediamine
Other nylon salt in nylon salt or polymerization monomer, such as nylon salt, caprolactam, 6-amino is own
Acid etc..
The preparation method of nylon salt to be purified is had no particular limits by the present invention, can use any known
Method.
In one embodiment of the present invention, the diamidogen added Dicarboxylic Acids containing pentanediamine is water-soluble
In liquid, until pH value in solution is 5.0～9.5, obtain nylon salt aqueous solution to be purified.The present invention's
In another embodiment, mix after first dicarboxylic acids being weighed with diamine, then add the mixture to water
In, prepare nylon salt to be purified.In another embodiment of the present invention, by part dicarboxylic acids and two
Unit's amine mixes after weighing, and is added to the water reaction, then adds remaining dicarboxylic acids or diamine, system
Obtain nylon salt to be purified.
Additionally, nylon salt to be purified is the most all by prepared by the sterling of diamidogen and diacid.Such as
EP1482055A1 discloses and controls E.C. 4.1.1.18 conversion production penta with adipic acid as pH adjusting agent
The pH value of diamidogen process, then crystallization obtains nylon salt to be purified；JP2004208646A disclose by
E.C. 4.1.1.18 and lysine dicarboxylate carry out enzyme reaction and obtain pentanediamine dicarboxylate crude product；Specially
In profit JP20030001871 and US20050003497A1, also it is directly added into pentanediamine by adipic acid
Enzymatic conversion liquid produces nylon salt.
In the present invention, the pentanediamine preparing nylon salt to be purified can be pentanediamine crude product, it is also possible to be penta
The aqueous solution of diamidogen crude product.
Pentanediamine crude product, refer to the pentanediamine water that obtains from pentanediamine fermentation liquid, enzymatic conversion liquid, saline solution/
The purity that organic solution is obtained by process for purification such as evaporation, rectification product more than 98%.
Pentanediamine crude product aqueous solution, refers to penta obtained from pentanediamine fermentation liquid, enzymatic conversion liquid or chemical method
Diamine salts solution adds free pentanediamine content that alkali the obtains aqueous solution at more than 10wt% further.Penta 2
Amine crude product aqueous solution can also be obtained in water by pentanediamine dissolving crude product.
Pentanediamine aqueous solution can also obtain concentration higher pentanediamine solution by further concentrating.
Nylon salt when the polymerization energy consumption cost too low because of concentration is too high, and the concentration of industrial nylon salt is the most all controlled
System is at more than 40wt%.Therefore, in the present invention, the concentration of pentanediamine aqueous solution is preferably more than 15wt%.
In one embodiment of the present invention, the pentanediamine aqueous solution of 10wt%, can pass through concentration and evaporation, obtain
Concentration is the pentanediamine solution of 25wt%.
The present invention concentration to nylon salt solution to be purified, not particularly requirement, nylon salt can be equably
Dissolve in the solution.It is said that in general, in pentanediamine saline solution, the concentration becoming the pentanediamine of salt is the lowest
In 10wt%, not higher than 30wt% (calculates) on the basis of solution weight.
The pH of the nylon salt solution to be purified in the present invention is 5.0～9.5, preferably 6.0～8.5, more preferably
PH is 7～8.5.
In the present invention, can be activated carbon, absorption tree for processing the adsorbent of nylon salt solution to be purified
Fat, the most wooden macroporous granules activated carbon, wooden macropore Powdered Activated Carbon or nonpolar macroporous absorption tree
Fat, this adsorbent is for removing 2,3,4,5-tetrahydropyridines in nylon salt solution to be purified.
The form that nylon salt aqueous solution to be purified is contacted by the present invention with adsorbent, there is no particular limitation,
Can be to use any existing mode.In one embodiment of the present invention, adsorbent is directly added into treats
After the aqueous solution of purification nylon salt stirs a period of time, by adsorbent and nylon salt solution separating；At this
In another embodiment of invention, adsorbent is loaded in post, after nylon salt solution to be purified is crossed post
Collect the effluent containing nylon salt.
After adsorbent processes, can pass through the conventional solid-liquid separating methods such as centrifugal, filtration will
Adsorbent and nylon salt solution separating, obtain the nylon salt solution of purification, in this solution, 2,3,4,5-tetra-
The content of pyridinium hydroxide significantly reduces, and can reach the requirement of polymerization technique.
The present invention acts on temperature not particularly requirement, the general room temperature of nylon salt to be purified to adsorbent
All can carry out at (20 DEG C) to 100 DEG C, preferably room temperature to 70 DEG C, this temperature be specifically as follows 30 DEG C,
60 DEG C, 70 DEG C or 90 DEG C.
In the present invention, the consumption of adsorbent and the source of nylon salt solution to be purified, 2,3,4,5-tetrahydropyridines
Content, the condition etc. of absorption have the biggest relation.The usage amount of adsorbent can be
Between 1wt%～20wt% (relative to the weight of the raw material pentanediamine added when preparing nylon salt), it is preferably
1wt%～12wt%.
The nylon salt solution of the purification of the present invention prepares the method for polymer can use any known skill
Art.Those skilled in the art should may determine that concrete technological parameter, and selects to add according to concrete needs
Add other auxiliary agent.
The list of references that description mentions need to be particularly pointed out and include that patent documentation, non-patent literature should be regarded as this
A part for invention.
Below by specific embodiment, the present invention is described in detail, so that the features and advantages of the present invention
Become apparent from.It should be understood that embodiment is only used for understanding the design of the present invention, protection scope of the present invention
It is not limited to embodiment listed herein.
Preparation method and the assay method of the materials such as sample used in embodiment and comparative example are as described below:
1, pentanediamine and the detection method of 2,3,4,5-tetrahydropyridine:
See CN102782146A, use gas chromatogram normalization method.
2, nylon method for detecting color:
GB-T 2409-1980, uses KONICA MINOLTA CM-3600A equipment.
The pentanediamine crude product aqueous solution of the present invention, then can be according to patent PCT/CN as do not specialized
2013/071044, PCT/CN 2013/071045, JP 2009096796A, JP 2009131239A etc.
The method provided prepares.
Embodiment 1 pentanediamine adipate
By the 1 of 10wt%, 5-pentanediamine aqueous solution concentrates in single effect evaporator, and evaporating pressure is
-0.09MPa (gauge pressure), with 121 DEG C of steam heating, concentration steps up, and obtains 1, and 5-pentanediamine content is
The 1,5-pentanediamine concentrated aqueous solution of 20wt%.
Become salt oven to replace wherein air three times by the way of vacuum nitrogen filling gas 100 liters of enamel, and use
Nitrogen is protected, and adds 40kg above-mentioned 1,5-pentanediamine concentrated aqueous solution to becoming, add thermosol under stirring in salt oven
Liquid is to 60 DEG C, and adds adipic acid (middle oil Liaoyang petrochemical corporation (complex), lower same) regulation in this solution
PH value of solution is 7.5, prepares pentanediamine adipic acid nylon salt solution to be purified.
The above-mentioned nylon salt solution to be purified of sample analysis, analysis result shows, 2,3,4,5-tetrahydropyridines are relative
Content in 1,5-pentanediamine is 0.42wt% (normalization method).
Above-mentioned pentanediamine adipate crude product solution adds 0.4 kilogram of wooden macropore Powdered Activated Carbon (on
Hai Jiuniu Industrial Co., Ltd., is called for short nine Ns of Shanghai), nitrogen is protected, and at a temperature of 60 DEG C, stirs 1 hour,
Filter paper filtering, obtains the pentanediamine adipic acid nylon salt solution of the purification of clarification.
With the pentanediamine adipate solution of GC detection purification, analysis result shows, 2,3,4,5-tetrahydrochysene pyrroles
Pyridine is 0.06% (normalization method) relative to the content of pentanediamine.
Embodiment 2 pentanediamine sebacate
By the 1 of 5wt%, 5-pentanediamine aqueous solution concentrates in single effect evaporator, and evaporating pressure is
-0.09MPa, with 121 DEG C of steam heating, concentration steps up, and obtains 1, and 5-pentanediamine content is 15wt%
Pentanediamine concentrated aqueous solution.
Become salt oven to replace wherein air three times by the way of vacuum nitrogen filling gas 100 liters of enamel, and use
Nitrogen is protected, and adds 50kg above-mentioned 1,5-pentanediamine concentrated aqueous solution to becoming, add thermosol under stirring in salt oven
Liquid is to 60 DEG C, and adds decanedioic acid (Hengshui, Hebei east wind chemical industry Co., Ltd) tune in this solution
Joint pH value of solution is 8.5, prepares pentanediamine sebacate solution to be purified.
The above-mentioned nylon salt solution to be purified of sample analysis, analysis result shows, 2,3,4,5-tetrahydropyridines are relative
Content in 1,5-pentanediamine is 0.24% (normalization method).
0.9 kilogram of wooden macropore Powdered Activated Carbon (river is added in above-mentioned pentanediamine sebacate crude product solution
Yinshih (St 33) Jin Lida Chemical Co., Ltd.), nitrogen is protected, and at a temperature of 60 DEG C, stirs 1 hour, filter paper filtering,
Obtain the pentanediamine sebacate solution of the purification of clarification.
With the pentanediamine decanedioic acid nylon salt solution of GC detection purification, analysis result shows, 2,3,4,5-tetra-
Pyridinium hydroxide is 0.05% (normalization method) relative to the content of 1,5-pentanediamine.
Embodiment 3 pentanediamine adipate
By the 1 of 10wt%, 5-pentanediamine aqueous solution (containing 4% butanol) concentrates in single effect evaporator, evaporation
Pressure is-0.09MPa, and with 121 DEG C of steam heating, concentration steps up, and obtains 1,5-pentanediamine content
1,5-pentanediamine concentrated aqueous solution (containing butanol 0.8%) for 25wt%.
Become salt oven to replace wherein air three times by the way of vacuum nitrogen filling gas 100 liters of enamel, and use
Nitrogen is protected, and adds 40kg above-mentioned 1,5-pentanediamine concentrated aqueous solution to becoming, be heated under stirring in salt oven
40 DEG C, and in this solution, addition adipic acid regulation pH value of solution is 8.2, prepares pentanediamine to be purified own
Diacid salt solution.
The above-mentioned nylon salt solution to be purified of sample analysis, analysis result shows, 2,3,4,5-tetrahydropyridines are relative
Content in 1,5-pentanediamine is 0.35% (normalization method).
Above-mentioned pentanediamine adipate crude product solution adds 1 kilogram of wooden macropore Powdered Activated Carbon (on
Hai Jiuniu), nitrogen is protected, and at a temperature of 60 DEG C, stirs 1 hour, filter paper filtering, obtains the purification of clarification
Pentanediamine adipate solution.
With the pentanediamine adipate solution of GC detection purification, analysis result shows, 2,3,4,5-tetrahydrochysene pyrroles
Pyridine is 0.07% (normalization method) relative to the content of 1,5-pentanediamine.
Embodiment 4 pentanediamine adipate
Become salt oven to replace wherein air three times by the way of vacuum nitrogen filling gas 100 liters of enamel, and use
Nitrogen is protected, to become salt oven adds 7.5kg1,5-pentanediamine (2,3,4,5-tetrahydropyridines relative to 1,5-penta 2
The content of amine is 0.31%) and 50kg water, at 30 DEG C, then to becoming, salt oven adds adipic acid, be adjusted to
In salt oven, the pH value of solution is 6.5, and solution is clarified completely, prepares pentanediamine adipate to be purified molten
Liquid.
0.75 kilogram of wooden macropore powder activity is added in above-mentioned pentanediamine adipate solution to be purified
Charcoal (Jin Lida Chemical Co., Ltd. of Jiangyin City), nitrogen is protected, at a temperature of 30 DEG C, is stirred 1 hour, filters
Paper filters, and obtains the pentanediamine adipate solution of the purification of clarification.
With the pentanediamine adipate solution of GC detection purification, analysis result shows, 2,3,4,5-tetrahydrochysene pyrroles
Pyridine is 0.09% (normalization method) relative to the content of 1,5-pentanediamine.
Embodiment 5 pentanediamine dodecanedioic acid salt
Become salt oven to replace wherein air three times by the way of vacuum nitrogen filling gas 100 liters of enamel, and use
Nitrogen is protected, and adds 6kg 1 in salt oven to becoming, and 5-pentanediamine (2,3,4,5-tetrahydropyridines relative to 1,5-penta 2
The content of amine is 0.31%) and 50kg water, at 70 DEG C, to becoming to add dodecanedioic acid in salt oven, (Shandong is triumphant
Match biotechnology Materials Co., Ltd), being adjusted to the pH value of solution in salt oven is 7.2, and solution is the most clear
Clearly, pentanediamine dodecanedioic acid saline solution to be purified is prepared.
0.12 kilogram of wooden macropore Powdered Activated Carbon (Shanghai nine is added in above-mentioned nylon salt solution to be purified
Cattle), nitrogen is protected, and at a temperature of 70 DEG C, stirs 1 hour, filter paper filtering, obtains the penta of the purification clarified
Diamidogen dodecanedioic acid saline solution.
Detect the pentanediamine dodecanedioic acid nylon salt solution of above-mentioned purification with GC, analysis result shows,
2,3,4,5-tetrahydropyridine is 0.06% (normalization method) relative to the content of 1,5-pentanediamine.
Embodiment 6 pentanediamine adipate
Become salt oven to replace wherein air three times by the way of vacuum nitrogen filling gas 100 liters of enamel, and use
Nitrogen is protected, and adds 20kg 1 in salt oven to becoming, and 5-pentanediamine (2,3,4,5-tetrahydropyridines relative to 1,5-penta 2
The content of amine is 0.28%) and 50kg water, at 70 DEG C, to becoming salt oven to add adipic acid, it is adjusted to salt oven
The pH value of solution is 7.8, and solution is clarified completely, prepares pentanediamine adipate solution to be purified.
In above-mentioned pentanediamine adipate solution to be purified, add 2.4 kilograms of wooden macropore powder sugars use
Activated carbon (China Forests Science Academe Forests Chemical Industry Research Institute), nitrogen is protected, at a temperature of 70 DEG C,
Stir 1 hour, filter paper filtering, obtain the pentanediamine adipate solution of the purification of clarification.
With the pentanediamine adipic acid nylon salt solution of GC detection purification, analysis result shows, 2,3,4,5-tetra-
Pyridinium hydroxide is relative to the content 0.02% (normalization method) of 1,5-pentanediamine.
Embodiment 7 mixes nylon salt
Enamel becomes salt oven replace wherein air three times by the way of vacuum nitrogen filling gas, and protects with nitrogen
Protect, to becoming, salt oven adds 5kg pure water, be subsequently adding 1.33kg 1,5-pentanediamine (2,3,4,5-tetrahydropyridines
Relative to 1, the content of 5-pentanediamine is 0.31%), stirring, add 1.90kg adipic acid, add 6-
Aminocaproic acid 2.0kg, solution ph 7.1, prepare nylon salt aqueous solution to be purified.
The wooden macropore Powdered Activated Carbon of 0.0133 kilogram, nitrogen is added in above-mentioned nylon salt solution to be purified
Gas shielded, at a temperature of 70 DEG C, stirs 1 hour, filter paper filtering, and the nylon salt of the purification obtaining clarification is molten
Liquid.
With GC detection purification nylon salt solution, analysis result shows, 2,3,4,5-tetrahydropyridines relative to
1,5-pentanediamine content 0.04% (normalization method).
Embodiment 8 mixes nylon salt
Porcelain becomes salt oven replace wherein air three times by the way of vacuum nitrogen filling gas, and protects with nitrogen,
To becoming, salt oven adds 25kg pure water, be subsequently adding 5.55kg 1,5-pentanediamine (2,3,4,5-tetrahydropyridine phases
For 1, the content of 5-pentanediamine is 0.31%), stirring, add 5.95kg hexamethylene diamine (Luo Diya group),
Stirring, adds adipic acid about 15.41kg, and solution ph is 7.1, prepares nylon salt to be purified water-soluble
Liquid.
The wooden macropore Powdered Activated Carbon of 0.25 kilogram, nitrogen is added in above-mentioned nylon salt solution to be purified
Protection, at a temperature of 90 DEG C, stirs 1 hour, filter paper filtering, obtains the nylon salt solution of the purification of clarification.
With GC detection purification nylon salt solution, analysis result shows, 2,3,4,5-tetrahydropyridines relative to
1,5-pentanediamine content 0.03% (normalization method).
Embodiment 9 mixes nylon salt
Porcelain becomes salt oven replace wherein air three times by the way of vacuum nitrogen filling gas, and protects with nitrogen,
To become in salt oven to add the 1 of 40.56kg, 5-pentanediamine aqueous solution (1,5-pentanediamine concentration 26.04wt%,
2,3,4,5-tetrahydropyridines are relative to 1, and 5-pentanediamine content is 0.31%), add 7.55kg adipic acid, then add
Enter SL-AH, regulate pH value 7.2, prepare nylon salt aqueous solution to be purified.
The wooden macroporous granules activated carbon of 1.27 kilograms, nitrogen is added in above-mentioned nylon salt solution to be purified
Protection, at a temperature of 80 DEG C, stirs 1 hour, filter paper filtering, obtains the nylon salt solution of the purification of clarification.
With GC detection purification nylon salt solution, analysis result shows, 2,3,4,5-tetrahydropyridines relative to
1,5-pentanediamine content 0.02% (normalization method).
Embodiment 10 mixes nylon salt
Porcelain becomes salt oven replace wherein air three times by the way of vacuum nitrogen filling gas, and protects with nitrogen,
Adding 5kg pure water in salt oven to becoming, be subsequently adding 1.33kg 1, (2,3,4,5-tetrahydropyridines are relative for 5-pentanediamine
In 1, the content of 5-pentanediamine is 0.31%), stirring, add 1.90kg adipic acid, add 6-amino
Caproic acid 2.0kg, solution ph 7.1, prepare nylon salt aqueous solution to be purified.
The wooden macroporous granules activated carbon of 1.0 kilograms, nitrogen is added in above-mentioned nylon salt solution to be purified
Protection, at a temperature of 70 DEG C, stirs 1 hour, filter paper filtering, obtains the nylon salt solution of the purification of clarification.
With GC detection purification nylon salt solution, analysis result shows, 2,3,4,5-tetrahydropyridines relative to
1,5-pentanediamine content 0.04% (normalization method).
Embodiment 11 mixes nylon salt
Porcelain becomes salt oven replace wherein air three times by the way of vacuum nitrogen filling gas, and protects with nitrogen,
Adding 25kg pure water in salt oven to becoming, (2,3,4,5-tetrahydropyridines are relative to be subsequently adding 5.55kg1,5-pentanediamine
In 1, the content of 5-pentanediamine is 0.31%), stirring, add 5.95kg hexamethylene diamine (Luo Diya group), stir
Mixing, add adipic acid about 15.41kg, solution ph is 7.1, prepares nylon salt aqueous solution to be purified.
Nonpolar macroporous adsorption resin (the Su Qing of 0.55 kilogram is added in above-mentioned nylon salt solution to be purified
Board), nitrogen is protected, and at a temperature of 90 DEG C, stirs 1 hour, filter paper filtering, obtains the Buddhist nun of the purification of clarification
Dragon saline solution.
With GC detection purification nylon salt solution, analysis result shows, 2,3,4,5-tetrahydropyridines relative to
1,5-pentanediamine content 0.06% (normalization method).
Embodiment 12 pentanediamine adipate
Become salt oven to replace wherein air three times by the way of vacuum nitrogen filling gas 100 liters of enamel, and use
Nitrogen is protected, and adds 20kg 1 in salt oven to becoming, and 5-pentanediamine (2,3,4,5-tetrahydropyridines relative to 1,5-penta 2
The content of amine is 0.28%) and 50kg water, at 70 DEG C, add adipic acid, regulate pH value 7.8, prepare
Nylon salt aqueous solution to be purified.
By above-mentioned nylon salt aqueous solution to be purified with the speed of 2BV/h join diameter 3cm, high 60cm,
It is filled with in the detached dowel of 350mL nonpolar macroporous adsorption resin (Rohm Hass Products), flow velocity
2BV/h.Collect eluent, obtain the nylon salt solution of purification.
Detect the nylon salt solution of above-mentioned purification with GC, analysis result shows, 2,3,4,5-tetrahydropyridine phases
For 1,5-pentanediamine content 0.05% (normalization method).
Embodiment 13 pentanediamine adipate
Become salt oven to replace wherein air three times by the way of vacuum nitrogen filling gas 100 liters of enamel, and use
Nitrogen is protected, and adds 20kg 1 to becoming in salt oven, and 5-pentanediamine is (open according to the clear 60-23328 of open patent
Method obtain, 2,3,4,5-tetrahydropyridines are relative to 1, and the content of 5-pentanediamine is 1.49wt%) and 50kg
Water, at 70 DEG C, adds adipic acid, regulates pH value 7.9, prepare nylon salt aqueous solution to be purified.
2 kilograms of wooden macropore Powdered Activated Carbons (nine Ns of Shanghai) are added in above-mentioned nylon salt solution to be purified,
Nitrogen is protected, and at a temperature of 90 DEG C, stirs 1 hour, filter paper filtering, obtains the pentanediamine of the purification of clarification
Adipate solution.
With the pentanediamine adipate solution of GC detection purification, analysis result shows, 2,3,4,5-tetrahydrochysene pyrroles
Pyridine is relative to 1,5-pentanediamine content 0.08% (normalization method).
Embodiment 14 pentanediamine adipate
Adipic acid pentanediamine salt (2,3,4,5-to be purified is obtained according to method disclosed in JP2004208646A
Tetrahydropyridine is relative to 1, and the content of 5-pentanediamine is 0.33wt%), put into and water is formed 30wt% concentration
Aqueous solution 30kg.
Adding 0.24 kilogram of wooden macropore Powdered Activated Carbon (nine Ns of Shanghai) in above-mentioned solution, nitrogen is protected,
At a temperature of 60 DEG C, stirring 1 hour, filter paper filtering, the pentanediamine adipate of the purification obtaining clarification is molten
Liquid.
With the pentanediamine adipate solution of GC detection purification, analysis result shows, 2,3,4,5-tetrahydrochysene pyrroles
Pyridine is relative to 1,5-pentanediamine content 0.10% (normalization method).
Embodiment 15 pentanediamine adipate
Adipic acid pentanediamine salt (2,3,4,5-tetra-to be purified is obtained according to method disclosed in EP1482055A1
Pyridinium hydroxide is relative to 1, and the content of 5-pentanediamine is 0.41wt%), put into the water forming 40wt% concentration in water
Solution 50kg.
(China Forest science is ground to add 0.44 kilogram of wooden macropore powder craboraffin in above-mentioned solution
Study carefully chemistry of forest product industrial research institute of institute), nitrogen is protected, and at a temperature of 70 DEG C, stirs 1 hour, filter paper filtering,
Obtain the pentanediamine adipate solution of the purification of clarification.
With the pentanediamine adipate solution of GC detection purification, analysis result shows, 2,3,4,5-tetrahydrochysene pyrroles
Pyridine is relative to 1,5-pentanediamine content 0.09% (normalization method).
Embodiment 16 pentanediamine terephthalate
(the triumphant match in Shandong, its 2,3,4,5-tetrahydropyridine is relative to 1,5-to take 6kg pentanediamine terephthalate
The content of pentanediamine is 0.38wt%), put into the aqueous solution 20kg preparing 30wt% concentration in water.
By above-mentioned nylon salt aqueous solution to be purified with the speed of 2BV/h join diameter 3cm, high 60cm,
It is filled with in the detached dowel of 350mL nonpolar macroporous adsorption resin (Rohm Hass Products), flow velocity
2BV/h.Collect eluent, obtain the nylon salt solution of purification.
Detect the nylon salt solution of above-mentioned purification with GC, analysis result shows, 2,3,4,5-tetrahydropyridine phases
For 1,5-pentanediamine content 0.04% (normalization method).
Comparative example 1
Become salt oven to replace wherein air three times by the way of vacuum nitrogen filling gas 100 liters of enamel, and use
Nitrogen is protected, and adds 20kg 1 in salt oven to becoming, and 5-pentanediamine (2,3,4,5-tetrahydropyridines relative to 1,5-penta 2
The content of amine is 0.28%) and 50kg water, at 70 DEG C, add adipic acid, regulate pH value 7.8, solution
Clarify completely, obtain pentanediamine adipate solution.
Comparative example 2
Become salt oven to replace wherein air three times by the way of vacuum nitrogen filling gas 100 liters of enamel, and use
Nitrogen is protected, and adds 20kg 1 in salt oven to becoming, and 5-pentanediamine (2,3,4,5-tetrahydropyridines relative to 1,5-penta 2
The content of amine is 0.28%) and 50kg water, at 70 DEG C, add adipic acid, regulate pH value 7.8, solution
Clarify completely, obtain pentanediamine adipate solution.
(China Forest science is ground to add 1.2 kilograms of coconut husk granulated carbon in above-mentioned pentanediamine adipate solution
Study carefully chemistry of forest product industrial research institute of institute), nitrogen is protected, and at a temperature of 70 DEG C, stirs 1 hour, filter paper filtering,
Obtain the pentanediamine adipate purification solution of clarification.
Detecting pentanediamine adipate purification solution with GC, analysis result shows, 2,3,4,5-tetrahydropyridines
Relative to 1,5-pentanediamine content 0.22% (normalization method).
The preparation of application examples polyamide
By 100 liters of polymeric kettle nitrogen displaced air, and nylon salt solution is transferred in polymeric kettle, oil
Bath temperature rises to 230 DEG C, and in treating still, pressure rises to 1.73MPa, starts aerofluxus, treats that temperature in the kettle reaches
When 265 DEG C, it is evacuated to-0.06MPa (vacuum gauge pressure), keeps this vacuum 20min, prepare corresponding Buddhist nun
Dragon.
Being filled with nitrogen in polymeric kettle to pressure is 0.5MPa, starts melted discharging, and utilizes pelleter to make
Grain.80 DEG C be dried vacuum drying 8 hours after detect.By embodiment 1-16 and comparative example 1,2 institute
The nylon salt obtained prepares polyamide according to said method, and the yellow colour index of detection gained polyamide, result is shown
In table 1.
Table 1
| 2,3,4,5-tetrahydropyridine content | Nylon yellow colour index | |
| Embodiment 1 | 0.06% | 4 |
| Embodiment 2 | 0.05% | 4 |
| Embodiment 3 | 0.07% | 5 |
| Embodiment 4 | 0.09% | 6 |
| Embodiment 5 | 0.06% | 4 |
| Embodiment 6 | 0.02% | 2 |
| Embodiment 7 | 0.04% | 3 |
| Embodiment 8 | 0.03% | 3 |
| Embodiment 9 | 0.02% | 2 |
| Embodiment 10 | 0.04% | 4 |
| Embodiment 11 | 0.06% | 5 |
| Embodiment 12 | 0.05% | 5 |
| Embodiment 13 | 0.08% | 6 |
| Embodiment 14 | 0.10% | 6 |
| Embodiment 15 | 0.09% | 6 |
| Embodiment 16 | 0.04% | 4 |
| Comparative example 1 | 0.28% | 15 |
| Comparative example 2 | 0.22% | 13 |
The 2,3,4,5-tetrahydropyridine that table 1 lists in the nylon salt that the embodiment of the present invention and comparative example prepare contains
Amount, and the yellow colour index of the nylon prepared by the polymerization of above-mentioned nylon salt.The data provided from table 1,
In the nylon salt of the purification prepared by the method for the present invention, the content of 2,3,4,5-tetrahydropyridine is all 0.1
Within wt%, the polymerization of this nylon salt the nylon generated is compared with the nylon of prior art, and yellow colour index is significantly
Declining, quality has obtained obvious improvement.
Unless limited otherwise, term used herein is the implication that those skilled in the art are generally understood that.
Embodiment described in the invention is merely for exemplary purpose, and is not used to limit the guarantor of the present invention
Protecting scope, those skilled in the art can be made within the scope of the invention various other and replace, change and change
Enter, thus, the invention is not restricted to above-mentioned embodiment, and be only defined by the claims.
Claims (13)
1. a nylon salt for purification, the salt formed with dicarboxylic acids including diamine, described diamine is extremely
Including 1 less, 5-pentanediamine, wherein, impurity 2 in described nylon salt, the content of 3,4,5-tetrahydropyridines is less than
0.1wt%, described content is with described 1, on the basis of the weight of 5-pentanediamine.
Nylon salt the most according to claim 1, wherein said diamine includes C4～C18Fat
One or more in race's diamine and aromatic diamine.
Nylon salt the most according to claim 1, wherein said dicarboxylic acids includes C4～C18Fat
One or more in fat race diacid, aromatic diacid and heterocycle diacid.
Nylon salt the most according to claim 3, wherein said dicarboxylic acids selected from succinic acid, oneself two
One or more in acid, decanedioic acid, dodecanedioic acid, p-phthalic acid, furan dicarboxylic acid.
Nylon salt the most according to any one of claim 1 to 4, wherein said impurity 2,3,4,5-
The content of tetrahydropyridine is less than 0.05wt%.
Nylon salt the most according to claim 5, the content of wherein said impurity 2,3,4,5-tetrahydropyridine
Less than 0.03wt%.
7. remove the method for impurity 2,3,4,5-tetrahydropyridine in nylon salt for one kind, including, it is provided that one is to be purified
Nylon salt；By described nylon salt to be purified through sorbent treatment, obtain the nylon salt of purification, wherein, constitute
The diamidogen of described nylon salt at least includes 1,5-pentanediamine.
Method the most according to claim 7, in the nylon salt of wherein said purification, impurity 2,3,4,5-
The content of tetrahydropyridine is less than 0.1wt%.
Method the most according to claim 7, wherein said absorbing agent treatment step includes, stirs shape
Being added by described adsorbent in the aqueous solution of described nylon salt to be purified under state, holding solution temperature is
20 DEG C～100 DEG C, separate described adsorbent, obtain the nylon salt of described purification.
Method the most according to claim 7, wherein said absorbing agent treatment step includes, by described
The aqueous solution of nylon salt to be purified, by being filled with the adsorption column of described adsorbent, collects containing of described adsorption column
The effluent of nylon salt, obtains the nylon salt of described purification.
11. according to the method according to any one of claim 7 to 10, and wherein said adsorbent is selected from big
Macroporous adsorbent resin or activated carbon, described adsorbent is preferably nonpolar macroporous adsorption resin or wooden macropore activity
Charcoal.
12. methods according to claim 11, the consumption of wherein said adsorbent is 1～20wt%,
It is preferably 1～12wt%, with described 1, on the basis of the weight of 5-pentanediamine.
13. methods according to claim 11, wherein prepare the step bag of described nylon salt to be purified
Include: dicarboxylic acids is joined containing 1, in the diamine aqueous solution of 5-pentanediamine, and regulate the pH of solution
Value is 5.0～9.5.
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| CN106861236A (en) * | 2017-02-27 | 2017-06-20 | 南京工业大学 | A kind of method of utilization hypercrosslinked polymeric resin adsorbing separation pentanediamine |
| CN109265353A (en) * | 2018-10-16 | 2019-01-25 | 南京工业大学 | Pentanediamine dodecanedioic acid salt and its crystal |
| CN110540511A (en) * | 2018-05-29 | 2019-12-06 | 上海凯赛生物技术股份有限公司 | method for extracting and purifying diamine salt |
| CN111592454A (en) * | 2019-02-21 | 2020-08-28 | 上海凯赛生物技术股份有限公司 | Method for producing diamine salt, diamine salt solution, diamine salt and polymer |
| CN111825557A (en) * | 2019-04-19 | 2020-10-27 | 上海凯赛生物技术股份有限公司 | High-purity nylon 5X salt and purification method thereof |
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| JP2012106935A (en) * | 2010-11-15 | 2012-06-07 | Mitsui Chemicals Inc | Method for preserving pentamethylenediamine or salt thereof |
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| CN106861236A (en) * | 2017-02-27 | 2017-06-20 | 南京工业大学 | A kind of method of utilization hypercrosslinked polymeric resin adsorbing separation pentanediamine |
| CN110540511A (en) * | 2018-05-29 | 2019-12-06 | 上海凯赛生物技术股份有限公司 | method for extracting and purifying diamine salt |
| CN110540511B (en) * | 2018-05-29 | 2024-05-03 | 上海凯赛生物技术股份有限公司 | Extraction and purification method of diamine salt |
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| CN109265353B (en) * | 2018-10-16 | 2021-06-29 | 南京工业大学 | Pentanediamine dodecanedioic acid salt and crystal thereof |
| CN111592454A (en) * | 2019-02-21 | 2020-08-28 | 上海凯赛生物技术股份有限公司 | Method for producing diamine salt, diamine salt solution, diamine salt and polymer |
| CN111592454B (en) * | 2019-02-21 | 2023-08-08 | 上海凯赛生物技术股份有限公司 | Preparation method of diamine salt, diamine salt solution, diamine salt and polymer |
| CN111825557A (en) * | 2019-04-19 | 2020-10-27 | 上海凯赛生物技术股份有限公司 | High-purity nylon 5X salt and purification method thereof |
| CN114196010A (en) * | 2022-01-29 | 2022-03-18 | 优纤科技（丹东）有限公司 | Preparation method of flame-retardant modified terpolymer nylon polymer |
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