CN106750268A - A kind of caprolactam and diamines and the continuous polymerization technique and the copolymer of diacid salt copolymer - Google Patents
A kind of caprolactam and diamines and the continuous polymerization technique and the copolymer of diacid salt copolymer Download PDFInfo
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- CN106750268A CN106750268A CN201611033481.1A CN201611033481A CN106750268A CN 106750268 A CN106750268 A CN 106750268A CN 201611033481 A CN201611033481 A CN 201611033481A CN 106750268 A CN106750268 A CN 106750268A
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- diamines
- caprolactam
- diacid
- diacid salt
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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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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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
- C08G69/04—Preparatory processes
Abstract
The invention discloses a kind of caprolactam and the continuous polymerization technique and the copolymer of diamines and diacid salt copolymer, belong to nylon technical field.In the copolymer, the weight/mass percentage composition of diamines and diacid salt reaches as high as 60%, and between 155.8 DEG C 219.3 DEG C, relative viscosity is between 2.4 3.6 for copolymer fusing point.Caprolactam and diamines and diacid salt copolymer are prepared using three-stage continuous polymerization, it is characterized in that the addition manner combined using solid nylon diamines and diacid salt and nylon diamines and diacid saline solution, caprolactam is set to be well mixed before the reaction with diamines and diacid salt, highly random copolymer is obtained by polymerization, when preparing caprolactam with diamines and diacid salt copolymer using the preparation method, process operability is strong.Obtained caprolactam has low fusing point, broader process window with diamines and diacid salt copolymer, is adapted to the application such as extrusion, inflation film, PUR and fiber.
Description
Technical field
The present invention relates to technical field of chemical synthesis, more particularly to a kind of caprolactam and diamines and diacid salt copolymer
Continuous polymerization technique and the copolymer.
Background technology
Nylon 6 has excellent physical and mechanical property, good wearability, excellent oil resistant, solvent resistant, corrosion resistance
Can, it is widely used the advantages of but also with self lubricity and good processing characteristics, but there is dry state or low temperature undershoot in nylon 6
Hit intensity is low, transparent difference, fusing point poor compared with flexibility under high and low temperature the shortcomings of, limit its application.To expand answering for nylon 6
With scope, the demand of more areas is met, people are modified to nylon 6, the characteristics of wherein modification by copolymerization has excellent effect,
Quickly grow.
Continuous production nylon 6/AB copolymerized products use the process units of nylon 6, i.e. one-part form polymerization technique at present
Or two-part polymerization technique, prior art there are problems that nylon diamines and diacid salt conversion ratio is low, diamines, it is impossible to produce
The copolymerized product of diamines high and diacid salt content.
The content of the invention
In view of this, the invention provides a kind of caprolactam and diamines and diacid salt copolymer continuous polymerization technique and
The copolymer, has more preferable random distribution by monomeric unit in the copolymer obtained in the technique, shows lower melting
Point is thus more suitable for practicality.
In order to reach above-mentioned first purpose, the caprolactam that the present invention is provided and diamines and diacid salt copolymer it is continuous
The technical scheme of polymerization technique and the copolymer is as follows：
The caprolactam that the present invention is provided is used with the continuous polymerization technique and the copolymer of diamines and diacid salt copolymer
Three-stage is polymerized, and is mixed subsequently into HTHP before the reaction using caprolactam (CPL) and nylon diamines and diacid salt
Reactor produces caprolactam and diamines and diacid salt copolymer, comprises the following steps：
1) mixture I is mixed to get in mixed flow container using caprolactam and solid nylon diamines and diacid salt, will be mixed
Thing I, nylon diamines and diacid saline solution mix in pipe-line mixer；
2) by step 1) material of mixing delivers to first reactor and is polymerized to form prepolymer；
3) material after first reactor delivers to the first acid amides exchanger, and the material after the first acid amides exchanger delivers to second
Reactor；
4) by step 3) material that obtains delivers to the second acid amides exchanger, and the material after the second acid amides exchanger delivers to the 3rd
Reactor；
5) by step 4) caprolactam that obtains carries out pelletizing with diamines and diacid salt Copolymer Melts by pelleter, so
Obtain caprolactam and diamines and diacid salt copolymer slice finished product after extracting, drying again afterwards.
The caprolactam that the present invention is provided may be used also with the continuous polymerization technique and the copolymer of diamines and diacid salt copolymer
It is applied to the following technical measures to achieve further.
Preferably, raw material is grouped into by each group of following weight parts：Mass content for 70-99.8% caprolactam,
Mass content is the auxiliary agent of 0.02-0.5% for the diamines and diacid salt, mass content of 0.2-30%.
Preferably, raw material is grouped into by each group of following weight parts：Mass content is caprolactam, the matter of 40-70%
Amount content is the auxiliary agent of 0.02-0.5% for the diamines and diacid salt, mass content of 30-60%.
Preferably, the caprolactam is fresh caprolactam or fresh caprolactam and the caprolactam by reclaiming
Mixture.
Preferably, the fresh caprolactam and fresh caprolactam in the mixture of the caprolactam by reclaiming
Mass content is not less than 50%.
Preferably, the salt that the nylon diamines and diacid salt are formed for the diamines of Formulas I and the diacid of Formula II
H2N-R1-NH2 I
HOOC-R2-COOH II
Wherein R1Representative contains 4 to 12 alkyl groups of carbon atom, wherein R2Representative contains 2 to 10 alkane of carbon atom
Base group.
Preferably, the nylon diamines and diacid salt be the salt of nylon 54,56 salt, 66 salt, 610 salt, 612 salt, 1010 salt,
1212 salt.
Preferably, the total amount that the amount of the solid nylon diamines and diacid salt is based on monomer is calculated as 0.2-30%.
Preferably, the preparation method of the mixture I is to be more than under 99.999% nitrogen atmosphere in purity, using physics
Shearing dispersion or stirring or mixed allocation or the method for grinding obtain suspension or solution of the particle diameter less than 1 μm, the temperature
80-190 DEG C, time 30s-2h.
Preferably, the nylon diamines and diacid saline solution mass concentration are in 62%-80%.
Preferably, the nylon diamines and diacid saline solution mass concentration are in 62%-75%.
Preferably, the amount of diamines and diacid salt is based on the total amount meter of monomer in the nylon diamines and diacid saline solution
It is 0-30%.
Preferably, the first reactor pressure 8-50bar, 245-285 DEG C of temperature, residence time 1-4h.
Preferably, the first reactor pressure 15-38bar, 260-280 DEG C of temperature, residence time 2-3h.
Preferably, the step 1) addition or it is not added with the catalyst of acid amides exchange reaction.
Preferably, the catalyst is shown in formula III and/or formula IV
R3-SO3-R4 III
Wherein R3Representative contains 1 to 16 alkyl group of carbon atom, or phenyl or aminomethyl phenyl；R4Represent H, Li, Na
Or K；
R5-COO-M IV
Wherein, R5Represent H or contain 1 to 7 alkyl group of carbon atom；M represents Zn, Mg or Sn.
Preferably, the catalyst is p-methyl benzenesulfonic acid, paratoluenesulfonic acid sodium salt, p-methyl benzenesulfonic acid potassium, dodecyl sulphur
One or more in sour sodium, zinc acetate, magnesium acetate, stannous octoate.
Preferably, the conversion ratio of nylon diamines and diacid salt is in 90-98% in first reactor.
Preferably, comprising three reactors of non-duct type, and first and second and second and the 3rd reactor it
Between strengthen acid amides exchange reaction more than 10,000 acid amides exchanger using draw ratio.
Preferably, the first acid amides exchanger temperature control is at 245-285 DEG C, material is in the first acid amides exchanger
Residence time be 0.5-2h, pressure is down to 3-6bar from 8-50bar.
Preferably, the second reactor temperature control is at 255-275 DEG C, in 3-6bar, material stops Stress control
It is 2-3h to stay the time.
Preferably, the 3rd temperature of reactor control is at 240-255 DEG C, Stress control in -50mbar~50mbar,
The residence time of material is 10-12h, and during nitrogen caused into the material on the 3rd reactor top, the consumption of the nitrogen is
0.1-1.5Nm3/ tons of section.
Preferably, using knockout tower, or other types simultaneously in two reactor heads of second and third reactor
Technique the reactor head separate moisture.
Described caprolactam is minimum with diamines and diacid salt copolymer product fusing point up to 155.8 DEG C, and relative viscosity exists
Between 2.4-3.6.
Compared with prior art, the caprolactam that the present invention is provided and diamines and the continuous polymerization technique of diacid salt copolymer
And the copolymer has the beneficial effect that：
1. the addition manner that solid nylon diamines and diacid salt and nylon diamines and diacid saline solution are combined, diamines are taken
60% can be up to diacid salt content, fully ensures that caprolactam, diamines and diacid salt, auxiliary agent etc. are equal in molecular level mixing
It is even, it is ensured that the stability and homogeneity of product.
2. promote acid amides exchange reaction by adding catalyst, caprolactam and diamines and two of degree of randomness high can be produced
Hydrochlorate copolymer.
3. the easy oligomer sedimentation of excessive concentration is produced when this technique solves that extract is concentrated in current production technology
Line clogging problem, it is only necessary to using 69% concentrate, when greatly reducing concentration energy consumption and increase technique stability and
Operability.
4. three reactors and two acid amides exchangers use different process parameter controls, and the controllability of technique is strong.
Brief description of the drawings
By reading the detailed description of hereafter preferred embodiment, various other advantages and benefit is common for this area
Technical staff will be clear understanding.Accompanying drawing is only used for showing the purpose of preferred embodiment, and is not considered as to the present invention
Limitation.And in whole accompanying drawing, identical part is denoted by the same reference numerals.In the accompanying drawings：
Caprolactam and diamines and the continuous polymerization technique and the copolymer of diacid salt copolymer that Fig. 1 is provided for the present invention
The step of flow chart.
Specific embodiment
The present invention is to solve the problems, such as prior art, there is provided a kind of caprolactam and diamines and diacid salt copolymer
Continuous polymerization technique and the copolymer, have more preferable random distribution by monomeric unit in the copolymer obtained in the technique,
Lower fusing point is shown thus more suitable for practicality.
Further to illustrate the present invention to reach technological means and effect that predetermined goal of the invention is taken, below in conjunction with
Accompanying drawing and preferred embodiment, to the continuous polymerization technique according to caprolactam proposed by the present invention and diamines and diacid salt copolymer
And the copolymer, its specific embodiment, structure, effect of feature, describe in detail as after.In the following description, different " one
What embodiment " or " embodiment " referred to is not necessarily same embodiment.Additionally, special characteristic, structure in one or more embodiments,
Or feature can be combined by any suitable form.
The terms "and/or", only a kind of incidence relation for describing affiliated partner, represents there may be three kinds of passes
System, for example, A and/or B, is specifically interpreted as：A and B can simultaneously be included, can be with individualism A, it is also possible to individualism
B, can possess above-mentioned three kinds of any one situations.
Embodiment 1
A. the fresh molten caprolactams of 378kg and the salt of 120kg solid nylons 66 are added in mixed flow container per hour, 80
Under the conditions of DEG C, by stirring 20min, mixture I is obtained.
B. by mixture I, 154.5kg nylon salt aqueous solution (concentration is wt.66%) and 1.92kg terephthalic acid (TPA)s
(PTA) mix in static mixer, be polymerized to form prepolymer subsequently into first reactor, the pressure of first reactor is
15bar, temperature is 260 DEG C, and the residence time is 2h, and the conversion ratio of nylon salt is 93%.
C. first reactor prepolymer is delivered into the first acid amides exchanger, the first acid amides exchanger temperature is 258 DEG C, is stopped
Time is 1h, and pressure drops to 4bar from 15bar.
D. the first acid amides exchanger material is delivered into second reactor, second reactor temperature is 260 DEG C, and reaction pressure is
4bar, residence time 2h.
E. second reactor material is delivered into the 3rd reactor by the second acid amides exchanger, the temperature of the 3rd reactor is
250 DEG C, reaction pressure is 10mbar, and the residence time is 11h.And the nitrogen of 0.6m3/ tons of section is caused into the 3rd reactor top
Moisture content is separated in material.After reaction terminates, obtain copolymer, then copolymer through supercooling, pelletizing, extract and be dried to obtain
Copolymerization PA6/66, its relative viscosity is 2.6, and fusing point is 170.6 DEG C.
Embodiment 2-10 be caprolactam and different nylon diamines and the example of diacid salt and different output, using with
The similar preparation technology of embodiment 1, its polymerization process condition and product index see the table below.
The operating parameter of embodiment 1~10 and result parameter summary sheet
Embodiment 11-18 is as a example by adding catalyst
In this group of embodiment, catalyst is one kind of auxiliary agent, in addition to this it is possible to common in being selected from nylon polymerization reaction
Additive as auxiliary agent.
Embodiment 12
A. the fresh molten caprolactams of 540kg and the salt of 30kg solid nylons 1010 are added in mixed flow container per hour,
Under the conditions of 100 DEG C, by stirring 20min, mixture I is obtained.
B. by mixture I, 45.5kg nylon 1010 saline solution (concentration is wt.66%), 1.5kgPTA, 1.5kg octanoic acid
Stannous mix in static mixer, are polymerized to form prepolymer subsequently into first reactor, and the pressure of first reactor is
15bar, temperature is 265 DEG C, and the residence time is 3h, and the conversion ratio of Nylon-1010 Salt is 97%.
C. first reactor prepolymer is delivered into the first acid amides exchanger, the first acid amides exchanger temperature is 266 DEG C, is stopped
Time is 1.5h, and pressure drops to 5bar from 15bar.
D. the first acid amides exchanger material is delivered into second reactor, second reactor temperature is 265 DEG C, and reaction pressure is
5bar, residence time 3h.
E. second reactor material is delivered into the 3rd reactor by the second acid amides exchanger, the temperature of the 3rd reactor is
255 DEG C, reaction pressure is 20mbar, and the residence time is 12h.And by 0.6m3The nitrogen of/ton section causes the 3rd reactor top
Moisture content is separated in material.After reaction terminates, copolymer is obtained.Copolymer through supercooling, pelletizing, extract and be dried to obtain copolymerization
PA6/1010.Copolymer relative viscosity is 2.6, and fusing point is 196.6 DEG C.
Embodiment 11 uses and uses similar to Example 12 with the identical preparation technology of embodiment 12, embodiment 13-18
Preparation technology, its polymerization process condition and product index see the table below.
Because caprolactam is different from the reactivity of diamines and diacid salt, reaction rate, product structure and product are caused
The difference of performance, by adding the catalyst of acid amides exchange reaction, promotes the acid amides of Nylon 6 Chains section and nylon AB segments to exchange anti-
The caprolactam and diamines and diacid product salt of degree of randomness high should be obtained.Comparative example 11 and 12, embodiment 13 and 14, implementation
Example 15 and 16, embodiment 17 and 18, using identical polymerization technique, the caprolactam and diamines and diacid salt for adding catalyst are produced
Product are than being not added with catalyst with lower fusing point.
, but those skilled in the art once know basic creation although preferred embodiments of the present invention have been described
Property concept, then can make other change and modification to these embodiments.So, appended claims are intended to be construed to include excellent
Select embodiment and fall into having altered and changing for the scope of the invention.
Obviously, those skilled in the art can carry out various changes and modification without deviating from essence of the invention to the present invention
God and scope.So, if it is of the invention these modification and modification belong to the claims in the present invention equivalent technologies scope it
Interior, then the present invention is also intended to comprising these changes and modification.
Claims (10)
1. the continuous polymerization technique of a kind of caprolactam and diamines and diacid salt copolymer, it is characterised in that gathered using three-stage
Close, mix subsequently into high-temperature high-voltage reaction device to produce oneself before the reaction using caprolactam and nylon diamines and diacid salt
Lactams and diamines and diacid salt copolymer, comprise the following steps：
1) be mixed to get mixture I in mixed flow container using caprolactam and solid nylon diamines and diacid salt, by mixture I,
Nylon diamines and diacid saline solution mix in pipe-line mixer；
2) by step 1) material of mixing delivers to first reactor and is polymerized to form prepolymer；
3) material after first reactor delivers to the first acid amides exchanger, and the material after the first acid amides exchanger delivers to the second reaction
Device；
4) by step 3) material that obtains delivers to the second acid amides exchanger, and the material after the second acid amides exchanger delivers to the 3rd reaction
Device；
5) by step 4) caprolactam that obtains carries out pelletizing, Ran Houzai with diamines and diacid salt Copolymer Melts by pelleter
Caprolactam and diamines and diacid salt copolymer slice finished product are obtained after extracting, drying.
2. the continuous polymerization technique of caprolactam according to claim 1 and diamines and diacid salt copolymer, its feature exists
In raw material is grouped into by each group of following weight parts：Mass content is the caprolactam of 70-99.8%, mass content is 0.2-
30% diamines and diacid salt, the auxiliary agent that mass content is 0.02-0.5%.
3. the continuous polymerization technique of caprolactam according to claim 1 and diamines and diacid salt copolymer, its feature exists
In raw material is grouped into by each group of following weight parts：Mass content is the caprolactam of 40-70%, mass content is 30-60%
Diamines and diacid salt, mass content for 0.02-0.5% auxiliary agent.
4. the continuous polymerization technique of caprolactam according to claim 1 and diamines and diacid salt copolymer, its feature exists
In the caprolactam is the mixture of fresh caprolactam or fresh caprolactam and the caprolactam by reclaiming.
5. the continuous polymerization technique of caprolactam according to claim 4 and diamines and diacid salt copolymer, its feature exists
In the fresh caprolactam is not less than with the mass content of fresh caprolactam in the mixture by the caprolactam for reclaiming
50%.
6. the continuous polymerization technique of caprolactam according to claim 1 and diamines and diacid salt copolymer, its feature exists
In the salt that the nylon diamines and diacid salt are formed for the diamines of Formulas I and the diacid of Formula II
H2N-R1-NH2 I
HOOC-R2-COOH II
Wherein R1Representative contains 4 to 12 alkyl groups of carbon atom, wherein R2Representative contains 2 to 10 alkyl bases of carbon atom
Group.
7. the continuous polymerization technique of caprolactam according to claim 6 and diamines and diacid salt copolymer, its feature exists
In the nylon diamines and diacid salt are the salt of nylon 54,56 salt, 66 salt, 610 salt, 612 salt, 1010 salt, 1212 salt.
8. the continuous polymerization technique of caprolactam according to claim 1 and diamines and diacid salt copolymer, its feature exists
In the total amount of the amount based on monomer of the solid nylon diamines and diacid salt is calculated as 0.2-30%.
9. the continuous polymerization technique of caprolactam according to claim 1 and diamines and diacid salt copolymer, its feature exists
In the preparation method of the mixture I is to be more than under 99.999% nitrogen atmosphere in purity, is disperseed or is stirred using the shearing of physics
Mix or mixed allocation or the method for grinding suspension or solution of the acquisition particle diameter less than 1 μm, 80-190 DEG C of the temperature, time
30s-2h；
Preferably, the nylon diamines and diacid saline solution mass concentration are in 62%-80%；
Preferably, the nylon diamines and diacid saline solution mass concentration are in 62%-75%；
Preferably, the total amount of the amount based on monomer of diamines and diacid salt is calculated as 0- in the nylon diamines and diacid saline solution
30%；
Preferably, the first reactor pressure 8-50bar, 245-285 DEG C of temperature, residence time 1-4h；
Preferably, the first reactor pressure 15-38bar, 260-280 DEG C of temperature, residence time 2-3h；
Preferably, the step 1) addition or it is not added with the catalyst of acid amides exchange reaction；
Preferably, the catalyst is shown in formula III and/or formula IV
R3-SO3-R4 III
Wherein R3Representative contains 1 to 16 alkyl group of carbon atom, or phenyl or aminomethyl phenyl；R4Represent H, Li, Na or K；
R5-COO-M IV
Wherein R5Represent H or contain 1 to 7 alkyl group of carbon atom；M represents Zn, Mg or Sn；
Preferably, the catalyst be p-methyl benzenesulfonic acid, paratoluenesulfonic acid sodium salt, p-methyl benzenesulfonic acid potassium, dodecyl sodium sulfate,
One or more in zinc acetate, magnesium acetate, stannous octoate；
Preferably, the conversion ratio of nylon diamines and diacid salt is in 90-98% in first reactor；
Preferably, comprising three reactors of non-duct type, and second and the 3rd make at first and second and between reactor
Acid amides exchanger with draw ratio more than 10,000 is strengthening acid amides exchange reaction；
Preferably, the first acid amides exchanger temperature control is in 245-285 DEG C, material stopping in the first acid amides exchanger
Stay the time for 0.5-2h, pressure is down to 3-6bar from 8-50bar；
Preferably, the second reactor temperature control is at 255-275 DEG C, Stress control is in 3-6bar, the stop of material
Between be 2-3h；
Preferably, the 3rd temperature of reactor control is at 240-255 DEG C, Stress control is in -50mbar~50mbar, material
Residence time be 10-12h, during nitrogen caused into the material on the 3rd reactor top, the consumption of the nitrogen is 0.1-
1.5Nm3/ ton is cut into slices；
Preferably, using knockout tower, or other kinds of work simultaneously in two reactor heads of second and third reactor
Skill separates moisture in the reactor head；
Preferably, described caprolactam and diamines and diacid salt copolymer product fusing point are between 155.8 DEG C -219.3 DEG C,
Relative viscosity is between 2.4-3.6.
10. common with diamines and diacid salt using caprolactam obtained in any described continuous polymerization technique in claim 1~9
Polymers, it is characterised in that
The caprolactam is 2.4-3.6 with the span of diamines and the relative viscosity of diacid salt copolymer；
The caprolactam is 155.8 DEG C -219.3 DEG C with the span of diamines and the fusing point of diacid salt copolymer.
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Address after: No. 3, Yan Jing Li Zhongjie, Chaoyang District, Beijing, Beijing Patentee after: China Textile Science Research Institute Co., Ltd. Address before: No. 3, Yan Jing Li Zhongjie, Chaoyang District, Beijing, Beijing Patentee before: Chinese Textile Scientific Research Inst. |
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