CN114920923B - Process method for continuous polymerization of ammonium carboxylate and caprolactam - Google Patents
Process method for continuous polymerization of ammonium carboxylate and caprolactam Download PDFInfo
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- CN114920923B CN114920923B CN202210756623.6A CN202210756623A CN114920923B CN 114920923 B CN114920923 B CN 114920923B CN 202210756623 A CN202210756623 A CN 202210756623A CN 114920923 B CN114920923 B CN 114920923B
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- 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
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- 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
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Abstract
The invention discloses a process method for continuously polymerizing ammonium carboxylate and caprolactam, which comprises the steps of (I) preparing ammonium carboxylate aqueous solution; (II) synthesizing ammonium carboxylate and caprolactam small molecular oligomer; (iii) mixing the small molecule oligomer with caprolactam; (IV) synthesizing ammonium carboxylate and caprolactam macromolecular oligomer; (V) Synthesis of a copolymer of ammonium carboxylate and caprolactam; (VI) post-treatment. The invention provides a process method for continuously copolymerizing diamine and dicarboxylic acid to form ammonium carboxylate salt, wherein the process method can change the properties of melting point, crystallinity, transparency and the like of a polymer prepared from caprolactam monomer, so as to prepare a series of ammonium carboxylate salt and caprolactam copolymer with low softening point, good transparency, softness and the like.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a process method for continuously polymerizing ammonium carboxylate and caprolactam.
Background
The polymer prepared from caprolactam monomer has regular molecular structure arrangement and high crystallinity, and the added ammonium carboxylate salt is continuously copolymerized with caprolactam, so that the proportion of the caprolactam monomer and the ammonium carboxylate salt can be changed according to different application fields and performance requirements by adding the ammonium carboxylate salt, thereby changing the copolymer structure, and simultaneously changing the properties of melting point, crystallinity, transparency and the like of the copolymer, thereby preparing the ammonium carboxylate salt and caprolactam series copolymer variety with adjustable properties of low softening point, good transparency, softness and the like, effectively realizing the high performance and functionalization of the ammonium carboxylate salt and caprolactam copolymer material, and expanding the application fields of the copolymer.
The existing diamine and dicarboxylic acid and caprolactam copolymerization process has the problems of low diamine dicarboxylic acid salt conversion rate, diamine volatilization and the like, and can not produce a copolymer with high diamine dicarboxylic acid salt content; meanwhile, in the prior art, caprolactam and ammonium carboxylate salt are blended and mixed once, and a large amount of ammonium carboxylate salt aqueous solution is directly added into caprolactam at one time, so that the ammonium carboxylate salt is greatly separated out to block a pipeline, and the production is influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a process method for continuously polymerizing ammonium carboxylate salt and caprolactam.
The invention is realized by the following technical scheme:
a process for the continuous polymerization of ammonium carboxylate salts with caprolactam comprising the steps of:
preparation of aqueous ammonium carboxylate salts
Mixing diamine and dicarboxylic acid with water as a solvent to form an ammonium carboxylate salt aqueous solution;
(II) Synthesis of ammonium carboxylate salt and caprolactam Small molecular oligomer
Mixing and concentrating the ammonium carboxylate salt aqueous solution and caprolactam to form ammonium carboxylate salt caprolactam small molecular oligomers;
(III) mixing small molecular oligomers with caprolactam
Mixing preheated caprolactam and the ammonium carboxylate salt caprolactam small molecular oligomer obtained in the step (II), and exchanging heat;
(IV) Synthesis of ammonium carboxylate salt and caprolactam macromolecular oligomer
Performing prepolymerization on the ammonium carboxylate caprolactam small molecular oligomer and caprolactam in a prepolymerizer to form ammonium carboxylate caprolactam large molecular oligomer;
(V) Synthesis of copolymer of ammonium carboxylate and caprolactam
Discharging excessive water from the ammonium carboxylate caprolactam macromolecular oligomer obtained in the step (IV) in a post-polymerizer, and performing post-polymerization for promoting molecular weight increase to obtain an ammonium carboxylate caprolactam copolymer;
(VI) post-treatment
And (5) granulating, extracting, dehydrating, drying and cooling the ammonium carboxylate caprolactam copolymer obtained in the step (V) to obtain the caprolactam diamine copolymer.
In the above technical scheme, the diamine is any one or a mixture of any two or more of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 8-octanediamine or 1, 10-decanediamine.
In the above technical scheme, the dicarboxylic acid is any one or a mixture of any two or more of 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 8-suberic acid, 1, 10-sebacic acid and terephthalic acid.
In the technical scheme, the whole process of materials needs nitrogen protection.
In the technical scheme, the concentration of the ammonium carboxylate aqueous solution obtained in the step (I) is 40% -60%; the pH value of the ammonium carboxylate aqueous solution is 5.5-11; the temperature of the mixture of diamine and dicarboxylic acid is room temperature to 100 ℃.
In the above technical scheme, the ammonium carboxylate aqueous solution and caprolactam in the step (ii) have equal mass; the concentration temperature is controlled between 80 ℃ and 180 ℃, and the mass concentration of the concentrated ammonium carboxylate aqueous solution is 60% -90%.
In the technical scheme, the preheating temperature of caprolactam in the step (III) is 120-180 ℃; the temperature after mixing and heat exchanging is 150-270 ℃.
In the technical scheme, the temperature of the pre-polymerizer in the step (IV) is controlled to be 160-280 ℃; the pressure is controlled between 0.5MPa and 1.5MPa.
In the technical scheme, the temperature of the post-polymerizer in the step (V) is controlled to be 260-320 ℃.
An ammonium carboxylate caprolactam continuous copolymer is obtained by a process method for continuously polymerizing ammonium carboxylate and caprolactam, wherein the weight percentage of the ammonium carboxylate and the caprolactam in the copolymer is as follows:
5% -70% of ammonium carboxylate salt;
30% -95% of caprolactam;
the melting point range of the copolymer is 170-290 ℃;
the relative viscosity of the copolymer ranges from 2.0 to 4.0.
The beneficial effects of the invention are as follows:
the invention provides a process method for continuously copolymerizing diamine and dicarboxylic acid to form ammonium carboxylate salt, wherein the process method can change the properties of melting point, crystallinity, transparency and the like of a polymer prepared from caprolactam monomer, so as to prepare a series of ammonium carboxylate salt and caprolactam copolymer with low softening point, good transparency, softness and the like.
Drawings
FIG. 1 is a schematic view of a production apparatus employed in the present invention;
FIG. 2 is a graph showing the effect of pH on the viscosity of a copolymer product obtained from an aqueous solution of adipic acid hexadi-ammonium salt of example 1 of the present invention;
FIG. 3 is a graph of the effect of glutarimide adipate salt on the melting point of the copolymer product in example 2 of the present invention;
FIG. 4 is a graph showing the effect of the hexadi-ammonium terephthalate salt on the melting point of the copolymer product in example 3 of the present invention.
Wherein:
1 diacid preparing tank 2 diamine melting kettle
3 dibasic acid aqueous solution conveying pump 4 diamine conveying pump
Salt-forming tank with stirring function 5 and caprolactam storage tank 6
Caprolactam preheater with 7 concentration tank 8
9 dynamic mixing unit 10 tube-in-tube heat exchanger
Pre-polymerization condensation spray system of pre-polymerization device 11 and pre-polymerization condensation spray system of pre-polymerization device 12
Post-polymerization condensation spray system of post-polymerization device 14
15 vacuum system 16 underwater pelletizer pelleting
17 extraction tower 18 continuous dehydrator
19 drying tower 20 nitrogen spraying system
21 cooling tower 22 feed bin.
Other relevant drawings may be made by those of ordinary skill in the art from the above figures without undue burden.
Detailed Description
In order to make the technical scheme of the invention better understood by the person skilled in the art, the technical scheme of the process method for continuously polymerizing ammonium carboxylate salts and caprolactam of the invention is further described below by a specific embodiment in combination with the attached drawings in the specification.
As shown in fig. 1, a process for continuously polymerizing ammonium carboxylate salts with caprolactam comprises the following steps:
preparation of aqueous ammonium carboxylate salts
Mixing diamine and dicarboxylic acid with water as a solvent to form an ammonium carboxylate salt aqueous solution;
the specific operation steps of the combining device are as follows:
the diamine is melted into liquid in a diamine melting kettle 1, dicarboxylic acid is prepared into dicarboxylic acid aqueous solution in a dicarboxylic acid preparing tank 2, the diamine liquid in the diamine melting kettle 1 and the dicarboxylic acid aqueous solution in the dicarboxylic acid preparing tank 2 are respectively sent into a salt forming tank 5 through a diamine conveying pump 4 and a dicarboxylic acid aqueous solution conveying pump 3, the temperature in the salt forming tank is controlled between room temperature and 100 ℃, and ammonium carboxylate aqueous solution with the mass concentration of 40-60% is formed through stirring in the salt forming tank, and the pH value of the ammonium carboxylate aqueous solution is controlled between 5.5 and 11; the pH is monitored by an on-line pH meter placed in the salt tank and adjusted by adjusting the material.
Because diamine is more volatile than dicarboxylic acid, the pH value needs to be controlled above a certain range to ensure the addition amount of diamine, and after the highest pH value of the ammonium carboxylate aqueous solution formed by diamine and dicarboxylic acid is determined, the viscosity of the copolymer can be changed by adjusting the pH value of the ammonium carboxylate aqueous solution formed by diamine and dicarboxylic acid, and the lower the pH value of the ammonium carboxylate aqueous solution is, the lower the viscosity of the copolymer is.
(II) Synthesis of ammonium carboxylate salt and caprolactam Small molecular oligomer
Mixing and concentrating the ammonium carboxylate salt aqueous solution and caprolactam to form ammonium carboxylate salt caprolactam small molecular oligomers;
the specific operation steps of the combining device are as follows:
the prepared ammonium carboxylate salt aqueous solution in the salifying tank 5 and a part of caprolactam in the caprolactam storage tank 6 are respectively injected into a concentration tank 7 through a metering pump control to be mixed and concentrated to form ammonium carboxylate salt and caprolactam small molecular oligomers; the mass of the ammonium carboxylate salt aqueous solution is the same as that of the caprolactam, the temperature of the concentration tank 7 is controlled between 80 ℃ and 180 ℃, and the mass concentration of the concentrated ammonium carboxylate salt aqueous solution is 60% -90%;
the concentration tank 7 is a vertical structural shell with sealed upper and lower ends, an outer spiral heating coil is arranged on the periphery of the shell, an inner spiral heating coil is arranged in the shell, a main feeding pipe and a secondary feeding pipe are arranged on the shell, a discharge hole is arranged at the bottom of the shell, a gas phase outlet is arranged at the top of the shell, a recovery device is connected with the gas phase outlet, volatile diamines are collected, a stirring shaft is arranged at the center of the top of the shell and stretches into the shell, and stirring blades are arranged on the stirring shaft. When the concentration tank 7 works, steam is introduced into the outer spiral heating coil and the inner spiral heating coil, the ammonium carboxylate solution enters the shell from the main feeding pipe, heated and evaporated, caprolactam entering the secondary feeding pipe is rotationally mixed through the stirring shaft and is promoted to evaporate, evaporated gas leaves the device from the gas phase outlet, the gas outlet is connected with the condensing spray tower of the recovery device, and the ammonium carboxylate solution self concentrates the concentration of the ammonium carboxylate solution to 60% -90% in the concentration tank. The mass concentration of the concentrated ammonium carboxylate aqueous solution is converted according to the material balance, and polymerization with caprolactam is neglected in calculation.
Caprolactam participates in the concentration process of the ammonium carboxylate aqueous solution to form small molecular oligomers, namely the mass concentration of the ammonium carboxylate aqueous solution is improved to between 60 and 90 percent, and the small molecular oligomers are formed, so that the volatilization of diamine is prevented.
(III) mixing small molecular oligomers with caprolactam
Mixing and preheating the preheated caprolactam and the ammonium carboxylate salt caprolactam small molecular oligomer obtained in the step (II);
the specific operation steps of the combining device are as follows:
the rest caprolactam output from the caprolactam storage tank 6 is preheated to 120-180 ℃ by a caprolactam preheater 8, and is mixed and preheated with the ammonium carboxylate salt caprolactam small molecular oligomer output from the concentration tank 7 by a tubular heat exchanger 10 added with a dynamic mixing unit 9; the temperature of the mixed liquid reaches 150-270 ℃ after heat exchange by the tube-in-tube heat exchanger 10.
The irregular flow of the materials of the tube array heat exchanger 10 of the dynamic mixing unit 9 is increased, the boundary resistance between the materials and the tube wall is greatly reduced, the heat exchange efficiency is greatly improved by 3-5 times, the effect on high-viscosity fluid is more remarkable, the heat exchanger of the dynamic mixing unit is increased due to the continuous irregular movement of the materials, the problems of ageing and deterioration of the materials, and the like, caused by uneven heating of the tube wall and the middle fluid for a long time, are avoided, and the uniform mixing of the oligomer and the caprolactam is ensured by the dynamic mixing unit.
The mass ratio of ammonium carboxylate salt to caprolactam is perceived by the composition of the desired end product, wherein a portion of the caprolactam equivalent to the ammonium carboxylate salt is first mixed with the ammonium carboxylate salt in a concentration tank, and the remaining caprolactam is mixed with the ammonium carboxylate salt caprolactam small molecular oligomer having been subjected to the first mixing in a dynamic mixing unit 9.
And caprolactam is added into the continuous copolymerization process twice, the small molecular oligomer is formed by concentrating the ammonium carboxylate salt aqueous solution in the step II at one time, and the small molecular oligomer of the ammonium carboxylate salt and caprolactam in the step III is mixed by a dynamic mixing unit at one time, so that a large amount of caprolactam is prevented from being directly added into the ammonium carboxylate salt aqueous solution, and a large amount of ammonium carboxylate salt is prevented from precipitating out and blocking a pipeline.
(IV) Synthesis of ammonium carboxylate salt and caprolactam macromolecular oligomer
The small molecular oligomer of the ammonium carboxylate caprolactam and the caprolactam are pre-polymerized in a pre-polymerizer at 160 ℃ to 280 ℃ and under the pressure of 0.5MPa to 1.5MPa, the reaction time is 3h to 6h, and the reaction is completed to form the large molecular oligomer of the ammonium carboxylate and the caprolactam;
the specific operation steps of the combining device are as follows:
the ammonium carboxylate salt caprolactam small molecular oligomer and caprolactam mixed solution output by the shell and tube heat exchanger 10 are polymerized in a front polymerizer 11, the top of the front polymerizer 11 is provided with an exhaust port, and the exhaust port is connected with a front polymerization condensation spray system 12.
In the process of prepolymerization, a large amount of heat is absorbed, the deviation between the material temperature and the temperature of heat conduction oil in the jacket of the prepolymerizer 11 is possibly larger, a serpentine coil is added in the prepolymerizer for heating, the thermal deformation of equipment caused by the temperature difference inside and outside the sleeve is relieved, the service life of the equipment is prolonged, and the macromolecular oligomer of ammonium carboxylate caprolactam is formed. Meanwhile, in order to prevent the volatilization of the diamine, the volatilization of the diamine is reduced in a mode of maintaining pressure in the pre-polymerizer,
meanwhile, in the copolymerization process of ammonium carboxylate and caprolactam, a large amount of water is required to be drained to promote the increase of the molecular weight of the copolymer. At the same time, the sudden pressure drop can separate water and caprolactam in the ammonium carboxylate salt caprolactam oligomer containing a large amount of moisture, the redundant moisture is discharged from the exhaust port of the front polymerizer in the form of saturated steam, the exhaust port is connected with the front polymerization condensation spray system, and the discharge port controls the discharge amount of saturated steam by controlling the feeding amount of the ammonium carboxylate salt caprolactam oligomer containing a large amount of moisture and caprolactam (namely, the amount of the mixed solution output by the tubular heat exchanger 10) and the pressure in the front polymerizer, so that the discharge amount of saturated steam is controlled, and the rapid copolymerization of ammonium carboxylate salt and caprolactam to form macromolecular copolymer caused by the large discharge of moisture is prevented, and the agglomeration in the front polymerizer is avoided.
(V) Synthesis of copolymer of ammonium carboxylate and caprolactam
Reacting the ammonium carboxylate caprolactam macromolecular oligomer obtained in the step (IV) in a post-polymerizer under the conditions of 260-320 ℃ and-1.0-0.5 MPa for 4-8 hours, discharging excessive water, and performing post-polymerization for promoting molecular weight increase;
the specific operation steps of the combining device are as follows:
the ammonium carboxylate salt caprolactam macromolecular oligomer output by the front polymerizer 11 enters the rear polymerizer 13, the tube array in the rear polymerizer 13 is heated by biphenyl, the temperature is controlled to be 260 ℃ to 320 ℃, the ammonium carboxylate salt caprolactam macromolecular oligomer discharges excessive moisture in the rear polymerizer 13, the excessive moisture is discharged from the exhaust port of the rear polymerizer 13 in the form of saturated steam, the exhaust port is connected with the rear polymerization condensation spray system 14, the discharge of the moisture is ensured through the vacuumizing system 15, the post polymerization for promoting the molecular weight increase is carried out, and the copolymer of the ammonium carboxylate salt and the caprolactam is primarily obtained by controlling the residence time of the oligomer in the rear polymerizer.
(VI) post-treatment
And (5) granulating, extracting, dehydrating, drying and cooling the ammonium carboxylate caprolactam copolymer obtained in the step (V) to obtain the caprolactam diamine copolymer.
The specific operation steps of the combining device are as follows:
the copolymer of ammonium carboxylate salt and caprolactam obtained by the post-polymerizer is discharged into a cooling water tank through a melt extrusion pump, pelletized through an underwater pelletizer 16, extracted by constant boiling water for 24 hours in an extraction tower 17, the extracted copolymer with water enters a continuous dehydrator 18 from the lower end, water is discharged from a dehydration port of the continuous dehydrator 18 in the rising process of the copolymer, the copolymer is discharged from the upper part of the dehydrator and enters a drying tower 19, the drying tower 19 is dried by high-temperature nitrogen until the water content is lower than 0.06%, the high-temperature nitrogen is dried, the copolymer enters a nitrogen spraying system 20 for recycling after being dried, the copolymer enters a cooling tower 21 for cooling by normal-temperature circulating nitrogen, and finally enters a stock bin 22 to obtain the caprolactam dibasic acid diamine copolymer.
The whole process method material needs nitrogen protection.
The diamine is any one or a mixture of any two or more of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 8-octanediamine or 1, 10-decanediamine.
The dicarboxylic acid is any one or a mixture of any two or more of 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 8-suberic acid, 1, 10-sebacic acid and terephthalic acid.
The carboxylic acid ammonium salt is any one or a mixture of any two or more of butanedioic acid butanediammonium salt, butanedioic acid penta-diammonium salt, butanedioic acid hexanediammonium salt, butanedioic acid decane-diammonium salt, penta-diammonium salt, hexanedioic acid hexanediammonium salt, penta-diammonium salt of penta-diammonium acid, hexanediammonium salt of hexanedioic acid, octanediammonium salt of hexanedioic acid, butanediammonium salt of hexanedioic acid, penta-diammonium salt of octanediamic acid, octanediammonium salt of octanediamine, octanediamine suberate, decane-diammonium salt of octanediamine, decane-diammonium salt of decane-dicarboxylic acid, decane-diammonium salt of butanedioic acid, decane-diammonium salt of terephthalic acid.
An ammonium carboxylate caprolactam copolymer, wherein the weight percentage of ammonium carboxylate and caprolactam in the copolymer is as follows:
5% -70% of ammonium carboxylate salt;
30% -95% of caprolactam;
the melting point range of the copolymer is 170-290 ℃;
the relative viscosity of the copolymer ranges from 2.0 to 4.0.
Example 1
Under the condition that the water is used as a solvent, hexamethylenediamine and hexanedioic acid generate 50 percent of hexanedioic acid ammonium salt aqueous solution in a salt forming tank at 50 ℃, concentrating the adipic acid hexadimonium salt aqueous solution and caprolactam with the same mass (adipic acid hexadimonium salt) by a 140 ℃ concentration tank, improving the mass concentration of the adipic acid hexadimonium salt aqueous solution to 80%, mixing adipic acid hexa-di-ammonium salt caprolactam small molecular polymer and the rest caprolactam by using a tubular heat exchanger added with a dynamic mixing unit, and performing prepolymerization on the mixed solution in a prepolymerizer at 250 ℃ for 4 hours to form adipic acid hexa-di-ammonium salt caprolactam oligomer; in a post-polymerizer at 280 ℃, the residence time is 6h to carry out the post-polymerization for promoting the molecular weight increase; then, granulating, extracting, dehydrating and drying to obtain the caprolactam hexamethylene diamine copolymer.
The pH of the aqueous solution of hexamethylene diammonium adipate (50% by mass, 101KPa at atmospheric pressure, 50 ℃ C., 298K) was in the range of 5.5-8.5, and the effect on the viscosity of the hexamethylene diamine caprolactamate copolymer was as shown in FIG. 2.
As can be seen from FIG. 2, the pH of the aqueous solution of hexamethylenediamine adipate was in the range of 5.5 to 8.5, and the excess hexamethylenediamine was volatilized during the polymerization without affecting the viscosity of the product. The pH value is reduced due to excessive adipic acid, and the adipic acid can become a blocking agent in the polymerization process, so that the viscosity of the product is reduced.
Example 2
Under the condition that water is used as a solvent, a salt forming tank is used for generating an adipic acid glutaric ammonium salt aqueous solution with the mass concentration of 50%, the adipic acid glutaric ammonium salt aqueous solution and the same mass (adipic acid glutaric ammonium salt) are concentrated through a 160 ℃ concentration tank, the concentration of the adipic acid glutaric ammonium salt aqueous solution is improved to 90%, a tubular heat exchanger added with a dynamic mixing unit is used for mixing with the rest caprolactam, the mixed carboxylic acid ammonium salt aqueous solution and the caprolactam are subjected to prepolymerization in a prepolymerizer with the temperature of 245 ℃, and the residence time is 3h, so that an oligomer of the carboxylic acid ammonium salt and the caprolactam is formed; in a post-polymerizer at 280 ℃, the residence time is 6h to carry out the post-polymerization for promoting the molecular weight increase; then, granulating, extracting, dehydrating and drying to obtain the caprolactam hexamethylene diamine copolymer.
The effect of the mass ratio of glutarimonium adipate to caprolactam on the melting point of the copolymer is shown in FIG. 3.
As can be seen from fig. 3, in the final copolymer, when the mass percentage of glutarimide adipate is in the range of 0 to 35%, the crystallization property of the copolymer is changed with the increase of the glutarimide adipate, the melting point of the glutarimide adipate caprolactam copolymer is reduced, the softness of the copolymer is improved, and the mechanical property detection is carried out, so that the strength of the copolymer is not obviously changed, and the toughness is obviously enhanced. The effect of the mass percentages of the different glutarimate adipates in the final copolymer on the mechanical properties of the copolymer is shown in Table 1.
TABLE 1 influence of the mass percentages of glutarimonium adipate on the physical properties of the copolymer
Example 3
Under the condition that hexamethylenediamine and terephthalic acid are taken as solvents, a salt forming tank is used for generating a hexamethylene diammonium terephthalate aqueous solution with the mass concentration of 45%, the hexamethylene diammonium terephthalate aqueous solution and caprolactam with the same mass (hexamethylene diammonium terephthalate) are concentrated by a 180 ℃ concentration tank, the mass concentration of the hexamethylene diammonium terephthalate aqueous solution is improved to 80%, a tube array heat exchanger added with a dynamic mixing unit is used for mixing with the caprolactam, the mixed ammonium carboxylate aqueous solution and the caprolactam are subjected to prepolymerization in a prepolymerizer with the temperature of 270 ℃, and the residence time is 6h, so that an oligomer of ammonium carboxylate and caprolactam is formed; in a secondary reactor at 300 ℃, the residence time is 8 hours to carry out the post polymerization for promoting the molecular weight increase; then, granulating, extracting, dehydrating and drying to obtain the caprolactam hexamethylene diamine terephthalate copolymer, wherein the extracting time is generally 8 hours.
The effect of the addition of concentrated aqueous solution of hexadi-ammonium terephthalate (80%) and caprolactam on the melting point of the copolymer is shown in FIG. 4.
As can be seen from FIG. 4, in the final copolymer, when the mass percentage of the hexamethylene diamine terephthalate is 45-65%, the crystallization property of the copolymer is changed along with the increase of the hexamethylene diamine terephthalate, particularly the introduction of benzene rings, the melting point of the hexamethylene diamine terephthalate caprolactam copolymer is increased, the brittleness of the copolymer is improved, the mechanical property detection is carried out, and the copolymer strength is found to be not obviously changed and the toughness is obviously reduced. The effect of different amounts of hexamethylene diamine terephthalate in the final copolymer on the physical properties of the copolymer is shown in Table 2.
TABLE 2 influence of the addition of the aqueous solution of hexadi-ammonium terephthalate on the mechanical properties of the copolymer
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (6)
1. A process for continuous polymerization of ammonium carboxylate and caprolactam is characterized in that: the method comprises the following steps:
preparation of aqueous ammonium carboxylate salts
Mixing diamine and dicarboxylic acid with water as a solvent to form an ammonium carboxylate salt aqueous solution; the concentration of the ammonium carboxylate aqueous solution obtained in the step (I) is 40% -60%; the pH value of the ammonium carboxylate aqueous solution is 5.5-11; the temperature of the mixture of diamine and dicarboxylic acid is room temperature to 100 ℃;
(II) Synthesis of ammonium carboxylate salt and caprolactam Small molecular oligomer
Mixing and concentrating the ammonium carboxylate salt aqueous solution and caprolactam to form ammonium carboxylate salt caprolactam small molecular oligomers; the mass of the ammonium carboxylate aqueous solution and the mass of the caprolactam in the step (II) are equal; the concentration temperature is controlled to be 80-180 ℃, and the mass concentration of the concentrated ammonium carboxylate aqueous solution is 60-90%;
(III) mixing small molecular oligomers with caprolactam
Mixing preheated caprolactam and the ammonium carboxylate salt caprolactam small molecular oligomer obtained in the step (II), and exchanging heat; the preheating temperature of caprolactam in the step (III) is 120-180 ℃; the temperature after mixed heat exchange is 150-270 ℃;
(IV) Synthesis of ammonium carboxylate salt and caprolactam macromolecular oligomer
Performing prepolymerization on the ammonium carboxylate caprolactam small molecular oligomer and caprolactam in a prepolymerizer to form ammonium carboxylate caprolactam large molecular oligomer;
(V) Synthesis of copolymer of ammonium carboxylate and caprolactam
Discharging excessive water from the ammonium carboxylate caprolactam macromolecular oligomer obtained in the step (IV) in a post-polymerizer, and performing post-polymerization for promoting molecular weight increase to obtain an ammonium carboxylate caprolactam copolymer;
(VI) post-treatment
And (5) granulating, extracting, dehydrating, drying and cooling the ammonium carboxylate salt caprolactam copolymer obtained in the step (V) to obtain the caprolactam diamine copolymer.
2. The process for the continuous polymerization of ammonium carboxylate salts with caprolactam according to claim 1, wherein: the diamine is any one or a mixture of any two or more of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 8-octanediamine or 1, 10-decanediamine.
3. The process for the continuous polymerization of ammonium carboxylate salts with caprolactam according to claim 1, wherein: the dicarboxylic acid is any one or a mixture of any two or more of 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 8-suberic acid, 1, 10-sebacic acid and terephthalic acid.
4. The process for the continuous polymerization of ammonium carboxylate salts with caprolactam according to claim 1, wherein: the whole process method material needs nitrogen protection.
5. The process for the continuous polymerization of ammonium carboxylate salts with caprolactam according to claim 1, wherein: the temperature of the pre-polymerizer in the step (IV) is controlled to be 160-280 ℃; the pressure is controlled to be 0.5-1.5 MPa.
6. The process for the continuous polymerization of ammonium carboxylate salts with caprolactam according to claim 1, wherein: and (3) controlling the temperature of the post-polymerizer in the step (V) to be 260-320 ℃.
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