CN114920923A - Process method for continuously polymerizing ammonium carboxylate and caprolactam - Google Patents
Process method for continuously polymerizing ammonium carboxylate and caprolactam Download PDFInfo
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- CN114920923A CN114920923A CN202210756623.6A CN202210756623A CN114920923A CN 114920923 A CN114920923 A CN 114920923A CN 202210756623 A CN202210756623 A CN 202210756623A CN 114920923 A CN114920923 A CN 114920923A
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- 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
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Abstract
The invention discloses a process method for continuously polymerizing ammonium carboxylate and caprolactam, which comprises the following steps of (I) preparing an ammonium carboxylate aqueous solution; (II) synthesizing ammonium carboxylate and caprolactam micromolecule oligomer; (III) mixing the small molecular oligomer with caprolactam; (IV) synthesizing ammonium carboxylate and caprolactam macromolecular oligomer; (V) synthesizing a copolymer of carboxylic acid ammonium salt and caprolactam; (VI) post-treatment. The invention provides a process method for forming ammonium carboxylate salt by diamine and dicarboxylic acid and continuously copolymerizing the ammonium carboxylate salt and caprolactam, which can change the properties of melting point, crystallinity, transparency and the like of a polymer prepared by caprolactam monomers, thereby preparing a series of copolymer varieties of ammonium carboxylate salt and caprolactam with adjustable properties of 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 made of caprolactam monomer has orderly arranged molecular structure and high crystallinity, and ammonium carboxylate salt is added to continuously copolymerize with caprolactam, so that the copolymer structure can be changed and the melting point, crystallinity, transparency and other properties of the copolymer can be changed simultaneously by adding ammonium carboxylate salt according to different application fields and performance requirements, thereby preparing the ammonium carboxylate salt and caprolactam series copolymer variety with adjustable properties such as low softening point, good transparency, softness and the like, effectively realizing high performance and functionalization of ammonium carboxylate salt and caprolactam copolymer materials, and expanding the application field.
The existing copolymerization process of diamine, dicarboxylic acid and caprolactam has the problems of low diamine dicarboxylic acid salt conversion rate, diamine volatilization and the like, and the copolymer with high diamine dicarboxylic acid salt content can not be produced; meanwhile, the existing process adopts a one-time blending and mixing mode for caprolactam and ammonium carboxylate, and a large amount of ammonium carboxylate salt is separated out to block a pipeline due to the fact that a large amount of ammonium carboxylate salt aqueous solution is directly added into caprolactam at one time, so that production is influenced.
Disclosure of Invention
The invention is provided for overcoming the defects in the prior art, and aims to provide a process method for continuously polymerizing ammonium carboxylate and caprolactam.
The invention is realized by the following technical scheme:
a process for continuously polymerizing ammonium carboxylate with caprolactam comprises the following steps:
(I) preparation of an aqueous solution of an ammonium carboxylate salt
Mixing diamine and dicarboxylic acid by taking water as a solvent to form an ammonium carboxylate aqueous solution;
(II) Synthesis of ammonium carboxylate and caprolactam Small molecular oligomer
Mixing and concentrating the aqueous solution of the ammonium carboxylate salt and caprolactam to form the ammonium carboxylate salt caprolactam micromolecule oligomer;
(III) mixing the small molecular oligomer with caprolactam
Mixing the preheated caprolactam and the small molecular oligomer of the carboxylic acid ammonium salt caprolactam obtained in the step (II) and exchanging heat;
(IV) Synthesis of ammonium carboxylate and caprolactam Macro oligomer
Pre-polymerizing the carboxylic acid ammonium salt caprolactam micromolecule oligomer and caprolactam in a pre-polymerizer to form carboxylic acid ammonium salt caprolactam macromolecule 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 rear polymerizer, and performing later polymerization for promoting molecular weight increase to obtain an ammonium carboxylate caprolactam copolymer;
(VI) post-treatment
And (V) granulating, extracting, dehydrating, drying and cooling the caprolactam copolymer of the ammonium carboxylate salt obtained in the step (V) to obtain the caprolactam diacid diamine copolymer.
In the above technical scheme, the diamine is any one of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 8-octanediamine or 1, 10-decanediamine or a mixture of any two or more thereof.
In the above technical solution, the dicarboxylic acid is any one of 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 8-suberic acid, 1, 10-sebacic acid, or terephthalic acid, or a mixture of any two or more thereof.
In the technical scheme, the process method needs nitrogen protection in the whole process of materials.
In the technical scheme, the concentration of the ammonium carboxylate aqueous solution obtained in the step (I) is 40-60%; the pH value range of the ammonium carboxylate salt aqueous solution is 5.5-11; the temperature of mixing the diamine and the dicarboxylic acid is between room temperature and 100 ℃.
In the technical scheme, 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 between 80 ℃ and 180 ℃, and the mass concentration of the concentrated ammonium carboxylate aqueous solution is 60 percent to 90 percent.
In the technical scheme, the preheating temperature of caprolactam in the step (III) is 120-180 ℃; the temperature after mixing and heat exchange 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 1.5 MPa.
In the above technical scheme, the temperature of the postpolymerizer in the step (V) is controlled to be 260-320 ℃.
The continuous copolymer of the ammonium carboxylate and the caprolactam is obtained by a process method for continuously polymerizing the ammonium carboxylate and the caprolactam, wherein the weight percentages of the ammonium carboxylate and the caprolactam in the copolymer are as follows:
5 to 70 percent of carboxylic acid ammonium salt;
30 to 95 percent of caprolactam;
the melting point range of the copolymer is 170-290 ℃;
the relative viscosity range of the copolymer is 2.0-4.0.
The invention has the beneficial effects that:
the invention provides a process method for forming ammonium carboxylate salt by diamine and dicarboxylic acid and continuously copolymerizing the ammonium carboxylate salt and caprolactam, which can change the properties of melting point, crystallinity, transparency and the like of a polymer prepared from a caprolactam monomer, thereby preparing a series of copolymer varieties of ammonium carboxylate salt and caprolactam with adjustable properties of low softening point, good transparency, softness and the like.
Drawings
FIG. 1 is a schematic view of the structure of a production apparatus used in the present invention;
FIG. 2 is a graph of data showing the effect of pH on the viscosity of a copolymer product for an aqueous solution of adipic acid diammonium salt in accordance with example 1 of the present invention;
FIG. 3 is a graph of data showing the effect of pentadiammonium adipate salt on the melting point of a copolymer product in example 2 of the present invention;
FIG. 4 is a graph of data showing the effect of hexamethylene diammonium terephthalate salt on the melting point of the copolymer product of example 3 of the present invention.
Wherein:
1 dibasic acid preparation tank and 2 diamine melting kettle
3 binary acid aqueous solution delivery pump and 4 binary amine delivery pump
5 salification tank 6 caprolactam storage tank of area stirring
7 concentration tank 8 caprolactam preheater
9 dynamic mixing unit 10 tube heat exchanger
13 post-polymerizer 14 post-condensing spray system
15 evacuation system 16 underwater granulator pelleter
17 extraction tower 18 continuous dehydrator
19 drying tower 20 nitrogen gas spraying system
The tower 22 silo is cooled 21.
For a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical scheme of the invention better understood by those skilled in the art, the technical scheme of the process for continuously polymerizing ammonium carboxylate and caprolactam of the present invention is further described by the specific embodiments in combination with the attached drawings of the specification.
As shown in figure 1, a process for continuously polymerizing carboxylic ammonium salt and caprolactam comprises the following steps:
(I) preparation of an aqueous solution of an ammonium carboxylate salt
Mixing diamine and dicarboxylic acid by taking water as a solvent to form ammonium carboxylate salt aqueous solution;
the specific operation steps of the combination device are as follows:
the method comprises the following steps of melting diamine into liquid in a diamine melting kettle 1, blending dicarboxylic acid into dicarboxylic acid aqueous solution in a dicarboxylic acid blending tank 2, respectively conveying the diamine liquid in the diamine melting kettle 1 and the dicarboxylic acid aqueous solution in the dicarboxylic acid blending tank 2 into a salt forming tank 5 through a diamine conveying pump 4 and a dicarboxylic acid aqueous solution conveying pump 3, controlling the temperature in the salt forming tank to be between room temperature and 100 ℃, forming ammonium carboxylate aqueous solution with the mass concentration of 40-60% through stirring in the salt forming tank, and controlling the pH value of the ammonium carboxylate aqueous solution to be between 5.5 and 11; the pH value is monitored by an online pH meter arranged in the salifying tank, and is adjusted by adjusting the materials.
Because diamine is more volatile than dicarboxylic acid, the addition of diamine can be ensured only by controlling the pH value to be above a certain range, 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 and caprolactam Small molecular oligomer
Mixing and concentrating the aqueous solution of the ammonium carboxylate salt and caprolactam to form the ammonium carboxylate salt caprolactam micromolecule oligomer;
the specific operation steps of the combination device are as follows:
respectively injecting the prepared ammonium carboxylate aqueous solution in the salifying tank 5 and a part of caprolactam in the caprolactam storage tank 6 into a concentration tank 7 through control of a metering pump for mixing and concentration to form ammonium carboxylate and caprolactam micromolecule oligomer; the adding mass of the ammonium carboxylate aqueous solution is the same as that of caprolactam, the temperature of the concentration tank 7 is controlled to be between 80 and 180 ℃, and the mass concentration of the concentrated ammonium carboxylate aqueous solution is between 60 and 90 percent;
the thickening tank 7 is a vertical structure shell with the upper end and the lower end sealed, an external spiral heating coil is arranged on the periphery of the shell, an internal spiral heating coil is arranged in the shell, a main feeding pipe and an auxiliary feeding pipe are arranged on the shell, a discharging port is arranged at the bottom of the shell, a gas phase outlet is arranged at the top of the shell, the gas phase outlet is connected with a recovery device, volatile binary amines are collected, a stirring shaft is arranged at the center of the top of the shell and extends into the shell, and stirring blades are arranged on the stirring shaft. When the concentration tank 7 works, steam is introduced into the external spiral heating coil and the internal spiral heating coil, the ammonium carboxylate solution enters the shell from the main feeding pipe and is heated and evaporated, the caprolactam entering the secondary feeding pipe is rotationally mixed with the stirring shaft and is promoted to be evaporated, the evaporated gas leaves the device from the gas phase outlet, the gas outlet is connected with the recovery device to condense the spray tower, and the concentration of the ammonium carboxylate solution is concentrated to 60% -90% in the concentration tank. The mass concentration of the concentrated ammonium carboxylate aqueous solution is obtained by conversion according to material balance, and polymerization with caprolactam is ignored in calculation.
During the concentration process of the ammonium carboxylate aqueous solution, caprolactam participates in the formation of micromolecular oligomer, namely the mass concentration of the ammonium carboxylate aqueous solution is increased to 60-90%, and the micromolecular oligomer is formed, so that the volatilization of diamine is prevented.
(III) mixing the small molecular oligomer with caprolactam
Mixing and preheating the preheated caprolactam and the small molecular oligomer of the carboxylic acid ammonium salt caprolactam obtained in the step (II);
the specific operation steps of the combination device are as follows:
the residual more 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 small molecular oligomers of the carboxylic acid ammonium salt caprolactam output from the concentration tank 7 by a tubular heat exchanger 10 additionally provided with a dynamic mixing unit 9; the temperature of the mixed liquid reaches 150-270 ℃ after heat exchange by the tube heat exchanger 10.
The irregular flow of its material of shell and tube heat exchanger 10 that has increased dynamic mixing unit 9 significantly reduces the boundary resistance of material and pipe wall portion, make heat exchange efficiency improve 3 ~ 5 times by a wide margin, it is showing more to the effect of high viscosity fluid very much, the heat exchanger that has increased dynamic mixing unit is because the continuous irregular motion of material, can avoid pipe wall portion and intermediate part fluid because the material that is heated for a long time inequality and produces ages with rotten scheduling problem, utilize dynamic mixing unit, oligomer and caprolactam misce bene have been guaranteed.
The mass ratio of ammonium carboxylate salt to caprolactam is determined by the composition of the desired end product, wherein a portion of caprolactam and ammonium carboxylate salt in equal amounts to the ammonium carboxylate salt is first mixed in a thickening tank and the remaining caprolactam is mixed with the first mixed small molecular oligomers of ammonium carboxylate salt caprolactam in a dynamic mixing unit 9.
Caprolactam is added into the continuous copolymerization process twice, wherein the step II and the ammonium carboxylate aqueous solution are concentrated together to form small molecular oligomers, and the step III and the ammonium carboxylate and the small molecular oligomers of caprolactam are mixed through a dynamic mixing unit, so that the phenomenon that a large amount of caprolactam is directly added into the ammonium carboxylate aqueous solution to cause the ammonium carboxylate to be separated out and block a pipeline is avoided.
(IV) Synthesis of ammonium carboxylate and caprolactam Macro oligomer
The carboxylic acid ammonium salt caprolactam micromolecule oligomer and caprolactam are subjected to pre-polymerization in a pre-polymerizer at the temperature of 160-280 ℃ and under the pressure of 0.5-1.5 MPa, the reaction time is 3-6 h, and the carboxylic acid ammonium salt and caprolactam macromolecule oligomer are formed after the reaction is finished;
the specific operation steps of the combination device are as follows:
the mixed solution of the ammonium carboxylate caprolactam micromolecule oligomer and caprolactam output by the tubular heat exchanger 10 is 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 poly-condensing spraying system 12.
The pre-polymerization process absorbs a large amount of heat, the temperature deviation between the material temperature and the temperature of the heat conducting oil in the jacket of the pre-polymerizer 11 is possibly large, the serpentine coil is added in the pre-polymerizer for heating, the thermal deformation of the equipment caused by the temperature difference between the inside and the outside of the sleeve is relieved, the service life of the equipment is prolonged, and the macromolecular oligomer of the ammonium carboxylate caprolactam is formed. Meanwhile, in order to prevent the volatilization of the diamine, the volatilization of the diamine is reduced in a pressure maintaining mode in the front polymerizer,
meanwhile, in the copolymerization process of the ammonium carboxylate and the caprolactam, a large amount of water needs to be drained to promote the increase of the molecular weight of the copolymer. Meanwhile, the sudden pressure reduction can separate water from caprolactam in the low carboxylic acid ammonium salt caprolactam polymer containing a large amount of water, the excessive water is discharged from the exhaust port of the pre-polymerizer in the form of saturated steam, and the exhaust port is followed by a pre-polymerization condensation spraying system, so that the exhaust amount of the saturated steam is controlled by controlling the feeding amount of the low carboxylic acid ammonium salt caprolactam low molecular weight polymer containing a large amount of water and caprolactam (namely the amount of mixed solution output by the tubular heat exchanger 10) and the pressure in the pre-polymerizer, and the high carboxylic acid ammonium salt and the caprolactam are prevented from quickly copolymerizing to form a macromolecular copolymer and blocking in the pre-polymerizer due to the large amount of water discharge.
(V) Synthesis of copolymer of ammonium carboxylate salt and caprolactam
Reacting the carboxylic acid ammonium salt caprolactam macromolecule oligomer obtained in the step (IV) for 4 to 8 hours in a post-polymerizer under the conditions of 260 to 320 ℃ and-1.0 to 0.5MPa, discharging excessive moisture, and performing later polymerization for promoting the molecular weight increase;
the specific operation steps of the combination device are as follows:
the ammonium carboxylate caprolactam macromolecule oligomer output by the front polymerizer 11 enters the rear polymerizer 13, a tube nest in the rear polymerizer 13 is heated by biphenyl, the temperature is controlled to be 260-320 ℃, the ammonium carboxylate caprolactam macromolecule oligomer discharges redundant moisture in the rear polymerizer 13, the redundant moisture is discharged from an exhaust port of the rear polymerizer 13 in the form of saturated steam, the exhaust port is connected with a rear condensation spraying system 14, the moisture discharge is ensured through a vacuum pumping system 15, the later polymerization for promoting the molecular weight increase is carried out, and the copolymer of ammonium carboxylate and caprolactam is preliminarily obtained by controlling the retention time of the oligomer in the rear polymerizer.
(VI) post-treatment
And (V) granulating, extracting, dehydrating, drying and cooling the caprolactam copolymer of the ammonium carboxylate salt obtained in the step (V) to obtain the caprolactam diacid diamine copolymer.
The specific operation steps of the combination device are as follows:
the copolymer of ammonium carboxylate and caprolactam obtained by a post-polymerizer is discharged into a cooling water tank through a melt extrusion pump, is cut into particles through an underwater granulator 16, is extracted with 24h of constant boiling water in an extraction tower 17, the extracted copolymer with water enters a continuous dehydrator 18 from the lower end, the 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 copolymer is dried by high-temperature nitrogen in the drying tower 19 at 120 ℃ until the water content is lower than 0.06%, the copolymer enters a nitrogen spraying system 20 for cyclic treatment and reutilization after the copolymer is dried by the high-temperature nitrogen, the copolymer enters a cooling tower 21 and is cooled by normal temperature cyclic nitrogen, and finally enters a storage bin 22 to obtain the caprolactam diacid diamine copolymer.
The whole process of the process requires 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 or terephthalic acid.
The carboxylic acid ammonium salt is succinic acid ammonium salt, succinic acid glutaric acid ammonium salt, succinic acid adipic acid diammonium salt, succinic acid suberic acid ammonium salt, succinic acid sebacic ammonium salt, glutaric acid succinic acid diammonium salt, glutaric acid diammonium salt, glutaric acid adipic acid diammonium salt, glutaric acid suberic acid ammonium salt, glutaric acid sebacic acid diammonium salt, adipic acid succinic acid diammonium salt, adipic acid glutaric acid diammonium salt, adipic acid diammonium salt, adipic acid suberic acid ammonium salt and adipic acid sebacic acid diammonium salt, any one or a mixture of any two or more of butanediammonium suberate, pentanediammonium suberate, hexanediammonium suberate, octanediammonium rate, decanediammonium rate, hexanediammonium rate sebacate, octanediammonium rate sebacate, decanediammonium rate sebacate, butanediammonium rate terephthalate, pentanediammonium rate terephthalate, hexanediammonium rate terephthalate, octanediammonium rate terephthalate and decanediammonium rate terephthalate.
An ammonium carboxylate caprolactam copolymer, wherein the weight percentages of ammonium carboxylate and caprolactam in the copolymer are:
5 to 70 percent of carboxylic acid ammonium salt;
30 to 95 percent of caprolactam;
the melting point range of the copolymer is 170-290 ℃;
the relative viscosity range of the copolymer is 2.0-4.0.
Example 1
Under the condition that hexamethylenediamine and adipic diacid are used as solvents, an adipic acid adipic diammonium salt aqueous solution with the mass fraction of 50% is generated in a 50 ℃ salt forming tank, the adipic acid diammonium salt aqueous solution and caprolactam with the same mass (adipic acid diammonium salt) are concentrated by a 140 ℃ concentration tank, the mass concentration of the adipic acid diammonium salt aqueous solution is improved to 80%, a tubular heat exchanger added with a dynamic mixing unit is utilized to mix adipic acid diammonium salt caprolactam micromolecule polymer with the rest caprolactam, the mixed solution is subjected to pre-polymerization in a pre-polymerization reactor at 250 ℃, the retention time is 4h, and adipic acid diammonium salt caprolactam oligomer is formed; in a post-polymerizer at 280 ℃, the post-polymerization for promoting the molecular weight increase is carried out for 6 hours; then, the caprolactam hexanedioic acid hexamethylene diamine copolymer is obtained by cutting, extracting, dehydrating and drying.
The pH value of adipic acid diammonium salt water solution (mass fraction is 50%, normal pressure is 101KPa, 50 ℃, 298K) is in the range of 5.5-8.5, and the influence on the viscosity of caprolactam adipic acid hexamethylene diamine copolymer is shown in figure 2.
As can be seen from FIG. 2, the pH value of the adipic acid diammonium salt aqueous solution is within the range of 5.5-8.5, the excess hexamethylenediamine can volatilize in the polymerization process, and the product viscosity is not influenced. The pH value reduction caused by excessive adipic acid can become an end-capping agent in the polymerization process, and the viscosity of the product is reduced.
Example 2
Under the condition that pentanediamine and adipic diacid are used as solvents, a salt forming tank at 25 ℃ generates an adipic acid glutaric diammonium salt aqueous solution with the mass concentration of 50%, the adipic acid glutaric diammonium salt aqueous solution and adipic acid glutaric diammonium salt aqueous solution with the same mass (adipic acid glutaric ammonium salt) are concentrated by 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 pre-polymerization in a pre-polymerization reactor at 245 ℃, and the retention time is 3 hours, so that an oligomer of the carboxylic acid ammonium salt and the caprolactam is formed; in a post-polymerizer at 280 ℃, the post-polymerization for promoting the molecular weight increase is carried out for 6 hours; then, granulating, extracting, dehydrating and drying to obtain the caprolactam hexanedioic acid pentanediamine copolymer.
The effect of the mass ratio of glutaric acid diammonium 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 the glutaric diammonium adipate salt is in the range of 0-35%, the crystallization performance of the copolymer is changed along with the increase of the amount of the glutaric diammonium adipate salt, the melting point of the glutaric diammonium adipate caprolactam copolymer is reduced, the flexibility of the copolymer is improved, and mechanical property detection shows 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 glutaryl ammonium adipate salts in the final copolymer on the mechanical properties of the copolymer is shown in table 1.
TABLE 1 influence of the mass percentage of glutaric acid diammonium adipate on the mechanical properties of the copolymers
Example 3
Under the condition that hexamethylenediamine and terephthalic acid are used as solvents, a salt forming tank at 80 ℃ generates a hexamethylenediammonium terephthalate aqueous solution with the mass concentration of 45%, the hexamethylenediammonium terephthalate aqueous solution and caprolactam with the same mass (hexamethylenediammonium terephthalate) are concentrated by a 180 ℃ concentration tank, the mass concentration of the hexamethylenediammonium terephthalate aqueous solution is improved to be 80%, a tubular heat exchanger added with a dynamic mixing unit is utilized to mix with the caprolactam, the mixed ammonium carboxylate aqueous solution and the caprolactam are subjected to pre-polymerization in a pre-polymerization reactor at 270 ℃, the retention time is 6 hours, and oligomers of ammonium carboxylate and caprolactam are formed; in a secondary reactor at 300 ℃, the later polymerization for promoting the molecular weight growth is carried out for 8 hours; then, granulating, extracting, dehydrating and drying to obtain the caprolactam-p-phthalic acid hexamethylene diamine copolymer, wherein the extraction time is generally 8 hours.
The effect of the addition of concentrated aqueous solution of hexamethylenediammonium 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 percent of the hexamethylene diammonium terephthalate is in the range of 45-65%, the crystallization performance of the copolymer is changed along with the increase of the hexamethylene diammonium terephthalate salt, particularly the introduction of benzene rings, the melting point of the hexamethylene diammonium terephthalate caprolactam copolymer is increased, the brittleness of the copolymer is improved, and mechanical property detection shows that the strength of the copolymer is not obviously changed and the toughness is obviously reduced. The effect of different amounts of hexamethylene diammonium terephthalate salt in the final copolymer on the mechanical properties of the copolymer is shown in table 2.
TABLE 2 influence of the amount of hexamethylenediammonium terephthalate solution added on the mechanical properties of the copolymers
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A process for continuously polymerizing ammonium carboxylate and caprolactam is characterized in that: the method comprises the following steps:
preparation of an aqueous ammonium carboxylate salt solution
Mixing diamine and dicarboxylic acid by taking water as a solvent to form ammonium carboxylate salt aqueous solution;
(II) Synthesis of ammonium carboxylate salt and caprolactam Small molecule oligomer
Mixing and concentrating the aqueous solution of the ammonium carboxylate salt and caprolactam to form the ammonium carboxylate salt caprolactam micromolecule oligomer;
(III) mixing the small molecular oligomer with caprolactam
Mixing the preheated caprolactam and the small molecular oligomer of the carboxylic acid ammonium salt caprolactam obtained in the step (II) and exchanging heat;
(IV) Synthesis of ammonium carboxylate and caprolactam Macro oligomer
Pre-polymerizing the carboxylic acid ammonium salt caprolactam micromolecule oligomer and caprolactam in a pre-polymerizer to form carboxylic acid ammonium salt caprolactam macromolecule 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 rear polymerizer, and performing later polymerization for promoting molecular weight increase to obtain an ammonium carboxylate caprolactam copolymer;
(VI) post-treatment
And (V) granulating, extracting, dehydrating, drying and cooling the caprolactam copolymer of the ammonium carboxylate salt obtained in the step (V) to obtain the caprolactam diacid diamine copolymer.
2. The process of claim 1, wherein the polymerization of the ammonium carboxylate salt with caprolactam is carried out by: 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 of claim 1, wherein the polymerization of the ammonium carboxylate salt with caprolactam is carried out by: 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 or terephthalic acid.
4. The process of claim 1, wherein the polymerization of the ammonium carboxylate salt with caprolactam is carried out by: the process method needs nitrogen protection in the whole process of materials.
5. The process of claim 1, wherein the ammonium carboxylate salt is continuously polymerized with caprolactam, the process comprising: the concentration of the ammonium carboxylate aqueous solution obtained in the step (I) is 40-60%; the pH value range of the ammonium carboxylate salt aqueous solution is 5.5-11; the temperature of mixing the diamine and the dicarboxylic acid is between room temperature and 100 ℃.
6. The process of claim 1, wherein the polymerization of the ammonium carboxylate salt with caprolactam is carried out by: in the step (II), the mass of the ammonium carboxylate salt aqueous solution is equal to that of caprolactam; the concentration temperature is controlled between 80 ℃ and 180 ℃, and the mass concentration of the concentrated ammonium carboxylate salt water solution is 60 percent to 90 percent.
7. The process of claim 1, wherein the polymerization of the ammonium carboxylate salt with caprolactam is carried out by: the preheating temperature of caprolactam in the step (III) is 120-180 ℃; the temperature after mixing and heat exchange is 150-270 ℃.
8. The process of claim 1, wherein the polymerization of the ammonium carboxylate salt with caprolactam is carried out by: the temperature of the front polymerizer in the step (IV) is controlled to be 160-280 ℃; the pressure is controlled between 0.5MPa and 1.5 MPa.
9. The process of claim 1, wherein the ammonium carboxylate salt is continuously polymerized with caprolactam, the process comprising: the temperature of the postpolymerizer in the step (V) is controlled to be 260-320 ℃.
10. An ammonium carboxylate caprolactam continuous copolymer characterized by: the process for continuous polymerization of ammonium carboxylate salts with caprolactam as claimed in any one of claims 1 to 9, wherein the weight percentages of ammonium carboxylate salts and caprolactam in the copolymer are:
5 to 70 percent of carboxylic acid ammonium salt;
30 to 95 percent of caprolactam;
the melting point range of the copolymer is 170-290 ℃;
the relative viscosity range of the copolymer is 2.0-4.0.
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