CN117264197A - Continuous production method and device for high-temperature-resistant nylon - Google Patents
Continuous production method and device for high-temperature-resistant nylon Download PDFInfo
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- CN117264197A CN117264197A CN202311038322.0A CN202311038322A CN117264197A CN 117264197 A CN117264197 A CN 117264197A CN 202311038322 A CN202311038322 A CN 202311038322A CN 117264197 A CN117264197 A CN 117264197A
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- 239000004677 Nylon Substances 0.000 title claims abstract description 76
- 229920001778 nylon Polymers 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000010924 continuous production Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 60
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 10
- 150000003951 lactams Chemical class 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000004985 diamines Chemical class 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 238000003860 storage Methods 0.000 claims description 33
- 238000007142 ring opening reaction Methods 0.000 claims description 20
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 10
- 229920006117 poly(hexamethylene terephthalamide)-co- polycaprolactam Polymers 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 238000005755 formation reaction Methods 0.000 abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 229920006119 nylon 10T Polymers 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- -1 bis (2-carbonyl-substituted piperidine) terephthalate Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 239000004687 Nylon copolymer Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 150000004799 α-ketoamides Chemical class 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
-
- 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
- C08G69/06—Solid state polycondensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/0004—Processes in series
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyamides (AREA)
Abstract
The invention relates to the field of high polymer material synthesis, and provides a continuous production method of high temperature resistant nylon, which aims at the problems of poor hue and poor uniformity of copolymerized nylon prepared by high temperature polymerization, and comprises the following steps of (1) mixing dibasic acid, diamine, lactam, a reaction auxiliary agent and water, and carrying out salt formation reaction to obtain nylon salt solution; 2, carrying out a prepolymerization reaction on the nylon salt solution in a tubular polymerization reactor, and drying after the reaction to obtain a powdery prepolymer; 3, carrying out primary polycondensation on the powdery prepolymer in a primary polycondensation device, and then carrying out secondary polycondensation in a secondary polycondensation device to obtain powdery high-temperature-resistant nylon; the reaction temperature of the prepolymerization and the polycondensation is 200-250 ℃, the polycondensation stage is carried out below the melting point of the materials, and the second-stage polycondensation temperature is higher than the first-stage polycondensation. The reaction temperature of the whole polymerization pipeline is relatively close to and lower than 250 ℃, so that the uniformity and the hue of the copolymerization component can be greatly improved. The invention also provides a device matched with the production method.
Description
Technical Field
The invention relates to the field of high polymer material synthesis, in particular to a continuous production method and device of high-temperature-resistant nylon.
Background
The high-temperature resistant nylon has the advantages of high strength, solvent resistance, abrasion resistance, convenient processing and forming and the like, and is widely applied to the fields of automobile parts, electronic appliances, engineering parts and the like as an important engineering plastic. The traditional high-temperature resistant nylon production adopts an intermittent kettle melt polymerization method (such as patent CN 105330846A), residual materials in the kettle are easy to generate, excessive transition materials for changing varieties are generated, the product quality is seriously affected, the production efficiency is low, and the product performance difference among different batches is large.
The invention patent CN115873236A provides a method for preparing high-temperature resistant nylon by continuous polymerization, but the method has high reaction temperature in the polycondensation stage, high equipment cost and limited productivity by screw extrusion, and the hue of the product is also easy to be adversely affected at high temperature. The invention patent CN113698288A discloses that the nylon salt solid-phase polymerization is adopted to produce high-temperature resistant nylon, so that the problems that the product quality is influenced by the residue in a high-viscosity melt reaction kettle and the oxidation at high temperature can be effectively solved, but the nylon salt solid-phase polymerization mode has certain influence on the preparation of the nylon copolymer with low-melting monomers such as PA6T/6, PA6T/66 and the like, the uniform mixing of the molecular layers of two nylon salts is difficult to realize, and the phase separation is easy to occur in the heating process due to the large difference of the melting points of the two nylon salt raw materials, so that the uniformity and the comprehensive performance of the final copolymer are influenced. An ideal solution is therefore needed.
Disclosure of Invention
The invention provides a continuous production method of high-temperature resistant nylon, which aims to solve the problems of poor hue and poor uniformity of copolymerized nylon prepared by high-temperature polymerization, and comprises the following steps: (1) salification: mixing dibasic acid, diamine, lactam, reaction auxiliary agent and water, and carrying out salt formation reaction to obtain nylon salt solution;
(2) Ring opening prepolymerization: the nylon salt solution is subjected to prepolymerization reaction in a tubular polymerization reactor, and is dried after the reaction to obtain powdery prepolymer;
(3) Solid phase polycondensation: the powder prepolymer is subjected to primary polycondensation in a primary polycondensation device, and then is subjected to secondary polycondensation in a secondary polycondensation device, so that powdery high-temperature resistant nylon is obtained;
the temperature of the prepolymerization reaction in the step (2) and the reaction temperature of the first-stage polycondensation in the step (3) are 200-250 ℃, the polycondensation stage is carried out below the melting point of the material, and the second-stage polycondensation temperature is higher than the first-stage polycondensation.
The polycondensation stage is carried out below the melting point of the materials, the materials are not easy to adhere, the problems of influence of long-time high-temperature oxidation of residual materials on the hue of products and excessive transition materials among different batches are solved, the formula replacement variety is conveniently adjusted and regulated on line in real time, the generation of the transition materials is reduced, and the starting cost is low. The reaction temperature of the whole polymerization (including prepolymerization and polycondensation) pipeline is relatively close, a relatively high heating medium system is not needed, the energy consumption can be greatly reduced, and the requirement on equipment is reduced.
Preferably, the temperature of the prepolymerization reaction in the step (2) is 210-250 ℃, the reaction temperature of the first-stage polycondensation in the step (3) is 200-230 ℃, and the reaction temperature of the second-stage polycondensation is 230-250 ℃.
Preferably, the high temperature resistant nylon obtained in the step (3) is PA6T/6, PA5T/6 or PA6T/66. The nylon salt solid-phase polymerization is adopted to prepare the monomer copolymerized nylon with low melting point, so that uniform mixing of the two nylon salts on the molecular level is difficult to realize, and because of the large difference of the melting points of the two nylon salt raw materials, phase separation is easy to occur in the heating process, and the uniformity and the comprehensive performance of the final copolymerized product are influenced. The prepolymerization stage is carried out in a tubular polymerization reactor, so that uniformity of copolymerization components can be greatly improved, uniformity and stability of product quality are ensured, ring opening/prepolymerization reaction efficiency is improved at high temperature and high pressure, and reaction time is reduced.
Preferably, the high temperature resistant nylon obtained in the step (3) is PA5T. PA5T is a bio-based high temperature resistant nylon, which is highly susceptible to side reactions during polymerization because the pentanediamine cyclizes to form piperidine at high temperature (> 250 ℃) and then the piperidine and terephthalic acid condense to form dipiperidine terephthalate, which is finally oxidized further to form a new carbonyl structure on the α -methylene beside the amine group-bis (2-carbonyl substituted piperidine) terephthalate, the presence of this α -keto amide group leading to yellowing of the product. As the residence time of the polymerization reaction at high temperature increases, the more bis (2-carbonyl-substituted piperidine) terephthalate is produced, and the color of PA5T becomes progressively darker. And the molar ratio of the dibasic acid to the diamine monomer is unbalanced, and the molecular weight of the polymer is difficult to increase due to the inactivation of the polyamide chain growth caused by the condensation of piperidine and the active oligomer. In addition, since the pentanediamine is easy to cyclize to form a stable six-membered ring structure-piperidine, the thermal degradation mechanism is mainly based on an amide bond cleavage reaction path, and piperidine derivatives are also contained in pyrolysis products, so that the hue quality of the products is affected. The reaction temperature of the whole polymerization (including prepolymerization and polycondensation) pipeline is relatively close and is lower than 250 ℃, so that the side reaction of the pentanediamine in the production process can be avoided, and the PA5T with good performance is obtained.
Preferably, the mixing conditions in step (1) are 50-70 ℃ and stirring is carried out for 1-3h.
Preferably, the salt forming reaction in the step (1) is carried out for 1-2h at the temperature of 120-160 ℃ and the pressure of 0.5-1.5 MPa. The invention adopts high temperature and high pressure salification to improve the reaction efficiency, save the concentration process and reduce the energy consumption.
Preferably, the temperature of the prepolymerization reaction in the step (2) is 220-250 ℃, the pressure is 1.5-2.5MPa, and the reaction time is 3-8h. The salt forming and prepolymerization stages of the invention are all solution systems, and the invention has low viscosity and is not easy to remain.
Preferably, the product of the prepolymerization in step (2) is injected into a drying column at a pressure of 1.0 to 2.0MPa, followed by separation by a cyclone to obtain a powdery prepolymer.
Preferably, the reaction pressure of the first-stage polycondensation in the step (3) is 1000 to 500mbar absolute and the reaction time is 1 to 6 hours. The first-stage polycondensation stage is carried out under the condition of solid materials, so that adhesion residues are reduced, oxidation is reduced, and the product quality is improved.
Preferably, the reaction pressure of the secondary polycondensation in the step (3) is less than or equal to 1mbar absolute pressure, and the reaction time is 2-6h.
Preferably, the entire production process is operated under the protection of nitrogen or inert gas, through which the material is also conveyed. The material is not easy to oxidize at high temperature, and the product quality is ensured.
The invention also provides a continuous production device of the high-temperature-resistant nylon, which is a matched device of the production method and comprises a mixing tank, a salifying kettle, a storage tank, an open-loop prepolymerization kettle, a drying tower, a cyclone separator and a polycondensation system which are sequentially connected, wherein the open-loop prepolymerization kettle is a tubular polymerization reactor.
Preferably, the polycondensation system comprises a storage tank, a first-stage polycondensation device, a buffer tank, a second-stage polycondensation device and a finished product tank which are sequentially connected, and the cyclone separator is connected with the storage tank.
Therefore, the invention has the beneficial effects that: (1) The reaction temperature of the whole polymerization pipeline is not higher than 250 ℃, so that the side reaction of bio-based monomer pentanediamine can be effectively avoided; (2) The salification adopts high-temperature high-pressure salification, so that the reaction efficiency is improved, the concentration process is omitted, and the energy consumption is reduced; (3) The prepolymerization stage is carried out in a tubular polymerization reactor, so that uniformity of copolymerization components can be greatly improved, uniformity and stability of product quality are ensured, ring opening/prepolymerization reaction efficiency is improved at high temperature and high pressure, and reaction time is reduced; (4) The salification/prepolymerization stages are all solution systems, so that the viscosity is low and residues are not easy to remain; (5) The first-stage polycondensation stage is carried out under the condition of solid materials, so that adhesion residues are reduced, oxidation is reduced, and the product quality is improved; (6) The polycondensation stage is carried out below the melting point of the materials, the materials are not easy to adhere, the problems of influence of long-time high-temperature oxidation of residual materials on the hue of the product and excessive transition materials among different batches are solved, the formula replacement variety is conveniently adjusted and regulated on line in real time, the generation of the transition materials is reduced, and the starting cost is low; (7) The reaction temperature of the whole polymerization pipeline is relatively close, a relatively high heating medium system is not needed, the energy consumption can be greatly reduced, and the requirement on equipment is reduced; (8) The whole polymerization pipeline and the container are operated under the protection of inert gas, and materials are conveyed through the inert gas, so that the materials are not easy to oxidize at high temperature, and the product quality is ensured.
Drawings
Fig. 1 is a schematic view of the apparatus of the present invention.
In the figure, a mixing tank 1, a salt forming kettle 2, a storage tank 3, a tubular polymerization reactor 4, a drying tower 5, a cyclone separator 6, a storage tank 7, a first-stage polycondenser 8, a buffer tank 9, a second-stage polycondenser 10 and a finished product tank 11.
Detailed Description
The technical scheme of the invention is further described through specific embodiments.
In the present invention, unless otherwise specified, the materials and equipment used are commercially available or are commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
General examples
A continuous production method of high-temperature-resistant nylon comprises the following steps:
(1) Salt formation: adding dibasic acid, diamine, lactam, reaction auxiliary agent and deionized water into a mixing tank, mixing, transferring into a salifying kettle, and reacting for 1-2h at 120-160 ℃ and 0.5-1.5 MPa.
(2) Ring opening prepolymerization: the nylon salt solution is subjected to prepolymerization reaction in a ring-opening prepolymerization kettle to carry out ring-opening of lactam and prepolymerization of nylon salt, wherein the reaction condition is 210-250 ℃ and 1.5-2.5MPa, and the reaction time is 3-8h; spraying the mixture into a drying tower under the pressure of 1.0-2.0MPa after the reaction, and separating the mixture by a cyclone separator to obtain powdery prepolymer.
(3) Solid phase polycondensation: the powder prepolymer is firstly conveyed into a primary polycondensation reactor through nitrogen or inert gas for primary tackifying, the absolute pressure is controlled to be 900-500mbar, the reaction temperature is controlled to be 200-230 ℃, and the residence time is controlled to be 1-6h; then the mixture enters a secondary polycondensation reactor through a buffer tank to obtain powdery high-temperature resistant nylon, the absolute pressure is controlled within 1mbar, the reaction temperature is controlled to be 230-250 ℃, and the residence time is controlled to be 2-6h.
Preferably, the invention also provides the continuous production device of high-temperature resistant nylon, which comprises a mixing tank, a salifying kettle, a storage tank, an open-loop prepolymerization kettle, a drying tower, a cyclone separator and a polycondensation system which are sequentially connected, wherein the polycondensation system comprises a storage tank, a primary polycondenser, a buffer tank, a secondary polycondenser and a finished product tank which are sequentially connected, and the cyclone separator is connected with the storage tank. The ring-opening prepolymerization reactor is a tubular polymerization reactor.
Example 1
A continuous production device of high-temperature-resistant nylon is shown in figure 1, and comprises a mixing tank 1, a salifying kettle 2, a storage tank 3, a tubular polymerization reactor 4, a drying tower 5, a cyclone separator 6, a storage tank 7, a primary polycondenser 8, a buffer tank 9, a secondary polycondenser 10 and a finished product tank 11 which are connected in sequence.
A continuous production method of high temperature resistant nylon PA6T/6 comprises the following steps:
(1) Salt formation: 249.20kg of terephthalic acid, 174.30kg of hexamethylenediamine, 113.16kg of caprolactam, 1.2kg of phosphoric acid catalyst and 200kg of desalted water are added into a mixing tank 1, the temperature is raised to 60 ℃, stirring is continued for 1h, the mixture is transferred into a salifying kettle 2, the temperature is raised to 150 ℃, the pressure is controlled to be 0.5MPa, the mixture is reacted for 1h, PA6T/6 salt solution is obtained, and the mixture is transferred into a storage tank 3 for storage.
(2) Ring opening prepolymerization: the nylon salt solution is subjected to prepolymerization reaction in a ring-opening prepolymerization kettle, namely a tubular polymerization reactor 4, so that lactam is subjected to ring-opening and nylon salt prepolymerization, wherein the reaction conditions are 220 ℃ (upper end temperature) and 1.5MPa, and the reaction is carried out for 5 hours; spraying into a drying tower 5 under the pressure of 1.0MPa after the reaction, separating by a cyclone separator 6 to obtain dry powdery prepolymer, and transferring to a storage tank 7 for storage.
(3) Solid phase polycondensation: the powder prepolymer is firstly conveyed into a primary polycondenser 8 through nitrogen for primary tackifying, the pressure is controlled to be in a micro negative pressure state, the absolute pressure is 800mbar, the reaction temperature is 230 ℃, and the residence time is 2 hours; then the mixture enters a secondary polycondensation device 10 through a buffer tank 9, the absolute pressure is controlled to be 0.5mbar, the reaction temperature is controlled to be 250 ℃, the retention time is controlled to be 3 hours, and the powdery high-temperature-resistant nylon PA6T/6 is obtained and is transferred to a finished product tank 11 for storage.
Example 2
The difference from example 1 is that the residence time in the secondary polycondenser in step (3) is 6h.
Example 3
A continuous production method of high temperature resistant nylon PA5T/6 comprises the following steps:
(1) Salt formation: 249.20kg of terephthalic acid, 153.27kg of pentanediamine, 113.16kg of caprolactam, 1.15kg of phosphoric acid catalyst and 200kg of desalted water are added into a mixing tank 1, the temperature is raised to 60 ℃, stirring is continued for 1h, the mixture is transferred into a salifying kettle 2, the temperature is raised to 150 ℃, the pressure is controlled to be 0.5MPa, the mixture is reacted for 1h, PA5T/6 salt solution is obtained, and the mixture is transferred into a storage tank 3 for storage.
(2) Ring opening prepolymerization: the nylon salt solution is subjected to prepolymerization reaction in a ring-opening prepolymerization kettle, namely a tubular polymerization reactor 4, so that lactam is subjected to ring-opening and nylon salt prepolymerization, wherein the reaction conditions are 220 ℃ (upper end temperature) and 1.5MPa, and the reaction is carried out for 5 hours; spraying into a drying tower 5 under the pressure of 1.0MPa after the reaction, separating by a cyclone separator 6 to obtain dry powdery prepolymer, and transferring to a storage tank 7 for storage.
(3) Solid phase polycondensation: the powder prepolymer is firstly conveyed into a primary polycondenser 8 through nitrogen for primary tackifying, the pressure is controlled to be in a micro negative pressure state, the absolute pressure is 800mbar, the reaction temperature is 220 ℃, and the residence time is 2 hours; then the mixture enters a secondary polycondensation device 10 through a buffer tank 9, the absolute pressure is controlled to be 0.5mbar, the reaction temperature is controlled to be 250 ℃, the retention time is controlled to be 3 hours, and the obtained powdery high-temperature-resistant nylon PA5T/6 is transferred to a finished product tank 11 for storage.
Example 4
The difference from example 3 is that the residence time in the secondary polycondenser in step (3) is 6h.
Example 5
A continuous production method of high temperature resistant nylon PA6T/66 comprises the following steps:
(1) Salt formation: 249.20kg of terephthalic acid, 146.10kg of adipic acid, 290.50kg of hexamethylenediamine, 1.5kg of phosphoric acid catalyst and 270kg of desalted water are added into a mixing tank 1, the temperature is raised to 60 ℃, stirring is continued for 1h, the mixture is transferred into a salifying kettle 2, the temperature is raised to 150 ℃, the pressure is controlled to be 0.5MPa, the mixture is reacted for 1h, PA6T/66 salt solution is obtained, and the mixture is transferred into a storage tank 3 for storage.
(2) Ring opening prepolymerization: the nylon salt solution is subjected to prepolymerization reaction in a ring-opening prepolymerization kettle, namely a tubular polymerization reactor 4, so that lactam is subjected to ring-opening and nylon salt prepolymerization, wherein the reaction conditions are 220 ℃ (upper end temperature) and 1.5MPa, and the reaction is carried out for 5 hours; spraying into a drying tower 5 under the pressure of 1.0MPa after the reaction, separating by a cyclone separator 6 to obtain dry powdery prepolymer, and transferring to a storage tank 7 for storage.
(3) Solid phase polycondensation: the powder prepolymer is firstly conveyed into a primary polycondenser 8 through nitrogen for primary tackifying, the pressure is controlled to be in a micro negative pressure state, the absolute pressure is 800mbar, the reaction temperature is 230 ℃, and the residence time is 2 hours; then the mixture enters a secondary polycondensation device 10 through a buffer tank 9, the absolute pressure is controlled to be 0.5mbar, the reaction temperature is controlled to be 250 ℃, the retention time is controlled to be 3 hours, and the powdery high temperature resistant nylon PA6T/66 is obtained and is transferred to a finished product tank 11 for storage.
Example 6
The difference from example 5 is that the residence time in the secondary polycondenser in step (3) is 6h.
Example 7
A continuous production method of high temperature resistant nylon PA10T comprises the following steps:
(1) Salt formation: 249.20kg of terephthalic acid, 258.46kg of decanediamine, 1.2kg of phosphoric acid catalyst and 300kg of desalted water are added into a mixing tank 1, the temperature is raised to 60 ℃, stirring is continued for 1h, the mixture is transferred into a salifying kettle 2, the temperature is raised to 150 ℃, the pressure is controlled to be 0.5MPa, the mixture is reacted for 1h, PA10T salt solution is obtained, and the mixture is transferred into a storage tank 3 for storage.
(2) Ring opening prepolymerization: the nylon salt solution is subjected to prepolymerization reaction in a ring-opening prepolymerization kettle, namely a tubular polymerization reactor 4, so that lactam is subjected to ring-opening and nylon salt prepolymerization, wherein the reaction conditions are 220 ℃ (upper end temperature) and 1.5MPa, and the reaction is carried out for 5 hours; spraying into a drying tower 5 under the pressure of 1.0MPa after the reaction, separating by a cyclone separator 6 to obtain dry powdery prepolymer, and transferring to a storage tank 7 for storage.
(3) Solid phase polycondensation: the powder prepolymer is firstly conveyed into a primary polycondenser 8 through nitrogen for primary tackifying, the pressure is controlled to be in a micro negative pressure state, the absolute pressure is 800mbar, the reaction temperature is 220 ℃, and the residence time is 3 hours; then the mixture enters a secondary polycondensation device 10 through a buffer tank 9, absolute pressure is controlled to be 0.5mbar, reaction temperature is controlled to be 250 ℃, and retention time is controlled to be 4 hours, so that powdery high-temperature resistant nylon PA10T is obtained, and the powdery high-temperature resistant nylon PA10T is transferred to a finished product tank 11 for storage.
Example 8
The difference from example 7 is the residence time in the secondary polycondenser of step (3) of 7h.
Comparative example 1
A continuous production method of high-temperature-resistant nylon PA6T/6 is different from that of example 1 in that the method described in patent CN112979941A is adopted.
Comparative example 2
A continuous production method of high-temperature-resistant nylon PA5T/6 is different from that of example 3 in that the method described in patent CN112979941A is adopted.
Comparative example 3
A continuous production method of high-temperature-resistant nylon PA6T/66 is different from example 5 in that PA6T/66 is prepared by adopting the method described in patent CN 112979941A. The raw material types and amounts were the same as in example 5.
Comparative example 4
A continuous production method of high-temperature-resistant nylon PA10T is different from that of example 7 in that the method described in patent CN112979941A is adopted.
Comparative example 5
A continuous production method of high-temperature-resistant nylon PA5T/6 is different from that of example 3 in that the method described in patent CN105330846A is adopted.
Performance testing
The products of the above examples and comparative examples were subjected to performance testing using the test equipment and test criteria of:
the characterization results are shown in the following table.
From the table, the invention is suitable for the production of various high temperature resistant nylon, especially bio-based high temperature resistant nylon PA5T, and the product has excellent thermal and mechanical properties, and the relative viscosity can be regulated and controlled by the reaction time. Comparative examples 1, 2 and 3 high temperature resistant nylon prepared by copolymerization of caprolactam, such as PA6T/6, PA5T/6 and PA6T/66 prepared by patent CN112979941A, have a plurality of melting peaks, and the mechanical strength is obviously lower than that of examples 1, 3 and 5, which shows that even mixing copolymerization of two components is difficult to realize by the method of comparative examples, obvious non-uniformity is generated, and the high temperature resistant nylon prepared by the method of the invention has single melting point, good uniformity and more excellent performance. The properties of comparative example 4 and example 7 are substantially identical, indicating that both inventive methods are applicable to single component high temperature nylon production. The bio-based high temperature resistant nylon PA5T prepared by the method in the embodiments 3 and 4 has good color phase and high relative viscosity, and can meet the subsequent use requirement, because the invention can prepare PA5T by controlling the whole reaction flow under the condition that the reaction temperature of a polymerization pipeline is not higher than 250 ℃, the side reaction of bio-based monomer pentanediamine is effectively avoided; comparative example 5 the PA5T prepared using the prior art has a phase difference, low relative viscosity of the product, and far less performance than the present invention.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalent changes and variations in the above-mentioned embodiments can be made by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. The continuous production method of the high-temperature-resistant nylon is characterized by comprising the following steps of:
(1) Salt formation: mixing dibasic acid, diamine, lactam, reaction auxiliary agent and water, and carrying out salt forming reaction to obtain nylon salt solution;
(2) Ring opening prepolymerization: the nylon salt solution is subjected to prepolymerization reaction in a tubular polymerization reactor, and is dried after the reaction to obtain powdery prepolymer;
(3) Solid phase polycondensation: the powder prepolymer is subjected to primary polycondensation in a primary polycondensation device, and then is subjected to secondary polycondensation in a secondary polycondensation device, so that powdery high-temperature resistant nylon is obtained;
the temperature of the prepolymerization reaction in the step (2) and the reaction temperature of the first-stage polycondensation in the step (3) are 200-250 ℃, the polycondensation stage is carried out below the melting point of the material, and the second-stage polycondensation temperature is higher than the first-stage polycondensation.
2. The continuous production method of high-temperature-resistant nylon according to claim 1, wherein the temperature of the prepolymerization reaction in the step (2) is 210-250 ℃, the reaction temperature of the first-stage polycondensation in the step (3) is 200-230 ℃, and the reaction temperature of the second-stage polycondensation is 230-250 ℃.
3. The continuous production method of high-temperature-resistant nylon according to claim 1 or 2, wherein the high-temperature-resistant nylon obtained in the step (3) is PA6T/6, PA5T/6 or PA6T/66.
4. The continuous production method of high-temperature-resistant nylon according to claim 1 or 2, wherein the high-temperature-resistant nylon obtained in the step (3) is PA5T.
5. The continuous production method of high-temperature-resistant nylon according to claim 1, wherein the salt forming reaction condition of the step (1) is 120-160 ℃ and 0.5-1.5MPa for 1-2h.
6. The continuous production method of high-temperature-resistant nylon according to claim 2, wherein the temperature of the prepolymerization reaction in the step (2) is 220-250 ℃, the pressure is 1.5-2.5MPa, and the reaction time is 3-8h.
7. The continuous production method of high-temperature-resistant nylon according to claim 1, wherein the reaction pressure of the first-stage polycondensation in the step (3) is 1000-500mbar absolute pressure, and the reaction time is 1-6h.
8. The continuous production method of high-temperature-resistant nylon according to claim 1 or 7, wherein the reaction pressure of the secondary polycondensation in the step (3) is less than or equal to 1mbar absolute pressure, and the reaction time is 2-6h.
9. The apparatus for use in the production process according to any one of claims 1 to 8, comprising a mixing tank, a salifying kettle, a storage tank, an open-loop prepolymerization kettle, a drying tower, a cyclone separator and a polycondensation system which are connected in this order, wherein the open-loop prepolymerization kettle is a tubular polymerization reactor.
10. The apparatus of claim 9, wherein the polycondensation system comprises a storage tank, a primary polycondenser, a buffer tank, a secondary polycondenser, and a finishing tank connected in sequence, and wherein the cyclone is connected to the storage tank.
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