CN116440803B - Preparation process and preparation device of polyamide - Google Patents
Preparation process and preparation device of polyamide Download PDFInfo
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- CN116440803B CN116440803B CN202310714935.5A CN202310714935A CN116440803B CN 116440803 B CN116440803 B CN 116440803B CN 202310714935 A CN202310714935 A CN 202310714935A CN 116440803 B CN116440803 B CN 116440803B
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 27
- 229920002647 polyamide Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 23
- 239000000463 material Substances 0.000 claims abstract description 81
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000007599 discharging Methods 0.000 claims abstract description 46
- 230000018044 dehydration Effects 0.000 claims abstract description 26
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000005485 electric heating Methods 0.000 claims description 21
- 238000001704 evaporation Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 15
- 238000011084 recovery Methods 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- -1 caprylic lactam Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 238000005266 casting Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000012544 monitoring process Methods 0.000 abstract description 3
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- 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
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/006—Processes utilising sub-atmospheric pressure; Apparatus therefor
-
- 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
- C08G69/48—Polymers modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polyamides (AREA)
Abstract
The invention provides a production process and a production device of polyamide, wherein the process comprises the following steps: feeding a polymerization monomer and a catalyst, heating, carrying out negative pressure reaction, cooling, feeding auxiliary materials, stirring, mixing and discharging to obtain liquid polyamide, and carrying out high-temperature casting to further obtain the cured polyamide material. The device provided by the invention has a single kettle structure, is simple in structure and high in automation degree, can conveniently carry out material feeding and discharging control, material proportioning control, temperature and pressure control and reaction process monitoring through the material feeding and discharging control unit, the temperature control unit and the dehydration control unit, solves the problems that the reaction device in the prior art is complex and needs repeated feeding and conveying, and is beneficial to realizing large-scale stable production of polyamide materials.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation process and a preparation device of polyamide.
Background
Polyamide commonly known as Nylon (PA) with the English name of Polyamide is a Polyamide containing repeated amide groups (NHCO) on the main chain]-a group of componentsAnd (3) collectively called. A common class of polyamides is the polycondensation from lactams or +.>The chemical structural formula of the obtained long chain molecule is as follows: h- [ NH (CH) 2 ) x CO]-OH. According to the number of carbon atoms contained in the unit structure, the naming of different varieties can be obtained. For example->Is obtained by ring-opening polymerization of caprolactam containing 6 carbon atoms.
The research on the polyamide synthesis process in China is relatively late, the national standard regulation is lacking, most of the current technology is small enterprises, the general technical strength is thin, and therefore the problems of the preparation method, the small volume of the finished product, the unstable product quality and the like exist.
One of the synthetic methods of polyamide is to make the polyamide monomer, such as caprolactam, caprylic lactam, butyl lactam, dodecalactam and other raw materials, and a certain proportion of catalyst, auxiliary materials, curing agent and the like, react in a decompression vacuum dehydration container for multiple times in a specific temperature range, and the synthetic process occurs in the ring-opening and polymerization processes, so that the prepared polyamide material is liquid in a short time and is easy for injection molding.
At present, multi-kettle equipment is mainly used for industrially producing polyamide, for example, patent CN110117360A discloses a complete equipment for industrially producing MC nylon, which comprises a melting kettle, a dehydration kettle and a recovery kettle, wherein the melting kettle is communicated with the dehydration kettle through a conveying pipe, the dehydration kettle is connected with a condenser through a pneumatic valve, the top end of the condenser is communicated with the recovery kettle through a first vacuum pipeline, and the bottom end of the dehydration kettle is connected with a casting machine through a casting pipe; the top end of the melting kettle is also connected with a first air outlet pipe, a second air outlet pipe is connected to the pneumatic valve ball, an air outlet valve is arranged on the second air outlet pipe, the second air outlet pipe is communicated with the first air outlet pipe, and the first air outlet pipe is connected with an exhaust fan; the upper top end of the recovery kettle is also connected with a vacuum unit through a second vacuum pipeline; the melting kettle is connected with a melting kettle oil loop system, and the dehydration kettle is connected with a dehydration kettle oil loop system and a water loop system. The melting kettle oil loop system and the dehydration kettle oil loop system are respectively provided with a low-temperature oil tank and a high-temperature oil tank, and the melting kettle and the dehydration kettle are heated and insulated by utilizing a conveying pipe, a vacuum pipeline and the high-low-temperature oil tank for heating and insulation, so that the caprolactam preparation efficiency is higher.
The temperature control system of the equipment comprises a plurality of high-low temperature oil tanks, the equipment structure is complex, the control difficulty of the temperature is high, and the energy consumption is high.
The literature "industrial preparation of MC nylon active material and large-scale pipe production", wang Jianjun, etc., discloses an industrial production flow of MC nylon active material: (1) feeding, namely feeding solid raw materials into a melting kettle by a feeding facility; (2) the melting material, the melting material kettle starts the temperature control system, and the raw materials are melted and heated to the appointed temperature; (3) feeding, namely starting a nitrogen charging switch of the melting kettle, metering and inputting raw materials into the reaction kettle, automatically closing a feeding valve after the feeding amount is reached, and recovering the melting kettle to normal pressure; (4) dewatering, starting a vacuum system, and dewatering the main raw materials for one time; (5) auxiliary materials are fed, an auxiliary feeding system is started, and required auxiliary materials are metered and fed into the reaction kettle; (6) dehydrating, starting a micro water content tester for raw materials, and measuring and controlling the water content of the raw materials; (7) after the water content of the raw materials meets the requirements, closing a vacuum system, starting a nitrogen charging switch of the reaction kettle, and completely inputting the raw materials in the reaction kettle into a transfer kettle, wherein the reaction kettle is restored to normal pressure; (8) feeding, namely starting a nitrogen charging switch of the transfer kettle, and metering and inputting raw materials into each stirring kettle according to the required quantity of each stirring kettle; (9) conveying, feeding and stirring, starting auxiliary feeding systems of all stirring kettles, metering the required auxiliary materials into the stirring kettles according to the amount, and stirring; and (3) discharging and casting, starting a stirring discharging valve, and casting the raw materials into a die.
The process is complex, involves multiple feeding and conveying processes, and the reaction equipment comprises a plurality of kettles such as a melting kettle, a reaction kettle, a transfer kettle, a stirring kettle and the like, so that the difficulty of process control is increased, and the energy consumption is high, so that the large-scale stable production is not facilitated.
The single kettle preparation system can greatly simplify the complexity of equipment and technology, but care needs to be taken that the reactions in each stage are carried out in the same reaction vessel, so that the reactions in each stage are easy to influence each other, especially, the process of the mutual coordination among negative pressure, boiling, temperature control and material metering control in the first reaction stage is difficult to master, if the boiling of materials is incomplete or excessive, the ring opening and polymerization crystallinity are insufficient, the material quality is undefined after the reaction is finished, the material proportion in the second reaction stage is disordered, and even all materials cannot be solidified.
Therefore, the one-step in-situ preparation device and the preparation process which have the advantages of simple equipment structure, high automation degree, convenience in feeding and discharging control, temperature control, ring opening and polymerization process monitoring are adopted, so that the polymerization proportion of the polyamide is reasonable, and the reaction is stably completed are necessary.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation process and a preparation device of polyamide, wherein the process is completed in a single reaction kettle, so that the problems of multiple preparation and multiple container conveying in the prior art are solved, the energy consumption is reduced, and the production efficiency is improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
on the one hand, the invention provides a reaction kettle device for a polyamide preparation process, which comprises a polymerization container, a feeding system, a discharging system, a sight glass, an evaporation tube, a recovery tank, a vacuum pump, a radar level gauge, a pressure sensor, a vacuum electromagnetic valve, a material temperature sensor, a control box, an electric heating protective sleeve and a stirrer.
The feeding system comprises three feeding ports and three electric valves for controlling feeding; the feed inlet is arranged at the top or at the side edge of the top of the polymerization container; the discharging system comprises a discharging hole and an electric valve for controlling discharging, and the discharging hole is arranged at the middle position of the bottom of the polymerization container.
The polymerization container top sets up the evaporating pipe and links to each other with the recovery jar through the evaporating pipe, and the evaporating pipe outer wall sets up the insulation can, and the position that the evaporating pipe front end links to each other with the polymerization container sets up and looks the cup, look the cup for transparent glass material for observe the boiling state of the material in the polymerization container, the recovery jar passes through the pipeline and links to each other with the vacuum pump.
The top or side of the polymerization container is respectively provided with a radar liquid level gauge, a pressure sensor, a vacuum electromagnetic valve and a material temperature sensor.
A plurality of agitators are arranged in the polymerization vessel.
The outer wall of the bottom of the polymerization container and the outer wall of part of the side edges are provided with electric heating protection sleeves, the electric heating protection sleeves adopt industrial ceramic heating rings, and the area of the electric heating protection sleeves is 60-70% of the outer surface area of the polymerization container.
The outside of the electric heating protective sleeve is provided with a control box, and the control box comprises a feeding and discharging control unit, a temperature control unit and a dehydration control unit. The feeding and discharging control unit is used for controlling the electric valve of the feeding hole, the electric valve of the discharging hole and the radar liquid level gauge. The temperature control unit is used for controlling the electric heating protection sleeve and the evaporating pipe insulation sleeve and is connected with the material temperature sensor. The dehydration control unit is used for controlling the vacuum pump, the vacuum electromagnetic valve and the stirrer, is connected with the pressure sensor, and is connected with a vacuum display meter, a timer for displaying the vacuum operation time length and a timer for displaying the stirring operation time length.
On the other hand, the invention also provides a process for preparing polyamide by adopting the reaction kettle device, which comprises the following steps:
(1) Feeding: starting a control box feeding and discharging control unit, and adding a polymerization monomer and a catalyst into a polymerization container through a feed inlet respectively;
(2) Heating: starting a control box temperature control unit, setting the working temperature of an electric heating protective sleeve, heating to the boiling point temperature of the polymerized monomer plus or minus 5 ℃, and preserving heat;
(3) Negative pressure reaction: starting a control box dehydration control system, starting a vacuum pump to reach a specified negative pressure state, and reacting for a certain time;
(4) And (3) cooling: after the reaction is finished, the vacuum pump is closed and the vacuum electromagnetic valve is started after the temperature displayed by the material temperature sensor is reduced to a temperature suitable for crystallization, and air or nitrogen is input into the polymerization container to enable the inside of the polymerization container to be in a normal pressure state;
(5) Feeding: starting a control box feeding and discharging control unit, adding auxiliary materials into the polymerization container according to the measurement according to the material quality displayed by the radar level gauge through a feeding port, and performing a second-stage reaction;
(6) Stirring and mixing: starting a control box dehydration control system, starting a stirrer to uniformly mix auxiliary materials with the previous materials, and reacting for a certain time;
(7) Discharging: and starting a control box feeding and discharging control unit to discharge the reaction materials through a discharge hole.
Compared with the prior art, the invention has the following beneficial effects:
the preparation process of the polyamide provided by the invention can be completed in a single reaction kettle, solves the problems that multiple preparation and transportation among multiple containers are required in the prior art, and can reduce energy consumption and be beneficial to improving production efficiency.
Drawings
FIG. 1 is a reactor apparatus of the polyamide production process of the present invention.
In the figure: 1-a polymerization vessel; 2-a first feed inlet; 3-a second feed inlet; 4-a third feed inlet; 5-a first electrically operated valve; 6-a second electric valve; 7-a third electric valve; 8-viewing cup; 9-evaporating pipes; 10-a recovery tank; 11-fourth electric valve; 12-a vacuum pump; 13-radar level gauge; 14-a pressure sensor; 15-a vacuum solenoid valve; 16-a material temperature sensor; 17-a control box; 18-an electrical heating protective sleeve; 19-a stirrer; 20-a discharge hole; 21-a fifth electrically operated valve.
Detailed Description
The invention is further illustrated below in conjunction with the detailed description.
The reaction kettle device of the polyamide preparation process shown in fig. 1 comprises a polymerization container 1, a feeding system, a discharging system, a vision cup 8, an evaporation tube 9, a recovery tank 10, a vacuum pump 12, a radar level gauge 13, a pressure sensor 14, a vacuum electromagnetic valve 15, a material temperature sensor 16, a control box 17, an electric heating protective sleeve 18 and a stirrer 19.
The feeding system comprises three feeding ports: first feed inlet 2, second feed inlet 3, third feed inlet 4 set up three electric valve who controls the feeding correspondingly: a first electrically operated valve 5, a second electrically operated valve 6 and a third electrically operated valve 7; the discharging system comprises a discharging hole 20 and a fifth electric valve 21 for controlling discharging, and the discharging hole is arranged at the middle position of the bottom of the polymerization container.
The top of the polymerization container 1 is provided with an evaporation tube 9 and is connected with a recovery tank 10 through the evaporation tube 9, the outer wall of the evaporation tube 9 is provided with a heat insulation sleeve, the front end of the evaporation tube 9 is provided with a viewing cup 8 at the position connected with the polymerization container 1, and the viewing cup 8 is made of transparent glass and is used for observing the boiling state of materials in the polymerization container 1. The recovery tank 10 is connected with a vacuum pump 12 through a pipeline, and a fourth electric valve 11 is arranged on the vacuum pump 12.
The top or side of the polymerization vessel 1 is provided with a radar level gauge 13, a pressure sensor 14, a vacuum solenoid valve 15 and a material temperature sensor 16, respectively.
The radar level gauge 13 is used for monitoring mass loss of materials in the ring-opening reaction process, firstly, under the action of a catalyst, a polymerization monomer is ring-opened to form an active center, so that the number of anions is increased, and meanwhile, water is also generated. In order to meet the final crystallization requirement, the vacuum pump 12 is started to pump away the water evaporated from the original materials and the water generated in the reaction. The second reason is that when caprolactam reaches a boiling point of 136-138 ℃ (10 mmhg/0.0013 Mpa), the pressure in the vessel is-0.1 Mpa, the caprolactam density is 1.01, and the material easily flows into the recovery tank 10 along the evaporation tube 9, thereby losing the quality of the material in the polymerization vessel 1. The radar level gauge 13 is required to accurately display the material quality after the cooling stage is finished, provide data for the quality of the added auxiliary materials, and is suitable for use in a vacuum environment in a container. The dosage of the auxiliary materials plays a vital role in the polymerization process, and has great influence on the polymerization time, the crystallization integrity and the like.
The pressure sensor 14 is used for sensing whether the negative pressure state in the polymerization container 1 reaches the pressure which is easy for material dehydration or not, and the timer starts timing after the pressure reaches the specified pressure. And after the reaction of each stage is finished, whether the normal pressure is recovered in the container is sensed, so that auxiliary materials are added or discharged.
After the reaction, the vacuum solenoid valve 15 is opened to allow air or nitrogen gas to enter the polymerization vessel 1.
The material temperature sensor 16 is used for sensing the material temperature, the sensor is arranged inside the container, and a circuit is connected with the temperature control unit to control the operation of the electric heating protective sleeve.
A plurality of agitators 19 are provided inside the polymerization vessel.
The electric heating protection sleeve 18 is arranged on the outer wall of the bottom of the polymerization container and the outer wall of a part of the side edges, the electric heating protection sleeve 18 adopts an industrial ceramic heating ring, the area of the electric heating protection sleeve is 60-70% of the outer surface area of the polymerization container, the uniform heating before the reaction is started can be ensured, and the rapid heat dissipation and the rapid cooling after the reaction are finished are facilitated. And a non-heating boiling space of the materials is reserved in the polymerization container 1, so that the mass loss caused by excessive boiling can be avoided. The insulating property of the industrial ceramic heating ring is good, and the safety production can be ensured.
The outside of the electric heating protective sleeve is provided with a control box 17, and the control box comprises a feeding and discharging control unit, a temperature control unit and a dehydration control unit.
The feeding and discharging control unit is used for controlling the electric valves 5, 6 and 7 of the feeding port, the electric valve 21 of the discharging port and the radar level gauge 13.
The temperature control unit is used for controlling the electric heating protective sleeve 18 and the evaporating pipe insulating sleeve, and is connected with the material temperature sensor 16, and the material temperature sensor 16 is connected with a temperature control meter on the control box.
The dehydration control unit is used for controlling the vacuum pump 12, the vacuum electromagnetic valve 15 and the stirrer 19, is connected with the pressure sensor 14, and is connected with a vacuum display meter, a timer for displaying the vacuum operation time length and a timer for displaying the stirring operation time length.
The process for preparing polyamide by adopting the reaction kettle device comprises the following steps:
(1) Feeding: starting a feeding and discharging control unit of the control box 17, and adding a polymerization monomer and a catalyst into the polymerization vessel 1 through the feed inlets 2 and 3 respectively;
(2) Heating: starting a temperature control unit of the control box 17, setting the working temperature of the electric heating protective sleeve 18, heating the polymerization monomer and the catalyst to the boiling point temperature of +/-5 ℃, and preserving heat;
(3) Negative pressure reaction: starting a dehydration control system of the control box 17, starting the vacuum pump 12 to reach a specified negative pressure state, and reacting for a certain time;
(4) And (3) cooling: after the reaction is finished, the vacuum pump 12 is closed and the vacuum electromagnetic valve 15 is started after the temperature displayed by the material temperature sensor 16 is reduced to a temperature suitable for crystallization, and air or nitrogen is input into the polymerization container to enable the inside of the polymerization container to be in a normal pressure state;
(5) Feeding: starting a feeding and discharging control unit of the control box 17, adding auxiliary materials into the polymerization container 1 through the feed inlet 3 according to the measurement according to the material quality displayed by the radar level gauge 13, and performing a second-stage reaction;
(6) Stirring and mixing: starting a dehydration control system of the control box 17, starting a stirrer 19 to uniformly mix auxiliary materials with the previous materials, and reacting for a certain time;
(7) Discharging: the feed and discharge control unit of the control box 17 is started, and finally the reaction materials are discharged through the discharge port 20.
Further, the polymerization monomer in the step (1) is selected from one or more of caprolactam, caprylic lactam, butyl lactam and dodecalactam; the catalyst is selected from one or more of sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium ethoxide and potassium ethoxide.
Further, the specified negative pressure in step (3) is from-0.1 MPa to-0.9 MPa; the reaction time is 20-60min.
Further, the temperature in step (4) is 120-150 ℃.
Further, in the step (5), the auxiliary material is selected from one or more of Toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI), polyphenyl polymethylene polyisocyanate (PAPI), triphenylmethane triisocyanate and diphenyl carbonate (DPC).
Further, the mass ratio of the polymerization monomer to the catalyst to the auxiliary materials is 100:0.1-10:0.1-20.
Further, after the step (7) is finished, casting the material into a mould at 140-180 ℃, and preserving heat for 5-30min to obtain the cured polyamide material.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. In addition, the raw materials related to the invention are common commercial products unless otherwise specified.
Example 1
Preparation of polycaprolactam
(1) Feeding: starting a feeding and discharging control unit of the control box 17, and adding 100kg of caprolactam monomer and 0.5kg of sodium hydroxide into the polymerization vessel 1 through the feed inlets 2 and 3 respectively;
(2) Heating: starting a temperature control unit of the control box 17, setting the working temperature of the temperature control meter to be about 135 ℃, and preserving heat;
(3) Negative pressure reaction: starting a dehydration control system of the control box 17, starting the vacuum pump 12, setting the vacuum degree to be-0.1 MPa, and reacting for 30min;
(4) And (3) cooling: after the reaction is finished, the temperature shown by the material temperature sensor 16 is reduced to about 130 ℃, the vacuum pump 12 is closed, the vacuum electromagnetic valve 15 is started, and air or nitrogen is input into the polymerization container to enable the inside of the polymerization container to be in a normal pressure state;
(5) Feeding: starting a material inlet and outlet control unit of a control box 17, wherein the mass of the material displayed by a radar level gauge 13 is 100kg, adding 6kg of auxiliary material TDI into a polymerization container 1 through a feed inlet 3, controlling the temperature to be about 130 ℃, and performing a second-stage reaction;
(6) Stirring and mixing: starting a dehydration control system of the control box 17, starting a stirrer 19 to uniformly mix auxiliary materials with the previous materials, and reacting for 3min;
(7) Discharging: starting a feeding and discharging control unit of the control box 17, and discharging the reaction materials through a discharging hole 20;
(8) Casting: casting the material into a mould which is preheated to 190 ℃, keeping the temperature of the mould for 30min, and taking out the product to obtain the solidified polycaprolactam material.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (6)
1. The reaction kettle comprises a polymerization container (1), a feeding system, a discharging system, a viewing cup (8), an evaporating pipe (9), a recovery tank (10), a vacuum pump (12), a radar level gauge (13), a pressure sensor (14), a vacuum electromagnetic valve (15), a material temperature sensor (16), a control box (17), an electric heating protective sleeve (18) and a stirrer (19);
the feeding system comprises three feeding ports: a first feed inlet (2), a second feed inlet (3), a third feed inlet (4), and three electric valves for controlling the feed: the first electric valve (5), the second electric valve (6) and the third electric valve (7); the discharging system comprises a discharging hole (20) and a fifth electric valve (21) for controlling discharging, and the discharging hole is arranged at the middle position of the bottom of the polymerization container (1);
the top of the polymerization container (1) is provided with an evaporation pipe (9) and is connected with a recovery tank (10) through the evaporation pipe (9), the outer wall of the evaporation pipe (9) is provided with a heat insulation sleeve, the front end of the evaporation pipe (9) is connected with the polymerization container (1), a viewing cup (8) is arranged at the position, which is used for observing the boiling state of materials in the polymerization container (1), of the viewing cup (8) is made of transparent glass, the recovery tank (10) is connected with a vacuum pump (12) through a pipeline, and a fourth electric valve (11) is arranged on the vacuum pump (12); the top or the side of the polymerization container (1) is respectively provided with a radar liquid level meter (13), a pressure sensor (14), a vacuum electromagnetic valve (15) and a material temperature sensor (16);
an electric heating protection sleeve (18) is arranged on the outer wall of the bottom and the outer wall of part of the side edges of the polymerization container (1), the electric heating protection sleeve (18) adopts an industrial ceramic heating ring, and the area of the electric heating protection sleeve is 60-70% of the outer surface area of the polymerization container;
the control box (17) comprises a feeding and discharging control unit, a temperature control unit and a dehydration control unit;
the feeding and discharging control unit is used for controlling the first electric valve (5), the second electric valve (6), the third electric valve (7), the fifth electric valve (21) and the radar liquid level gauge (13);
the temperature control unit is used for controlling the electric heating protective sleeve (18) and the evaporating pipe heat preservation sleeve, and is connected with the material temperature sensor (16), and the material temperature sensor (16) is connected with a temperature control meter on the control box;
the dehydration control unit is used for controlling the vacuum pump (12), the vacuum electromagnetic valve (15) and the stirrer (19) and is connected with the pressure sensor (14), and the dehydration control unit is connected with a vacuum display meter, a timer for displaying the vacuum operation time length and a timer for displaying the stirring operation time length.
2. A process for preparing a polyamide using the reaction vessel of claim 1, comprising the steps of:
(1) Feeding: starting a feeding and discharging control unit of a control box (17), and adding a polymerization monomer and a catalyst into a polymerization container (1) through a first feeding port (2) and a second feeding port (3) respectively;
(2) Heating: starting a temperature control unit of a control box (17), setting the working temperature of an electric heating protective sleeve (18), heating a polymerization monomer and a catalyst to the boiling point temperature of +/-5 ℃, and preserving heat;
(3) Negative pressure reaction: starting a dehydration control system of a control box (17), starting a vacuum pump (12) to reach a specified negative pressure state, and reacting for a certain time;
(4) And (3) cooling: after the reaction is finished, the vacuum pump (12) is closed and the vacuum electromagnetic valve (15) is started after the temperature displayed by the material temperature sensor (16) is reduced to a temperature suitable for crystallization, and air or nitrogen is input into the polymerization container to enable the inside of the polymerization container to be in a normal pressure state;
(5) Feeding: starting a feeding and discharging control unit of a control box (17), adding auxiliary materials into the polymerization container (1) through a second feeding port (3) according to the measurement according to the material quality displayed by a radar level gauge (13), and performing a second-stage reaction;
(6) Stirring and mixing: starting a dehydration control system of the control box (17), starting a stirrer (19) to uniformly mix auxiliary materials with the previous materials, and reacting for a certain time;
(7) Discharging: and starting a feeding and discharging control unit of the control box (17), and finally discharging the reaction materials through a discharge hole (20).
3. The preparation process according to claim 2, wherein the polymerization monomer in the step (1) is one or more selected from caprolactam, caprylic lactam, butyl lactam and dodecalactam; the catalyst is selected from one or more of sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium ethoxide and potassium ethoxide.
4. The process according to claim 2, wherein the specified negative pressure in step (3) is-0.1 MPa to-0.9 MPa; the reaction time is 20-60min; the temperature in the step (4) is 120-150 ℃.
5. The preparation process according to claim 2, wherein the auxiliary material in the step (5) is selected from one or more of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, triphenylmethane triisocyanate and diphenyl carbonate; the mass ratio of the polymerization monomer to the catalyst to the auxiliary materials is 100:0.1-10:0.1-20.
6. The preparation process according to claim 2, wherein after the step (7) is finished, the material is cast into a mold at 140-180 ℃, and the heat is preserved for 5-30min, so as to obtain the cured polyamide material.
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