CN117089002A - Polyvinyl chloride blended resin and production method thereof - Google Patents
Polyvinyl chloride blended resin and production method thereof Download PDFInfo
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- CN117089002A CN117089002A CN202310929236.2A CN202310929236A CN117089002A CN 117089002 A CN117089002 A CN 117089002A CN 202310929236 A CN202310929236 A CN 202310929236A CN 117089002 A CN117089002 A CN 117089002A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/02—Monomers containing chlorine
- C08F114/04—Monomers containing two carbon atoms
- C08F114/06—Vinyl chloride
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention discloses a polyvinyl chloride blending resin and a production method thereof, wherein the polyvinyl chloride blending resin comprises the following components in parts by weight: vinyl chloride: 100 parts of deionized water: 120-300 parts of dispersing agent: 0.1-0.25 part of initiator: 0.10-0.20 parts; one or two of a PH regulator and a terminator are also included; the invention combines the polymerization kettle and the external circulation reaction device, the outlet of the lower end of the polymerization kettle is communicated with the inlet of the external circulation reaction device, the inlet of the upper end of the polymerization kettle is communicated with the outlet of the external circulation reaction device, and the system is used for producing the polyvinyl chloride blended resin. The invention solves the problems of slow reaction rate and difficult heat exchange in the traditional polyvinyl chloride blended resin production, shortens the reaction time and improves the production efficiency; the product of the invention can greatly reduce the viscosity of plastisol, improve the processing performance and reduce the cost.
Description
Technical Field
The invention belongs to the suspension polymerization reaction in the field of chemical production, relates to the technical field of blended PVC resin production, and in particular relates to a production system and a method for producing blended PVC by polymerization in a polyvinyl chloride polymerization kettle external circulation reaction device.
Background
The blended polyvinyl chloride resin (BPVC) is formed by copolymerization of Vinyl Chloride Monomer (VCM). Compared with general polyvinyl chloride (PVC), the particle size of the resin is greatly reduced due to the addition of a large amount of dispersing agents and emulsifying agents in the auxiliary agent, so that the resin has the characteristics of high apparent density, low porosity, small and uniform particle size and the like.
At present, common production processes of the domestic and foreign BPVC products comprise methods such as bulk polymerization, suspension polymerization, emulsion polymerization and the like. The suspension method is convenient to implement and has lower production cost than the bulk method and the emulsion method, and has obvious advantages that the method is a more common PVC blending resin production method because the blending resin is produced by the suspension method only by slightly changing the raw material formula, the process conditions and the feeding mode of the original general PVC resin and does not need to replace most of process equipment.
Chinese patent No. CN99107855.1 "production method of blended resin for PVC paste" discloses
A process for preparing the resin blend used for polyvinyl chloride paste includes such steps as stirring vinyl chloride monomer and assistant including water-soluble disperser, granulating agent, oil-soluble trigger and molecular weight regulator, adding them together, stirring at ordinary temp for 10-20 min, heating to 40-60 deg.C, polymerizing reaction for 0.3-2 hr, decreasing the rotation speed of stirrer for 5-6.5 hr, adding terminator and defoaming agent, centrifugal separation and drying. The reaction time is longer, and the reaction rate is lower because the heat exchange area of the polymerization kettle is small and the initiator can not be used in an increased amount.
Disclosure of Invention
The invention aims to solve the problems of larger consumption of dispersing agent and smaller consumption of initiator in the prior art, and further provides a polyvinyl chloride blending resin with smaller consumption of dispersing agent and larger consumption of initiator.
The invention aims to solve the problems of poor heat exchange effect and long polymerization time of polymerization reaction in the prior art, and further provides a production method of polyvinyl chloride blended resin with good polymerization reaction heat exchange effect and short polymerization reaction time. Shortens the reaction time and improves the production efficiency.
The invention is realized by introducing an emulsion pump on the existing suspension polymerization device to emulsify the vinyl chloride monomer, water, dispersant, initiator and other functional auxiliary agents, so that small monomer droplets are of proper droplet size and stable performance, the consumption of the dispersant can be reduced, and the particle size of the resin can be reduced; the slurry is circulated outside the kettle through the circulation device outside the kettle, and the heat transfer effect of the polymerization kettle can be improved, the addition amount of the initiator is increased, and the polymerization reaction time is shortened through circulation for a certain number of times. The suspension method polyvinyl chloride blended resin with uniform particle distribution, lower plasticizer absorptivity and good blending performance can be prepared by improving the particle structure of the resin, improving the apparent density of the resin and reducing the amount of plasticizer absorption.
In the polyvinyl chloride blending resin and the production method thereof, during the reaction process of materials in a polymerization kettle, part of the materials are pumped to an external circulation reaction device by a slurry circulating pump to perform temperature control reaction, and then return to the polymerization kettle to continuously participate in the polymerization reaction. When the materials in the polymerization kettle react to release heat, the heat is not concentrated in the polymerization kettle, but is continuously and circularly carried into the external circulation reaction device by part of the materials to perform heat exchange and reaction, so that the temperature in the polymerization kettle can be effectively controlled, and correspondingly, the pressure in the polymerization kettle can be effectively controlled. Therefore, the external circulation reaction device of the polymerization kettle can control the temperature and the pressure in the polymerization kettle within a certain range, so that the material polymerization reaction can be normally carried out. And the material sucking port and the material returning port are respectively arranged at the bottom of the kettle and the upper part of the kettle body, so that the slurry circulating pump is easy to suck materials, and the materials after heat exchange reaction enter tangentially along the stirring direction from the upper part of the kettle body, are also easy to be uniformly mixed with other polymer materials, and obtain a better polymerization reaction effect.
The invention adopts the technical proposal for solving the problems existing in the prior art that:
the polyvinyl chloride blending resin comprises the following components in parts by weight:
vinyl chloride: 100 parts of the total weight of the mixture,
deionized water: 120-300 parts of a compound containing,
dispersing agent: 0.1 to 0.25 part of a compound,
and (3) an initiator: 0.10-0.20 parts.
The dispersing agent is a composite dispersing agent consisting of high-alcoholysis-degree polyvinyl alcohol, low-alcoholysis-degree polyvinyl alcohol and hydroxypropyl methyl cellulose according to the weight ratio of 5:1:5-15:1:5. The composite dispersing agent can improve the particle characteristics of the polyvinyl chloride blended resin and improve the product quality.
The polyvinyl chloride blending resin has the alcoholysis degree of 69-89% of high-alcoholysis-degree polyvinyl alcohol, the alcoholysis degree of 53-57% of low-alcoholysis-degree polyvinyl alcohol, the methoxy content of hydroxypropyl methyl cellulose of 27.0-30.0% and the hydroxypropoxy content of 4.0-12.0%. The composite dispersing agent can improve the stability of the polyvinyl chloride blending resin reaction system and prevent the polymerization of vinyl chloride monomers in the external circulation device.
The initiator is a high-activity initiator or a low-activity initiator; the technical indexes of the high-activity initiator are as follows: the half-life period is 0.01-1 h at 50-70 ℃, the active oxygen content is 3-20%, and the low-activity initiator has the technical indexes that: the half-life period is 2-6 h at 50-70 ℃, the active oxygen content is 2-7%, and the initiator can be compounded by the high-activity or low-activity initiator; the preparation concentration of the initiator is 0.01-10%. The low-efficiency initiator can improve the dispersibility of the initiator in the vinyl chloride and avoid the generation of quick-reaction fish eyes; the high-efficiency initiator can improve the polymerization reaction rate, greatly shorten the polymerization reaction time of the polyvinyl chloride resin, improve the production efficiency and increase the yield; the compound use of the initiator with high activity and low activity can ensure the uniform reaction rate in the whole process and improve the control stability; the initiator has a preparation concentration of 0.01-10%, is easier to disperse in vinyl chloride monomer, and improves the initiation efficiency.
The polyvinyl chloride blending resin also comprises one or two of a PH regulator and a terminator, wherein the PH regulator is 0.06-0.10 part, and the terminator is 0.10-0.30 part. The higher the PH value is, the faster the decomposition rate of the initiator is, the vinyl chloride is also relatively easy to decompose and release hydrogen chloride, which is unfavorable for the polymerization reaction, and the lower the PH value is, which is unfavorable for controlling the adhesion of the polymerization kettle, so the reaction can be effectively controlled by adding the PH regulator, and the product quality is improved; the monomer is reduced in the later stage of the polymerization reaction, the probability of the polymerization reaction is increased, the contents of the produced low molecular weight polymer and branched polymer are increased, the content of terminal double bonds is increased, and the chlorine atom on allyl chloride is more unstable, so that the thermal stability and mechanical property of the product are affected, and the phenomenon can be avoided by adding the terminator, and the product quality is improved.
The invention adopts the technical proposal for solving the problems existing in the existing production of polyvinyl chloride blending resin that:
the invention relates to a production method of polyvinyl chloride blending resin, which comprises a polymerization kettle and an external circulation reaction device, wherein an outlet at the lower end of the polymerization kettle is communicated with an inlet of the external circulation reaction device, an inlet at the upper end of the polymerization kettle is communicated with an outlet of the external circulation reaction device, and the production method comprises the following steps in sequence:
1) Cleaning the whole system device, pressurizing with nitrogen, testing leakage and vacuumizing;
2) The temperature self-control module is used for controlling the reaction temperature in the whole process and is connected with the polymerization kettle and the external circulation reaction device, valves of an inlet and an outlet of a heat exchange groove on the external circulation reaction device are pneumatic regulating valves, and the water temperature in the heat exchange groove is controlled to be 50-65 ℃;
3) According to the formula of claim 1, vinyl chloride monomer, deionized water, dispersing agent and initiator are respectively metered into a polymerization kettle, fully mixed for 10-60 min under the stirring action, an outlet regulating valve of the polymerization kettle, a slurry circulating pump, an emulsifying pump and an inlet regulating valve of the polymerization kettle are started, materials are emulsified at a reaction flow rate of 1-3 m/s through the outlet regulating valve of the polymerization kettle and the slurry circulating pump of an external circulating reaction device and then are sent to the external circulating reaction device for heat exchange and reaction through the emulsifying pump, and the materials continuously flow back to the polymerization kettle after the external circulating reaction device circulates for one week; reciprocating for a plurality of cycles; the revolution of the emulsification pump is 5000-18000 rpm;
4) The temperature self-control module is used for controlling the reaction temperature in the whole process, ensuring that the heat transfer quantity of the polymerization kettle and the external circulation reaction device is equal to the heat release quantity of the polymerization reaction, enabling the reaction to be carried out stably, and enabling the reaction materials to enter the discharging system when the pressure drop of the polymerization kettle reaches 0.1-0.30 MPa.
The production method of the polyvinyl chloride blending resin comprises the following steps of: the device comprises a circulating power device, an emulsifying device, a metering device, a tubular reaction device and a temperature control device, wherein the tubular reaction device is positioned in the temperature control device, an inlet connected with an outlet at the lower end of a polymerization kettle and an outlet connected with an inlet at the upper end of the polymerization kettle are arranged on the tubular reaction device, the inlet end of the tubular reaction device is communicated with the metering device, the emulsifying device and the circulating power device through pipelines, and a discharge hole and a valve are arranged at the inlet end of the tubular reaction device.
The tubular reaction device consists of a tubular reactor and a spiral nozzle, wherein the spiral nozzle is positioned in the tubular reactor and is close to the inlet end, and the tubular reaction device is formed by connecting one or a plurality of tubular reactors in series through bent pipes. The heat exchange area of the tubular reactor is large, heat in the center of a pipeline is removed more easily under the cooperation of the spiral nozzle, the temperature control is more accurate, liquid or slurry is changed into fine liquid beads to be sprayed out to form mist after being tangent to and collided with a continuously-reduced spiral surface, the dispersibility is improved, the streamline design from an inlet to an outlet in a nozzle cavity enables the resistance coefficient to be reduced to the minimum, and the occurrence of blocking condition is reduced to the greatest extent. The heat exchange area is improved by the serial structure, and the structure is simple, and the manufacture, the installation and the maintenance are convenient.
The tubular reaction device consists of a tubular reactor, a spiral nozzle, two main reaction pipes, a reactor switching valve and a valve control piece, wherein the spiral nozzle is positioned in the tubular reactor and is close to an inlet end, at least two tubular reactors are arranged between the two main reaction pipes in a mutually parallel mode to form a ladder shape, the reactor switching valve is arranged at an inlet and an outlet of each group of parallel reaction pipes, and the inlet and the outlet of each group of parallel reaction pipes are respectively communicated with the two main reaction pipes. The parallel ladder-shaped reaction tubes further improve the heat exchange area, reduce the length of each path, effectively prevent blockage and facilitate maintenance.
The tubular reaction device consists of tubular reactors, a spiral nozzle, two total reaction tubes, a reactor switching valve and a valve control piece, wherein the spiral nozzle is positioned in the tubular reactors and is close to an inlet end, at least two tubular reactors are connected in series through a bent pipe to form a group of tubular reactors, at least two groups of tubular reactors are arranged between the two total reaction tubes in a mutual parallel mode and are communicated with the total reaction tubes, the reactor switching valve is arranged at an inlet and an outlet of each group of parallel reaction tubes, and the inlet and the outlet of each group of parallel reaction tubes are respectively communicated with the two total reaction tubes. The heat exchange area is further improved by the group of parallel reaction tubes, the length of each path is reduced, and the blockage is effectively prevented.
According to the production method of the polyvinyl chloride blending resin, a tubular reactor is a 316 stainless steel tube or a stainless steel threaded tube or a stainless steel finned tube with a pressure resistance of 1-10 MPa and a mirror polished inner wall, a flushing port, a sampling port and a valve are respectively arranged at the inlet end and the outlet end of the tubular reactor, and a reactor switching valve and a valve control member are an electromagnetic valve and a PLC control cabinet. According to the scheme, materials can react in the pipe and are not easy to block, the common pipe is used, the inner wall is not smooth, the pipe cannot bear reaction pressure according to the reaction characteristic of polyvinyl chloride, and the inner wall can generate serious phenomenon of 'sticking to a kettle', so that heat exchange is affected. The threaded pipe has a threaded wall structure and a larger specific surface area, is beneficial to the formation of secondary flows such as centrifugal flow, vortex flow and the like, and can improve the turbulence degree of fluid in the pipe. Meanwhile, the spiral wall structure can promote the mixing of the near-wall fluid and the central fluid, thereby being beneficial to heat transfer and enabling the radial temperature distribution to be more uniform. In addition, the threaded pipe has the advantages of simple internal structure, mature manufacturing process, low equipment investment cost, high controllability and the like. According to the scheme, the heat exchange efficiency can be improved, fins are added on the surface of the reaction tube, the outer surface area of the heat exchange tube is increased, and therefore the purpose of improving the heat exchange efficiency is achieved. The flushing port and the sampling port are convenient for cleaning dirt in the tubular reactor, and the fluidity and the heat transfer property are improved. The electromagnetic valve and the PLC control cabinet can realize automatic control, and the temperature control effect is more accurate.
The production method of the polyvinyl chloride blending resin has the effective heat transfer area of 1-100 m 2 The diameter of the tubular reactor is 10-100 mm. This scheme has promoted the effective heat transfer area of material, guarantees the abundant heat transfer of material.
The production method of the polyvinyl chloride blending resin is characterized in that the curvature radius of the bent pipe used for connecting the tubular reactor is 2-6 times of the radius of the tubular reactor. Ensures that the local pressure loss and the friction resistance of the pipe are minimum, and is favorable for preventing the occurrence of blocking.
The circulating power device and the metering device are sequentially positioned on a pipeline at the inlet end of the tubular reaction device, the circulating power device is a slurry circulating pump or a centrifugal pump, the emulsifying device is a pipeline type emulsifying pump or a pipeline type emulsifying machine or an online type emulsifying pump, and the metering device is a speed flowmeter or a mass flowmeter. The circulating power device can provide power for the circulating system on one hand and can improve the dispersibility of materials on the other hand; the emulsifying device is used for emulsifying the vinyl chloride monomer, water, a dispersing agent, an initiator and other functional auxiliary agents, so that small monomer droplets are formed into proper droplet sizes, the performance is stable, the consumption of the dispersing agent can be reduced, and the particle size of the resin is reduced; the metering device can detect the speed or flow of material circulation, and is beneficial to process control of heat transfer efficiency, reaction rate, product quality and the like of a circulation system.
The tubular reactor is of a straight tube type or a coil type, and is arranged vertically or parallel to the ground. The straight pipe type heat exchange device is convenient to manufacture and install, and has large coil pipe type heat exchange area and small occupied space.
The temperature control device comprises a heat exchange tank and a submersible pump, wherein the submersible pump is positioned at the bottom of the heat exchange tank, a spray pipe is arranged at the outlet end of the submersible pump, at least two spray heads are arranged on the spray pipe, the spray heads are positioned above the liquid level of the heat exchange tank, and the tubular reaction device is immersed in the liquid of the heat exchange tank. The immersible pump makes the interior solution of heat transfer groove fully flow, and the difference in temperature is little, promotes the control by temperature change rate of accuracy, still is favorable to the heat dissipation, and the shower nozzle can further improve radiating efficiency, and the heat transfer groove is convenient for install, preparation and maintenance, has reduced the cost. The tubular reactor and the heat exchange tank are detachable, so that scaling matters in the heat exchange tank and on the reactor can be cleaned in time, the high efficiency of polymerization heat exchange is ensured, and the reaction period can be effectively shortened.
The temperature control device comprises a fan, a heat exchanger and an air cooling groove, wherein the outlet end of the fan is connected with the heat exchanger, the air cooling groove is cylindrical, two ends of the air cooling groove shrink towards the center to form an air channel, one end of the heat exchanger is communicated with the air channel, and the tubular reaction device is positioned in the middle of the air cooling groove. The scheme can replace water cooling by air cooling, reduces water pollution and is suitable for areas with scarce water resources.
The volume of the polymerization kettle is 0.05-30m 3 。
The invention has the following advantages:
the polyvinyl chloride blended resin has the advantages that the average grain diameter of the resin is smaller than 40 mu m, the grain size distribution is concentrated, the oil absorption rate is about 10%, and the apparent density is between 0.55 and 0.68. The polyvinyl chloride viscosity-reducing resin with low oil absorption rate has the characteristics of high apparent density, low porosity, small and uniform particle size and high strength, is used by being mixed with paste resin, and can reduce paste processing viscosity, improve processing performance and reduce cost.
The invention provides a production method of polyvinyl chloride blending resin, which provides a brand-new polyvinyl chloride blending resin production system, and is used for carrying out joint control on the out-kettle circulation speed and the number of times of materials, so that the feeding amount and the circulation number are more accurate; the multi-kettle-pipe type series polymerization production technology is formed, the conversion rate of materials is effectively improved to more than 80%, the recovery amount of unreacted raw material monomers is less, and the energy consumption of the whole production system is lower; the production method of combining in-kettle polymerization and out-kettle emulsification is adopted, and as an emulsification pump (the pump can be a pipeline type emulsification pump, a pipeline type emulsifying machine and an on-line type emulsification pump) is introduced to carry out emulsification shearing on materials, the adding amount of a dispersing agent can be effectively reduced. The tubular reactor can increase series stages according to the heat removal requirement of the reaction, increase the heat exchange area and realize the controllability of the polymerization temperature; the advantages of the traditional polymerization kettle and the tubular reaction device are combined, so that the traditional polyvinyl chloride production reaction rate is low, the production efficiency low caused by the fact that the reaction heat cannot be effectively replaced in the reaction process is effectively solved, the reaction time is shortened, the production efficiency is improved, and the maximization of the yield is facilitated.
Drawings
FIG. 1 is a process flow diagram of example 5 of the method of producing a polyvinyl chloride blending resin of the invention.
FIG. 2 is a process flow diagram of example 6 of a method of producing a polyvinyl chloride blending resin of the invention.
FIG. 3 is a process flow diagram of example 7 of the method of producing a polyvinyl chloride blending resin of the invention.
FIG. 4 is a process flow diagram of example 8 of the method of producing a polyvinyl chloride blending resin of the invention.
FIG. 5 is a process flow diagram of example 9 of a method of producing a polyvinyl chloride blending resin of the invention.
FIG. 6 is a process flow diagram of process example 10 for producing a polyvinyl chloride blending resin of the invention.
In the figure, a spiral nozzle 1, a heat exchange tank inlet 2, a slurry circulating pump 3, an outlet 4, a polymerization kettle 5, an inlet 6, a sampling port 7, a spray header 8, a tubular reactor 9, an elbow 10, a heat exchange tank outlet 11, a heat exchange tank 12, a total reaction pipe 13, a submersible pump 14, a flushing port 15, a discharge port 16, a reactor switching valve 17, a mass flowmeter 18, an emulsification pump 19, an air cooling tank 20, a heat exchanger 21 and a fan 22.
The invention is further described below with reference to the accompanying drawings, to which the invention is not limited.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by one of ordinary skill in the art without undue burden on the person of ordinary skill in the art based on embodiments of the present invention, are within the scope of the present invention.
Example 1
The polyvinyl chloride blending resin provided by the invention comprises the following components in parts by weight:
vinyl chloride monomer: 100 parts of deionized water: 120 parts of dispersing agent: 0.1 part of an initiator: 0.1 part of terminator: 0.05 part.
Example 2
The polyvinyl chloride blending resin provided by the invention comprises the following components in parts by weight:
vinyl chloride monomer: 100 parts of deionized water: 120 parts of dispersing agent: 0.15 part of an initiator: 0.15 parts of pH regulator: 0.06 parts of terminator: 0.10 parts.
Example 3
The polyvinyl chloride blending resin provided by the invention comprises the following components in parts by weight:
vinyl chloride monomer: 100 parts of deionized water: 150 parts of dispersing agent: 0.20 parts of an initiator: 0.20 parts of pH regulator: 0.10 parts of terminator: 0.20 parts.
Example 4
The polyvinyl chloride blending resin provided by the invention comprises the following components in parts by weight:
vinyl chloride monomer: 100 parts of deionized water: 300 parts of dispersing agent: 0.20 parts of an initiator: 0.20 parts of pH regulator: 0.08 part of terminator: 0.15 parts.
Example 5
The invention relates to a production method of polyvinyl chloride blending resin, which comprises a 75L polymerization kettle and an external circulation reaction device, wherein an outlet at the lower end of the polymerization kettle is communicated with an inlet of the external circulation reaction device, an inlet at the upper end of the polymerization kettle is communicated with an outlet of the external circulation reaction device, and the production method comprises the following steps in sequence:
1) Cleaning the whole system device, pressurizing with nitrogen, testing leakage and vacuumizing;
2) The temperature self-control module is used for controlling the reaction temperature in the whole process and is connected with the polymerization kettle and the external circulation reaction device, valves of an inlet and an outlet of a heat exchange groove on the external circulation reaction device are pneumatic regulating valves, and the water temperature in the heat exchange groove is controlled to be (55+/-0.5);
3) According to the formula of the embodiment 1, 15kg of vinyl chloride monomer, 45kg of deionized water, 15g of dispersing agent and 15g of initiator are respectively metered into a polymerization kettle, fully mixed for 30min under the stirring action, an outlet regulating valve of the polymerization kettle, a slurry circulating pump, an emulsifying pump and an inlet regulating valve of the polymerization kettle are started, materials are emulsified by the outlet regulating valve of the polymerization kettle and the slurry circulating pump of an external circulation reaction device at a reaction flow rate of 1.5m/s and then conveyed to the external circulation reaction device for heat exchange and reaction by the emulsifying pump, and the materials continuously flow back to the polymerization kettle after being circulated for one week by the external circulation reaction device; reciprocating for a plurality of cycles; the revolution of the emulsification pump is 18000rpm;
4) The temperature self-control module is used for controlling the reaction temperature of the whole process to be (57+/-0.5) DEG C, ensuring that the heat transfer capacity of the polymerization kettle and the external circulation reaction device is equal to the heat release capacity of the polymerization reaction, enabling the reaction to be carried out stably, adding 7.5g of terminator when the pressure drop of the polymerization kettle reaches 0.1MPa, and allowing the reaction materials to enter a discharge system after 10 min.
Referring to fig. 1, the external circulation reaction apparatus of the present invention includes: the device comprises a circulating power device, an emulsifying device, a metering device, a tubular reaction device and a temperature control device, wherein the tubular reaction device is positioned in the temperature control device, and is provided with an inlet connected with an outlet 4 at the lower end of a polymerization kettle 5 and an outlet connected with an inlet 6 at the upper end of the polymerization kettle; the circulating power device is a slurry circulating pump 3, the emulsifying device is a pipeline type emulsifying pump 19, and the metering device is a mass flowmeter 18; the tubular reactor consists of a tubular reactor 9, a spiral nozzle 1, two total reaction pipes 13, a reactor switching valve 17 and a valve control member, wherein the spiral nozzle is positioned in the tubular reactor and is close to an inlet end, the tubular reactor is a straight pipe type, pressure-resistant 10MPa 316 stainless steel pipe with mirror polished inner walls, and the effective heat transfer area is 10m 2 The diameter is 50mm, three tubular reactors are connected in series through a bent pipe 10 to form a group of tubular reactors, five groups of tubular reactors are arranged between two total reaction pipes in parallel and parallel to the ground and are communicated with the total reaction pipes, a reactor switching valve is arranged at the inlet and the outlet of each group of parallel reaction pipes, the inlet and the outlet of each group of parallel reaction pipes are respectively communicated with the two total reaction pipes, a reactor switching valve and a valve control part are an electromagnetic valve and a PLC control cabinet, and the curvature radius of the bent pipe is 4 times of the radius of the tubular reactor; the inlet end of the main reaction tube is sequentially communicated with a mass flowmeter, a pipeline type emulsifying pump and a slurry circulating pump through a connecting pipeline, the slurry circulating pump is communicated with the outlet at the lower end of the polymerization kettle, the outlet end of the main reaction tube is communicated with the inlet at the upper end of the polymerization kettle, and the main reaction tube is connected with the outlet at the upper end of the polymerization kettleThe reaction tube is provided with a flushing port 15 and a sampling port 7; the connecting pipeline is separated to form a discharge port 16 of a discharge pipeline of the polymerization kettle; the temperature control device comprises a heat exchange tank 12 and a submersible pump 14, wherein an inlet 2 and an outlet 11 are arranged on the heat exchange tank, a heat exchange medium of the heat exchange tank can be water or oil or other liquid, the submersible pump is positioned at the bottom of the heat exchange tank, a spray pipe is arranged at the outlet end of the submersible pump, three spray heads 8 are arranged on the spray pipe, the spray heads are positioned above the liquid level of the heat exchange tank, and the tubular reaction device is immersed in the liquid of the heat exchange tank.
In the above embodiment, each group of the tubular reactors may be formed by connecting two, five or seven tubular reactors in series through bent pipes, and the number of parallel groups may be two, three, seven or ten. The choice of the data is related to the size of the polymerizer, the heat transfer capacity and the size of the heat exchange tank. The reactor switching valve 17 and valve controls are existing valves and quick wrenches.
The method for detecting the viscosity reduction rate of the blended resin paste comprises the following steps: 100 parts by weight of polyvinyl chloride paste resin (TPH) was added with 60 parts by weight of Dioctylphthalate (DOP), and after stirring for one hour with a planetary stirrer at 300rpm, the viscosity was measured at 25℃with a viscometer to 4100 mp.s. After adding 20 parts by weight of a blending resin to the above paste to prepare a paste, the paste viscosity was measured to determine the paste viscosity reduction rate.
The experimental results of the polyvinyl chloride blended resin are shown in table 1.
TABLE 1 polyvinyl chloride blend resin test results
Example 6
Referring to fig. 2, embodiment 6 is different from embodiment 5 in that: with the formulation of example 2, the number of revolutions of the emulsification pump was 10000rpm, the reaction flow rate was 1.0m/s, the tubular reactor was formed by connecting 15 tubular reactors in series with each other through bent pipes, and the tubular reactor was a 316 stainless steel threaded pipe with a pressure resistance of 5MPa and a mirror finish on the inner wall, and the diameter was 10mm. The experimental results of the polyvinyl chloride blended resin are shown in Table 2.
TABLE 2 detection results of polyvinyl chloride blend resins
Example 7
Referring to fig. 3, embodiment 7 is different from embodiment 5 in that: with the formulation of example 3, the number of revolutions of the emulsification pump was 5000rpm, the reaction flow rate was 2.0m/s, the coil of the tubular reactor in the tubular reactor was arranged perpendicular to the ground, the tubular reactor was 5 groups, the pressure resistance was 3MPa, the inner wall was mirror-polished, and the effective heat transfer area was 100m 2 The diameter is 100mm. The experimental results of the polyvinyl chloride blended resin are shown in Table 3.
TABLE 3 detection results of polyvinyl chloride blend resins
Example 8
Referring to fig. 4, embodiment 8 is different from embodiment 5 in that: the temperature control device comprises a fan 22, a heat exchanger 21 and an air cooling groove 20, wherein the outlet end of the fan is connected with the heat exchanger, the air cooling groove is cylindrical, two ends of the air cooling groove shrink towards the center to form an air channel, one end of the heat exchanger is communicated with the air channel, and the tubular reaction device is positioned in the middle of the air cooling groove. The results of the polyvinyl chloride blend resin experiments are shown in Table 4.
TABLE 4 detection results of polyvinyl chloride blend resins
Example 9
Referring to fig. 5, embodiment 9 is different from embodiment 6 in that: the temperature control device comprises a fan, a heat exchanger and an air cooling groove, wherein the outlet end of the fan is connected with the heat exchanger, the air cooling groove is cylindrical, the two ends of the air cooling groove shrink towards the center to form an air channel, one end of the heat exchanger is communicated with the air channel, and the tubular reaction device is positioned in the middle of the air cooling groove. The experimental results of the polyvinyl chloride blend resin are shown in Table 5.
TABLE 5 detection results of polyvinyl chloride blend resins
Example 10
Referring to fig. 6, embodiment 10 is different from embodiment 7 in that: the temperature control device comprises a fan, a heat exchanger and an air cooling groove, wherein the outlet end of the fan is connected with the heat exchanger, the air cooling groove is cylindrical, the two ends of the air cooling groove shrink towards the center to form an air channel, one end of the heat exchanger is communicated with the air channel, and the tubular reaction device is positioned in the middle of the air cooling groove. The experimental results of the polyvinyl chloride blend resin are shown in Table 6.
TABLE 6 detection results of polyvinyl chloride blend resins
Example 11
Referring to fig. 2, embodiment 11 is different from embodiment 6 in that: the volume of the polymerization kettle is 7m 3 The water temperature in the heat exchange tank is controlled at (62+/-0.5), the polymerization reaction temperature is controlled at (65+/-0.5), the reaction flow rate is 3m/s, and the tubular reactor is a 316 stainless steel straight pipe with pressure resistance of 10MPa and mirror polishing inner wall and diameter of 50mm. The results of the polyvinyl chloride blend resin experiments are shown in Table 7.
TABLE 7 detection results of polyvinyl chloride blend resins
Example 12
Referring to fig. 2, embodiment 12 is different from embodiment 11 in that: the volume of the polymerization kettle is 30m 3 The reaction flow rate was 2m/s, and the number of revolutions of the emulsification pump was 12000rpm. The experimental result of the polyvinyl chloride blended resin is shown inTable 8.
TABLE 8 detection results of polyvinyl chloride blend resins
Comparative example 1
After the 75L polymerization kettle is pressurized and leak tested, vacuumizing to-0.10 MPa, 45kg of deionized water, 60g of dispersing agent, 0.015g of PH value regulator, 9g of initiator and 15kg of vinyl chloride monomer are sequentially added. The polymerization reaction is carried out at the stirring rotation speed of 390rpm and the temperature of 57 ℃, and the terminator is added when the reaction pressure is reduced to 0.2 MPa. The polyvinyl chloride suspension slurry can be obtained, and the slurry is dried for 24 hours by a 55 ℃ oven, so that the polyvinyl chloride blended resin finished product can be obtained. The results are shown in Table 9.
TABLE 9PVC resin test results
Claims (18)
1. The polyvinyl chloride blending resin is characterized by comprising the following components in parts by weight:
vinyl chloride: 100 parts of the total weight of the mixture,
deionized water: 120-300 parts of a compound containing,
dispersing agent: 0.1 to 0.25 part of a compound,
and (3) an initiator: 0.10-0.20 parts.
2. The polyvinyl chloride blending resin according to claim 1, wherein the dispersing agent is a composite dispersing agent consisting of high-alcoholysis-degree polyvinyl alcohol, low-alcoholysis-degree polyvinyl alcohol and hydroxypropyl methyl cellulose according to a weight ratio of 5:1:5-15:1:5.
3. The polyvinyl chloride blending resin according to claim 2, wherein the high alcoholysis degree polyvinyl alcohol has an alcoholysis degree of 69 to 89%, the low alcoholysis degree polyvinyl alcohol has an alcoholysis degree of 53 to 57%, and the hydroxypropyl methylcellulose has a methoxy content of 27.0 to 30.0% and a hydroxypropoxy content of 4.0 to 12.0%.
4. A polyvinyl chloride blending resin according to claim 1, wherein the initiator is a high-activity initiator or a low-activity initiator; the technical indexes of the high-activity initiator are as follows: the half-life period is 0.01-1 h at 50-70 ℃, the active oxygen content is 3-20%, and the low-activity initiator has the technical indexes that: the half-life period is 2-6 h at 50-70 ℃, the active oxygen content is 2-7%, and the initiator can be compounded by the high-activity or low-activity initiator; the preparation concentration of the initiator is 0.01-10%.
5. The polyvinyl chloride blending resin according to claim 1, further comprising one or both of a PH adjuster and a terminator, wherein the PH adjuster is 0.06 to 0.10 parts, and the terminator is 0.10 to 0.30 parts.
6. A method for producing a polyvinyl chloride-blended resin according to any one of claims 1 to 5, comprising a polymerizer and an external circulation reaction device, wherein an outlet at the lower end of the polymerizer is connected to an inlet of the external circulation reaction device, and an inlet at the upper end of the polymerizer is connected to an outlet of the external circulation reaction device, and the steps are performed in the following order:
1) Cleaning the whole system device, pressurizing with nitrogen, testing leakage and vacuumizing;
2) The temperature self-control module is used for controlling the reaction temperature in the whole process and is connected with the polymerization kettle and the external circulation reaction device, valves of an inlet and an outlet of a heat exchange groove on the external circulation reaction device are pneumatic regulating valves, and the water temperature in the heat exchange groove is controlled to be 50-65 ℃;
3) According to the formula of claim 1, vinyl chloride monomer, deionized water, dispersing agent and initiator are respectively metered into a polymerization kettle, fully mixed for 10-60 min under the stirring action, an outlet regulating valve of the polymerization kettle, a slurry circulating pump, an emulsifying pump and an inlet regulating valve of the polymerization kettle are started, materials are emulsified at a reaction flow rate of 1-3 m/s through the outlet regulating valve of the polymerization kettle and the slurry circulating pump of an external circulating reaction device and then are sent to the external circulating reaction device for heat exchange and reaction through the emulsifying pump, and the materials continuously flow back to the polymerization kettle after the external circulating reaction device circulates for one week; reciprocating for a plurality of cycles; the revolution of the emulsification pump is 5000-18000 rpm;
4) The temperature self-control module is used for controlling the reaction temperature in the whole process, ensuring that the heat transfer quantity of the polymerization kettle and the external circulation reaction device is equal to the heat release quantity of the polymerization reaction, enabling the reaction to be carried out stably, and enabling the reaction materials to enter the discharging system when the pressure drop of the polymerization kettle reaches 0.1-0.30 MPa.
7. The method for producing a polyvinyl chloride-blended resin as claimed in claim 6, wherein the external circulation reaction device comprises: the device comprises a circulating power device, an emulsifying device, a metering device, a tubular reaction device and a temperature control device, wherein the tubular reaction device is positioned in the temperature control device, an inlet connected with an outlet at the lower end of a polymerization kettle and an outlet connected with an inlet at the upper end of the polymerization kettle are arranged on the tubular reaction device, the inlet end of the tubular reaction device is communicated with the metering device, the emulsifying device and the circulating power device through pipelines, and a discharge hole and a valve are arranged at the inlet end of the tubular reaction device.
8. The method for producing polyvinyl chloride blended resin according to claim 7, wherein the tubular reaction device is composed of a tubular reactor and a spiral nozzle, the spiral nozzle is positioned in the tubular reactor and near the inlet end, and the tubular reaction device is formed by connecting one or a plurality of tubular reactors in series through bent pipes.
9. The method for producing polyvinyl chloride blended resin according to claim 7, wherein the tubular reaction device is composed of a tubular reactor, a spiral nozzle, two main reaction tubes, a reactor switching valve and a valve control member, wherein the spiral nozzle is positioned in the tubular reactor and is close to the inlet end, at least two tubular reactors are arranged between the two main reaction tubes in parallel connection with each other to form a ladder shape, the reactor switching valve is arranged at the inlet and the outlet of each group of parallel reaction tubes, and the inlet and the outlet of each group of parallel reaction tubes are respectively communicated with the two main reaction tubes.
10. The method for producing polyvinyl chloride blended resin according to claim 7, wherein the tubular reaction device is composed of a tubular reactor, a spiral nozzle, two total reaction tubes, a reactor switching valve and a valve control member, wherein the spiral nozzle is positioned in the tubular reactor and is close to an inlet end, at least two tubular reactors are connected in series through a bent pipe to form a group of tubular reactors, at least two groups of tubular reactors are arranged between the two total reaction tubes in parallel and are communicated with the total reaction tubes, the reactor switching valve is arranged at an inlet and an outlet of each group of parallel reaction tubes, and the inlet and the outlet of each group of parallel reaction tubes are respectively communicated with the two total reaction tubes.
11. The production method of polyvinyl chloride blending resin according to any one of claims 8 to 10, wherein the tubular reactor is a 316 stainless steel tube or a stainless steel threaded tube or a stainless steel finned tube with a pressure-resistant inner wall mirror finished at 1 to 10MPa, the inlet end and the outlet end of the tubular reactor are respectively provided with a flushing port, a sampling port and a valve, and the reactor switching valve and the valve control member are an electromagnetic valve and a PLC control cabinet.
12. The process for producing a polyvinyl chloride-blended resin as claimed in claim 11, wherein the effective heat transfer area of the tubular reactor is 1 to 100m 2 The diameter of the tubular reactor is 10-100 mm.
13. The method for producing a polyvinyl chloride-blended resin according to claim 12, wherein the radius of curvature of the elbow pipe for connecting the tubular reactor is 2 to 6 times the radius of the tubular reactor.
14. The method for producing polyvinyl chloride blended resin according to claim 13, wherein the circulating power device and the metering device are sequentially positioned on a pipeline at the inlet end of the tubular reaction device, the circulating power device is a slurry circulating pump or a centrifugal pump, the emulsifying device is a pipeline emulsifying pump or a pipeline emulsifying machine or an online emulsifying pump, and the metering device is a speed flowmeter or a mass flowmeter.
15. The method for producing a polyvinyl chloride-blended resin according to claim 14, wherein the tubular reactor is a straight tube type or a coil type, and the tubular reactor is disposed vertically or parallel to the ground.
16. The method for producing the polyvinyl chloride blending resin according to claim 15, wherein the temperature control device comprises a heat exchange tank and a submersible pump, the submersible pump is positioned at the bottom of the heat exchange tank, a spray pipe is arranged at the outlet end of the submersible pump, at least two spray heads are arranged on the spray pipe, the spray heads are positioned above the liquid level of the heat exchange tank, and the tubular reaction device is immersed in the liquid of the heat exchange tank.
17. The method for producing polyvinyl chloride blended resin according to claim 16, wherein the temperature control device comprises a fan, a heat exchanger and an air cooling tank, the outlet end of the fan is connected with the heat exchanger, the air cooling tank is cylindrical, two ends of the air cooling tank shrink towards the center to form an air channel, one end of the heat exchanger is communicated with the air channel, and the tubular reaction device is positioned in the middle of the air cooling tank.
18. The method for producing a polyvinyl chloride-blended resin as claimed in claim 6, wherein the volume of the polymerizer is 0.05-30m 3 。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0006697A2 (en) * | 1978-06-29 | 1980-01-09 | General Electric Company | An improved process for forming emulsion/suspension polymers and polymers so formed |
| CN108047365A (en) * | 2018-01-15 | 2018-05-18 | 阳泉煤业（集团）有限责任公司 | A kind of polyvinyl chloride resin polymerizing reactor and its polymerization technology |
| CN114057927A (en) * | 2021-11-23 | 2022-02-18 | 无锡洪汇新材料科技股份有限公司 | Method for preparing vinyl chloride-vinyl acetate copolymer |
-
2023
- 2023-07-26 CN CN202310929236.2A patent/CN117089002A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0006697A2 (en) * | 1978-06-29 | 1980-01-09 | General Electric Company | An improved process for forming emulsion/suspension polymers and polymers so formed |
| CN108047365A (en) * | 2018-01-15 | 2018-05-18 | 阳泉煤业（集团）有限责任公司 | A kind of polyvinyl chloride resin polymerizing reactor and its polymerization technology |
| CN114057927A (en) * | 2021-11-23 | 2022-02-18 | 无锡洪汇新材料科技股份有限公司 | Method for preparing vinyl chloride-vinyl acetate copolymer |
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