CN114870781B

CN114870781B - ABS resin production process system containing internal circulation device and preparation method thereof

Info

Publication number: CN114870781B
Application number: CN202210650427.0A
Authority: CN
Inventors: 李杨; 冷雪菲; 韩丽; 王艳色
Original assignee: Dalian University of Technology
Current assignee: Dalian University of Technology
Priority date: 2022-06-10
Filing date: 2022-06-10
Publication date: 2023-06-30
Anticipated expiration: 2042-06-10
Also published as: CN114870781A

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to an ABS resin production process system with an internal circulation device and a preparation method thereof. The system comprises an internal circulation reactor, a plug flow reactor and a static mixing reactor which are sequentially connected in series through pipelines; the internal circulation reactor consists of 3 static mixers which are sequentially connected in series; the number of the plug flow reactors is 3. The invention effectively solves the problems of poor running stability, higher energy consumption, wide molecular weight distribution of rubber particles, poor dispersibility and the like in the prior art, and the internal circulation reactor pumps the rubber particles with smaller size and unreacted monomers back into the system for continuous reaction, thereby being beneficial to improving the rubber grafting rate and the monomer conversion rate, stabilizing the product quality, ensuring that the improved device runs stably and reduces the energy consumption, and the prepared ABS resin product has the characteristics of narrow molecular weight distribution, uniform dispersion, high impact strength, good industrial production prospect and remarkable economic benefit.

Description

ABS resin production process system containing internal circulation device and preparation method thereof

Technical Field

The invention belongs to the field of high polymer material synthesis and preparation processes, and particularly relates to an ABS resin production process system with an internal circulation device and a preparation method thereof.

Background

ABS resin is a three-component thermoplastic resin of a typical two-phase structure consisting of SAN (copolymer of styrene and acrylonitrile) continuous phase and dispersed rubber phase. The rubber phase particles are grafted with a portion of the monomer to form the necessary interfacial adhesion between the non-grafted copolymer matrix and promote uniform dispersion of the colloidal particles in the matrix. The ABS resin has several times, even tens of times, higher impact resistance than SAN matrix resin due to the presence of the toughening rubber particles. The ABS components impart their respective unique properties, wherein the Acrylonitrile (AN) component imparts chemical resistance, weather resistance, heat resistance to the resin; the butadiene (Bd) component imparts toughness and low temperature resistance (low temperature impact resistance) to the resin; the styrene (St) component imparts excellent electrical properties, processability and surface gloss to the resin. Therefore, the ABS resin has the advantages of impact resistance, high rigidity, oil resistance, low temperature resistance, chemical resistance, excellent mechanical strength and electrical performance, easy processing, good dimensional stability and surface glossiness, and is a high polymer material with excellent comprehensive performance, and widely applied to large-scale and small-scale electronic appliances, instrument panels of transportation vehicles and motorcycles, wheel covers, bags in the light industry field, toys, plates and the like.

ABS resin is prepared by using classical polybutadiene rubber or butadiene and styrene copolymer rubber as toughening agent, dissolving the toughening agent in styrene and acrylonitrile according to a certain proportion, and adopting an initiator initiation method. At present, ABS resin production mainly comprises two preparation processes of an emulsion grafting-SAN blending method and a continuous bulk method. However, the production process for preparing the ABS resin by the emulsion grafting-SAN blending method has long and complex flow, is an intermittent operation process, has large wastewater quantity, has a plurality of process control points of emulsion polymerization, grafting, blending and the like, and has complicated post-treatment process. The continuous bulk polymerization method is to dissolve the toughening rubber component in styrene, acrylonitrile and a small amount of solvent according to a certain proportion, and at a certain temperature, the dissolved glue solution, an initiator and a molecular weight regulator are subjected to a graft polymerization process by a free radical reaction, and an ABS resin product is obtained by a devolatilization and granulation process. Compared with the emulsion grafting-SAN blending method, the continuous bulk ABS resin preparation process is simpler, the process flow is compact, the ABS resin product is pure, the energy consumption is low, the waste water emission is less, the product odor is low, the influence on the environment is small, and the ABS resin preparation process is a production process which is more important to develop in China at present. However, the continuous bulk polymerization process for preparing ABS resin has high requirements on the types of rubber and the control of a reactor and the strengthening of the mass transfer and heat transfer processes.

The United states Dow chemical (DOW) first developed the production process of High Impact Polystyrene (HIPS), and inspired by it, general Electric (GE), dow chemical (Dow), monsanto (Monsanto), basoff (BASF), japan, and the like, all developed unique ABS bulk process production processes based thereon. Of these, the most representative production process, for example, the plug flow reactor cascade technology developed by DOW consists of 4 reactors in series, each with multiple baffles to reduce back mixing; the complete mixing kettles controlled by Mitsui Toyao Co., ltd., japan are connected in series, and part of materials are circulated in the kettle outside by a gear pump, so that stable rubber particles with controllable particle size are formed. Compared with a plug flow reactor, the reaction kettle of the full-mixing kettle process has the advantages of poor stirring effect, wide molecular weight distribution, yellow color and poor performance of the produced ABS product. Therefore, the domestic continuous mass ABS resin production device is a serial multistage plug flow tubular reactor developed by DOW, belongs to full kettle operation, has good stirring effect, avoids the problem of material wall hanging, and has good product performance and color. However, the multistage plug flow tube type series reactor has high requirements on mass transfer and heat transfer of the device, large process fluctuation of each stage of reactor, poor system stability, uneven rubber particle size, explosion aggregation and other problems.

In order to solve the outstanding problems of poor running stability, higher energy consumption, wide molecular weight distribution of rubber particles, poor dispersibility and the like of a reactor in the conventional bulk ABS production process at present, development of brand-new production process equipment for high-performance ABS resin is needed.

Disclosure of Invention

In order to solve the problems of poor system stability, higher energy consumption of a reactor and the like of an ABS production process system in the prior art, the prepared rubber particles have wide molecular weight distribution, poor dispersibility and the like, the invention provides a production process system of high-performance ABS resin comprising an internal circulation reactor and a static mixing reactor.

In order to achieve the purpose of the invention, the technical scheme of the invention is as follows:

an ABS resin production process system with an internal circulation device comprises an internal circulation reactor, a primary plug flow reactor, a secondary plug flow reactor, a tertiary plug flow reactor and a static mixing reactor which are sequentially connected in series through pipelines;

the internal circulation reactor is a series loop consisting of a first-stage static mixer, a second-stage static mixer, a third-stage static mixer and a circulating pump which are sequentially communicated through pipelines; the feed inlet is connected with the filter in series and then is communicated with a circulating loop pipeline between the first-stage static mixer and the circulating pump through a feed pipe, a discharge port is arranged between the third-stage static mixer and the circulating pump, and the discharge port is communicated with the inlet of the first-stage plug flow reactor through a branch pipe;

All the raw materials which are configured according to the proportion are input into a pipeline for mixing by a feed pump, and then are conveyed into an internal circulation reactor through a pipeline by a feed inlet through a filter; the circulating pump in the internal circulating reactor can pump the rubber particles with smaller size and unreacted monomers back into the system for continuous reaction, thereby being beneficial to improving the rubber grafting rate and the monomer conversion rate and stabilizing the product quality.

Further, the first-stage static mixer, the second-stage static mixer and the third-stage static mixer in the internal circulation reactor are internally provided with guide plates, and no stirrer is arranged;

the first, second and third static mixers of the internal circulation reactor are independent heat conduction pipe systems, temperature control systems and pressure control systems;

the temperature and pressure in the first, second and third stage static mixers of the internal circulation reactor are gradually increased.

Further, the primary plug flow reactor, the secondary plug flow reactor and the tertiary plug flow reactor are tubular reactors, each plug flow reactor is divided into an upper region, a middle region and a lower region, and each region is provided with a guide plate and a stirring shaft with a flat paddle; the independent series static mixing reactor is divided into an upper region, a middle region and a lower region, each region is provided with a guide plate, and no stirrer is arranged;

The upper, middle and lower three areas of the plug flow reactor are respectively an independent heat conduction pipe system, a temperature control system and a pressure control system.

Further, the stirring speeds of the primary plug flow reactor, the secondary plug flow reactor and the tertiary plug flow reactor are sequentially reduced; the temperature and the pressure in the first-stage plug flow reactor, the second-stage plug flow reactor, the third-stage plug flow reactor and the static mixing reactor are gradually increased; the temperature settings in the upper, middle and lower three areas of the primary plug flow reactor, the secondary plug flow reactor and the tertiary plug flow reactor are gradually increased; the upper and middle regions of the independent series static mixing reactors are heat-removed, and the lower region is heated.

Further, the three-stage static mixer, the three-stage plug flow reactor and the independent series static mixing reactor of the internal circulation reactor are all provided with jackets, heat conduction oil pipes are laid in the jackets and the interlayer of the guide plates, and are communicated with a heat conduction oil pump, and heat conduction oil circulation is utilized for conducting heat and removing heat.

Further, at least one part of the static mixer, the primary plug flow reactor, the secondary plug flow reactor, the tertiary plug flow reactor, the independent static mixing reactor and the pipeline which are connected in series in the internal circulation reactor is made of carbon steel and stainless steel materials, and the internal surface is provided with an antirust coating.

Further, the carbon steel is a low temperature carbon steel.

Further, the solid content of the mixture at the inlet of the upper section of the first plug flow reactor is 12-15%, and the material residence time is 0.5-2.0 hours;

the solid content of the mixture at the inlet of the upper section of the second plug flow reactor is 45-50%, and the material residence time is 0.5-2.0 hours;

the solid content of the mixture at the inlet of the upper section of the three-stage plug flow reactor is 58-62%, and the material residence time is 0.5-2.0 hours.

Further, the upper, middle and lower three area heat conducting pipes of each plug flow reactor are independent loops, the temperature is independently controlled, and the temperature is controlled between 100 ℃ and 190 ℃.

Further, the temperatures of the three areas of the primary plug flow reactor, the secondary plug flow reactor and the tertiary plug flow reactor are gradually increased from top to bottom, wherein,

the temperature of the primary plug flow reactor ranges from 100 ℃ to 110 ℃;

the temperature range of the secondary plug flow reactor is 110-130 ℃;

the temperature range of the three-stage plug flow reactor is 130-150 ℃.

Further, the pressures of the primary plug flow reactor, the secondary plug flow reactor and the tertiary plug flow reactor are between 0.25 and 0.7MPa, the pressures are gradually increased, and the preferable pressures are 0.42MPa, 0.53MPa and 0.65MPa in sequence; the stirring speed of the primary plug flow reactor, the secondary plug flow reactor and the tertiary plug flow reactor is set at 0.3-25r/min, the higher stirring speed is controlled in the early stage of the reaction, the size and the distribution of rubber particles are properly regulated and controlled in the later stage of the reaction, and the stirring speed is preferably 10-25r/min, 2-8r/min and 0.3-1r/min in sequence.

Further, the static mixing reactor has three regions from top to bottom, the upper and middle regions do not need to be heated, the heat needs to be removed to be lower than 100 ℃, the temperature of the lower region is controlled between 100 ℃ and 190 ℃, the preferable range is 130 ℃ to 190 ℃, the more preferable range is 145 ℃ to 150 ℃, the pressure is 0.25 MPa to 0.7MPa, the preferable pressure is 0.6 MPa to 0.7MPa, and particularly 0.68MPa, and no stirring exists.

The solid content of the mixture at the inlet of the upper section of the static mixing reactor is 68-75% _， The residence time is 0.5-2.0 hours, and the solid content of the mixture at the outlet of the lower section is controlled between 82-86%.

Further, sampling ports are arranged at the outlets of the internal circulation mixer, the plug flow reactor and the static mixing reactor and used for monitoring the solid content.

Further, the device also comprises a devolatilizer and a granulator, wherein the material output end of the static mixing reactor is connected with the devolatilizer and the granulator in series through pipelines. The devolatilizer flashes out unreacted styrene and acrylonitrile monomers and solvent, and recycles the monomers, and the melted materials pass through a granulator to obtain an ABS resin finished product.

Further, the internal circulation mixer, the plug flow reactor, the static mixing reactor, the devolatilizer, the granulator and other devices start to operate simultaneously after the devices are started.

On the other hand, the invention provides a method for preparing high-performance ABS resin by using the production process system of the ABS resin, which mainly comprises the following steps:

step one, conveying styrene, acrylonitrile monomers, antioxidants and toughening rubber particles which are prepared in proportion to a feed pipe by a feed pump, simultaneously continuously adding an initiator solution, a chain transfer agent solution and a dilution circulating liquid which are dissolved according to the formula proportion to the feed pipe by respective metering pumps and feed pumps, filtering and then entering a first-stage static mixer, a second-stage static mixer and a third-stage static mixer in an internal circulation reactor for prepolymerization, wherein the first-stage static mixer, the second-stage static mixer and the third-stage static mixer in the internal circulation reactor control the reaction temperature to be 100-110 ℃, and the pressure is set to be 0.25-0.45MPa, preferably 0.35MPa; the prepolymerization residence time is 0.2 to 1 hour, and the solid content at the outlet is controlled to be 12 to 15 percent;

pumping smaller-sized rubber particles and unreacted monomers in the prepolymerized materials in the internal circulation reactor back to an internal system by a circulation pump for continuous reaction, pumping the materials reaching the size requirement into the primary plug flow reactor, controlling the reaction temperature to 100-110 ℃, controlling the pressure to 0.25-0.45MPa and controlling the stirring speed to 10-25r/min; the residence time is 0.5-2.0 hours, and the solid content of the material at the outlet is 45-50%; the three areas of the primary plug flow reactor are sequentially set to 102.2 ℃, 104.2 ℃ and 106.8 ℃ from top to bottom, and the reactor pressure is preferably 0.42MPa;

Pumping materials from the first-stage plug flow reactor into the second-stage plug flow reactor, controlling the reaction temperature to be 110-130 ℃, controlling the pressure to be 0.45-0.55MPa, and controlling the stirring speed to be 2-8r/min; the retention time of the materials is 0.5 to 2.0 hours, and the solid content of the materials at the outlet is 58 to 62 percent; the temperature of the two-stage plug flow reactor is set to 115.1 ℃, 118.2 ℃, 122.2 ℃ and the reactor pressure is preferably 0.53MPa in sequence from top to bottom;

step four, pumping materials from a secondary plug flow reactor to a tertiary plug flow reactor, controlling the reaction temperature to be 130-150 ℃, controlling the pressure to be 0.55-0.7MPa and controlling the stirring speed to be 0.3-1r/min; the retention time of the materials is 0.5 to 2.0 hours, and the solid content of the materials at the outlet is 68 to 75 percent; the temperature of the three-stage plug flow reactor is set to be 130.1 ℃, 133.5 ℃ and 138.5 ℃ in sequence from top to bottom, and the reactor pressure is preferably 0.65MPa;

step five, pumping the materials from the three-stage plug flow reactor to the static mixing reactor, wherein the upper and middle regions do not need to be heated, and the lower region controls the reaction temperature to be 130-190 ℃ and the pressure to be 0.6-0.7MPa; the retention time of the materials is 0.5 to 2.0 hours, and the solid content of the materials at the outlet is 82 to 86 percent; after the material reaches the conversion rate, the material is sent to a devolatilizer to flash-evaporate unreacted styrene and acrylonitrile monomers and solvent, and the solvent is recycled, and the melted material is pelletized to obtain an ABS resin finished product.

Further, the toughening rubber is at least 1 of polybutadiene rubber, styrene-butadiene binary copolymer rubber, styrene-isoprene-butadiene ternary integrated rubber, amino/siloxy/silahyd functional styrene-butadiene copolymer rubber, amino/siloxy/silahyd functional styrene-isoprene-butadiene copolymer integrated rubber.

Further, the solvent is toluene or ethylbenzene; the initiator is 1, 1-di-tert-butyl cyclohexane peroxide; the chain transfer agent is n-dodecyl mercaptan; the antioxidant is 1-octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the diluted circulation liquid is selected from at least 1 of propane, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, cyclohexane, n-heptane, methylcyclohexane and ethylbenzene.

Further, the toughening rubber accounts for 5-15% of the mixed glue solution containing styrene, acrylonitrile, an initiator, a chain transfer agent and a solvent, the styrene accounts for 40-75% of the total glue solution, the toluene or ethylbenzene accounts for 10-20% of the total glue solution, and the acrylonitrile accounts for 5-20% of the total glue solution; the dosage of the n-dodecyl mercaptan chain transfer agent is 0.10-0.40% of the sum of the mass of acrylonitrile and styrene; the dosage of the antioxidant 1-octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate is 0.30-0.3% of the total mass of acrylonitrile and styrene.

The prepared ABS resin is a rubber toughened polystyrene-acrylonitrile resin product, the toughened rubber is at least 1 of polybutadiene rubber, styrene-butadiene binary copolymer rubber, styrene-isoprene-butadiene ternary integrated rubber, amino/siloxy/silaxy functional styrene-butadiene copolymer rubber and amino/siloxy/silaxy functional styrene-isoprene-butadiene copolymer integrated rubber, the disperse phase is rubber particles grafted with styrene and acrylonitrile block copolymers, and the continuous phase is macromolecular styrene and acrylonitrile copolymer SAN. Polybutadiene rubber, styrene-butadiene binary copolymer rubber, styrene-isoprene-butadiene ternary integrated rubber, amino/siloxy/silahydryl functional styrene-butadiene copolymer rubber and amino/siloxy/silahydryl functional styrene-isoprene-butadiene copolymer integrated rubber are products obtained by anionic solution polymerization.

The invention has the beneficial effects that:

1. the production process system of the high-performance ABS resin provided by the invention can effectively improve the stability of system operation and obviously reduce the energy consumption and the explosion risk of the device;

2. The dispersibility of rubber can be obviously improved, the monomer conversion rate is improved, and the prepared ABS resin product has the characteristics of narrow grouping of molecular weight of rubber particles, uniform dispersion of the rubber particles, high impact strength and excellent processability;

3. the internal circulation reactor can pump the rubber particles with smaller size and unreacted monomers back to the system for continuous reaction, and the device is suitable for low-viscosity liquid reaction, can be used as a prepolymerization device, and is beneficial to improving the rubber grafting rate and the monomer conversion rate and stabilizing the product quality.

Drawings

FIG. 1 is a schematic diagram of an ABS resin production process system with an internal circulation device.

Reference numerals illustrate: r1-an internal circulation mixer; r2-primary plug flow reactor; r3-secondary plug flow reactor; r4-three-stage plug flow reactor; r5-static mixing reactor; a-a first stage static mixer; b a second stage static mixer, c-a third stage static mixer; d-filter.

Detailed Description

In order that the above objects, features and advantages of the invention will be more clearly understood, a further description of the invention will be made. It should be noted that, without conflict, the embodiments of the present invention and features in the embodiments may be combined with each other.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein; it will be apparent that the embodiments in the specification are only some, but not all, embodiments of the invention.

Preferred embodiments of the present invention will be described in detail below with reference to examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention may be made by those skilled in the art without departing from the spirit and scope of this invention.

The experimental methods used in the following examples are conventional methods unless otherwise specified.

Materials, reagents and the like used in the following examples are commercially available unless otherwise specified; the operations referred to are those conventional in the art unless specifically indicated.

The test instrument for testing the embodiment of the invention comprises the following components:

tensile property test: the test rate was 5.0mm/min and the test temperature was 23℃as determined by a universal material tester (Industt Lang Gongsi) according to ISO 527-1:1993; instrumented cantilever notched impact test: according to ISO180-93 standard, cantilever impact tester (CEAST company, italy) is adopted to test at 23deg.C with pendulum weight of 50J; transmission Electron Microscope (TEM) analysis: adopting the American FEI company, carrying out microscopic morphological observation on the ABS resin, firstly carrying out ultrathin section, then carrying out TEM observation after oxidizing for 24 hours by using osmium tetroxide, and measuring the pressure to be 200kV; scanning Electron Microscope (SEM) analysis: spraying gold on the section of the broken ABS sample by using a K550X-type gold spraying instrument produced by EMITECH company in England, and placing the broken ABS sample under a QUANTA200 scanning electron microscope produced by FEI company in America to observe the section morphology at an acceleration voltage of 20kV; polymer solids (X) test: pre-weighing clean crucible m ₀ Taking a polymer material m in a reaction kettle, then placing the crucible and the material in a vacuum drying oven at 80 ℃ to dry to constant weight, about 24 hours, and weighing the mass m of the crucible and the dry material at the moment ₁ The calculation formula of the solid content of the material is as follows:

X＝(m ₁ -m ₀ )/(m-m ₀ )

example 1

As shown in FIG. 1, an ABS resin production process system with an internal circulation device comprises an internal circulation mixer R1, a first plug flow reactor R2, a second plug flow reactor R3, a third plug flow reactor R4 and a static mixing reactor R5 which are sequentially connected in series through pipelines; the material output end of the static mixing reactor R5 is sequentially connected with the devolatilizer and the granulator in series through a pipeline (not shown). The devolatilizer is used for flashing out unreacted styrene and acrylonitrile monomers and solvent, recycling and reusing, and the melted materials pass through a granulator to obtain an ABS resin finished product.

The internal circulation reactor R1 is a series loop formed by a first-stage static mixing reactor a, a second-stage static mixer b, a third-stage static mixer c and a circulating pump which are sequentially communicated through pipelines; the feed inlet is connected with a filter D in series and then is communicated with a circulating loop pipeline between the first-stage static mixing reactor a and a circulating pump through a feed pipe, a discharge port is arranged between the third-stage static mixer c and the circulating pump, and the discharge port is communicated with an inlet of the first-stage plug flow reactor R2 through a branch pipe;

All the raw materials which are prepared according to the proportion enter a pipeline for mixing at a feed inlet, and then are input into the feed inlet through a filter d; the circulating pump in the internal circulating reactor R1 can pump the rubber particles with smaller size and unreacted monomers back into the system for continuous reaction, thereby being beneficial to improving the rubber grafting rate and the monomer conversion rate and stabilizing the product quality.

The first-stage static mixer a, the second-stage static mixer b and the third-stage static mixer c in the internal circulation reactor R1 are respectively provided with a guide plate, and no stirrer is arranged;

the first, second and third stage static mixers R1-abc of the internal circulation reactor R1 are respectively an independent heat conduction pipe system, a temperature control system and a pressure control system, the temperature range in the third stage static mixer R1-abc is 100-190 ℃, the temperature is preferably 100-110 ℃, the pressure range is 0.25-0.7MPa, and the pressure is preferably 0.25-0.45MPa;

the temperature and pressure in the first-stage, second-stage and third-stage static mixers R1-abc of the internal circulation reactor R1 are gradually increased, the total residence time is 0.2-1.0 h, and the solid content at the outlet is 12-15%.

The primary plug flow reactor R2, the secondary plug flow reactor R3 and the tertiary plug flow reactor R4 are tubular reactors, each plug flow reactor is divided into an upper region, a middle region and a lower region, and each region is provided with a guide plate and a stirring shaft with a flat paddle; the static mixing reactor R5 which is independently connected is divided into an upper region, a middle region and a lower region, each region is provided with a guide plate, and no stirrer is arranged;

The upper, middle and lower three areas of the plug flow reactor R2-4 are independent heat conduction pipe systems, temperature control systems and pressure control systems.

The stirring paddle in the plug flow reactor is in transmission connection with the stirring motor arranged at the bottom of the plug flow reactor, and the stirring paddle motor is arranged at the bottom of the plug flow reactor, so that the plug flow reactor has higher stability and operates more stably. The stirring speeds of the first-stage plug flow reactor R2, the second-stage plug flow reactor R3 and the third-stage plug flow reactor R4 are sequentially reduced; the temperature and the pressure in the primary plug flow reactor R2, the secondary plug flow reactor R3, the tertiary plug flow reactor R4 and the static mixing reactor R5 are gradually increased; the temperature settings in the upper, middle and lower three areas of the primary plug flow reactor R2, the secondary plug flow reactor R3 and the tertiary plug flow reactor R4 are gradually increased; the upper and middle regions of the static mixing reactor R5 are heat-removed, and the lower region is heated.

The internal circulation reactor R1, the plug flow reactors R2-4 and the static mixing reactor R5 are all provided with jackets, guide plates are arranged in the jackets, and heat conduction oil pipes are laid in the interlayers of the guide plates; and a heat conduction oil pipe is arranged in the jacket and is communicated with a heat conduction oil pump, and heat conduction oil is utilized for circulation heat conduction and heat removal.

The upper, middle and lower three sections of guide plates of the plug flow reactor R2-4 are respectively communicated with a heat conducting oil pump, the temperature can be independently controlled, the temperature is set to be adjustable within the range of 100-190 ℃, the temperatures of the primary, secondary and tertiary plug flow reactors are gradually increased, the preferable temperature ranges are sequentially 100-110 ℃, 110-130 ℃, 130-150 ℃ and the pressure is set to be adjustable within the range of 0.25-0.7MPa, and the pressures of the primary, secondary and tertiary plug flow reactors are gradually increased, the preferable pressure ranges are sequentially 0.25-0.45MPa, 0.45-0.55MPa and 0.55-0.65MPa.

The upper, middle and lower three sections of guide plates of the independently connected static mixing reactor R5 are respectively communicated with a heat conducting oil pump, the temperature can be independently controlled, the upper and middle sections do not need to be heated, heat removal is needed, the temperature is controlled to prevent the explosion phenomenon, the temperature in the lower section is increased, the temperature is set to be adjustable within the range of 100-190 ℃, the temperature is preferably 130-190 ℃, the monomer conversion rate is improved, and the pressure is 0.25-0.7MPa, preferably 0.6-0.7MPa; the residence time of the static mixing reactor is 0.5-2.0 hours, and the solid content of the mixture at the outlet of the lower section is 82-86%.

The internal circulation reactor R1, the primary plug flow reactor R2, the secondary plug flow reactor R3, the tertiary plug flow reactor R4, the independently connected static mixing reactor R5 and at least one part of the pipeline are made of carbon steel and stainless steel materials, and the inner surface is provided with an antirust coating.

And sampling ports are arranged at the outlets of the internal circulation reactor R1, the three-stage plug flow reactors R2-4 and the independently connected static mixing reactor R5 and are used for monitoring the solid content.

Example 2

The high performance ABS resin manufactured by example 1 was used. The weight percentages of the components entering the internal circulation reactor R1 are as follows: the polystyrene-butadiene-isoprene ternary integrated rubber accounts for 8.4% of the mixed glue solution weight ratio of styrene, acrylonitrile, an initiator, a chain transfer agent and a solvent, the styrene accounts for 63.6% of the glue solution weight ratio, the acrylonitrile accounts for 14% of the glue solution weight ratio, and the ethylbenzene accounts for 14% of the glue solution weight ratio. The initiator was 70ppm based on the styrene and acrylonitrile solution and the flow was controlled to 0.7g/h. The chain transfer agent accounts for 35ppm of the solution of styrene and acrylonitrile, and the flow rate is controlled to be 0.5g/h.

The setting temperature of the internal circulation reactor is 100-110 ℃, the preferable temperature of a first static mixer R1-abc, a second static mixer R2-abc and a third static mixer R1-abc in the internal circulation reactor are 102.1 ℃, 102.4 ℃, 102.8 ℃ and the pressure of the internal circulation reactor are 0.32MPa, 0.33MPa and 0.35MPa in sequence, the plug flow reactor R2-4 is a tubular reactor, the R2-4 three-stage plug flow reactor is divided into an upper region, a middle region and a lower region, and a guide plate and a shaft with a flat paddle are respectively arranged in the upper region, the middle region and the lower region for stirring; the upper, middle and lower three sections of guide plates of the R-4 three-stage plug flow reactor are respectively communicated with a heat conduction oil pump, the temperature can be independently controlled, the temperature is set to be adjustable within the range of 100-190 ℃, the pressure is 0.25-0.7MPa, the pressures of the primary, secondary and tertiary plug flow reactors are gradually increased, and the preferable pressures are 0.42MPa, 0.53MPa and 0.65MPa in sequence; the stirring speed of the R2-4 three-stage plug flow reactor is set at 0.3-25R/min, the higher stirring speed is controlled in the early reaction stage, the size and the distribution of rubber particles are properly reduced in the later reaction stage, and the stirring speed is preferably 10-25R/min, 2-8R/min and 0.3-1R/min in sequence; the residence time of the R2-4 three-stage plug flow reactor is 0.5-2.0 hours, and the solid content at the outlet of the lower section area is 45-50%, 58-62% and 68-75% respectively.

The internal circulation reactor R1 is set for a residence time of 0.2 to 1 hour, preferably 0.5 to 0.8 hour, and the solid content at the outlet is 14 to 15%.

The first plug flow reactor R2 is provided with the upper, middle and lower three areas with the temperature of 103.2 ℃, 104.5 ℃, 105.8 ℃ and the pressure of 0.42MPa, the stirring speed of 16R/min and the solid content at the outlet of 48-50 percent.

The second plug flow reactor R3 is provided with the upper, middle and lower three areas with the temperature of 115.5 ℃, 118.6 ℃, 122.5 ℃, the pressure of 0.53MPa, the stirring speed of 4R/min and the solid content at the outlet of 61-62 percent.

The third plug flow reactor R4 is provided with the upper, middle and lower three areas with the temperature of 130.2 ℃, 132.5 ℃, 135.5 ℃ and the pressure of 0.65MPa, the stirring speed of 0.4R/min and the solid content at the outlet of 68-75 percent.

The temperature of the upper and middle sections of the static mixing reactor R5 is removed, explosion polymerization is prevented, the temperature of the lower section is 148 ℃, stirring is not carried out, the pressure is 0.68MPa, and the solid content at the outlet is 84-86%.

By controlling the narrow molecular weight distribution of rubber particles in the internal circulation reactor R1, the solid content of the mixture in the three-stage plug flow reactors R2-4 and the independently connected static mixing reactor R5 obtains reasonable rubber particle size and distribution of rubber particles, thereby effectively improving the impact performance of the ABS resin product prepared by the bulk method, and the test results are shown in Table 1.

Table 1 test results

Remarks:

1. samples were taken every 1 hour to test the solids content of the polymer at the outlet of the internal recycle reactor R1.

2. Samples were taken every 4 hours to test the solids content and average rubber particle size of the polymer at the outlet of the static mixing reactor R5.

3. And taking an ABS product for injection molding every 4 hours, and testing the impact strength and the elongation at break of the product once.

Example 3

The high performance ABS resin manufactured by example 1 was used. The internal circulation reactor R1 is a prepolymerization reactor, a continuous rubber phase is subjected to a prepolymerization process of grafting SAN in the reactor, a circulation pump in the internal circulation reactor R1 can pump rubber particles with smaller size and unreacted monomers back into the system for continuous reaction, the improvement of the rubber grafting rate and the monomer conversion rate and the stabilization of the product quality are facilitated, and the internal circulation reactor R1 is beneficial to obtaining rubber particles with narrower molecular weight molecules. The materials sequentially enter a first-stage, a second-stage and a third-stage plug flow reactors and a static mixing reactor R5 to further generate a SAN grafting reaction process. The weight percentages of the components in the raw material liquid entering the grafting reactor are as follows: the polystyrene-butadiene-isoprene ternary integrated rubber accounts for 8.4% of the mixed glue solution containing styrene, acrylonitrile, an initiator, a chain transfer agent and a solvent, the styrene accounts for 63.6% of the glue solution, the acrylonitrile accounts for 14% of the glue solution, and the ethylbenzene accounts for 14% of the glue solution. The initiator was 70ppm based on the styrene and acrylonitrile solution and the flow was controlled at 0.7g/h. The chain transfer agent accounts for 35ppm of the solution of styrene and acrylonitrile, and the flow rate is controlled to be 0.5g/h.

The setting temperature of the first, second and third stage static mixers R1-abc in the internal circulation reactor R1 is 100.2 ℃, 100.4 ℃, 100.6 ℃ and the pressure is 0.25MPa, 0.27MPa and 0.29MPa in sequence, the material residence time is 0.2-1 hour, preferably 0.2-0.5 hour, and the solid content at the outlet is 13-14%.

The first plug flow reactor R2 is provided with the upper, middle and lower three areas with the temperature of 102.1 ℃, 104.2 ℃, 106.8 ℃ and the pressure of 0.40MPa, the stirring speed of 16R/min and the solid content at the outlet of 45-47 percent.

The second plug flow reactor R3 is provided with the upper, middle and lower three areas with the temperature of 114.8 ℃, 118.1 ℃, 122.1 ℃, the pressure of 0.52MPa, the stirring speed of 4R/min and the solid content at the outlet of 58-60 percent.

The third plug flow reactor R4 is provided with the upper, middle and lower three areas with the temperature of 130.1 ℃, 133.3 ℃, 138.5 ℃, the pressure of 0.63MPa, the stirring speed of 0.4R/min and the solid content at the outlet of 68-70 percent.

The temperature of the upper middle section area of the independently connected static mixing reactor R5 is removed, explosion polymerization is prevented, the temperature of the lower section area is 145.1 ℃, stirring is not carried out, the pressure is 0.65MPa, and the solid content at the outlet is 82-84%.

By controlling the narrow molecular weight distribution of rubber particles in the internal circulation reactor R1, the solid content of the mixture in the three-stage plug flow reactors R2-4 and the independently connected static mixing reactor R5 obtains reasonable rubber particle size and distribution of rubber particles, thereby effectively improving the impact performance of the ABS resin product prepared by the bulk method, and the test results are shown in Table 2.

Table 2 test results

Remarks:

1. samples were taken every 1 hour to test the solids content of the polymer at the outlet of the internal recycle mixer R1.

Example 4

The high performance ABS resin manufactured by example 1 was used. The internal circulation mixer R1 is a prepolymerization reactor, a continuous rubber phase is subjected to a prepolymerization process of grafting SAN in the reactor, a circulation pump in the internal circulation reactor R1 can pump rubber particles with smaller size and unreacted monomers back into the system for continuous reaction, the rubber grafting rate and the monomer conversion rate are improved, the product quality is stabilized, and the internal circulation R1 reactor is favorable for obtaining rubber particles with narrower molecular weight molecules. The materials sequentially enter a first-stage, a second-stage and a third-stage plug flow reactors and a static mixing reactor R5 to further generate a SAN grafting reaction process. The weight percentages of the components in the raw material liquid entering the grafting reactor are as follows: the polystyrene-butadiene-isoprene ternary integrated rubber accounts for 8.4% of the mixed glue solution containing styrene, acrylonitrile, an initiator, a chain transfer agent and a solvent, the styrene accounts for 63.6% of the glue solution, the acrylonitrile accounts for 14% of the glue solution, and the ethylbenzene accounts for 14% of the glue solution. The initiator was 70ppm based on the styrene and acrylonitrile solution and the flow was controlled at 0.7g/h. The chain transfer agent accounts for 35ppm of the solution of styrene and acrylonitrile, and the flow rate is controlled to be 0.5g/h.

The setting temperature of the first, second and third stage static mixers R1-abc in the internal circulation reactor R1 is 101.0 ℃, 101.2 ℃, 101.4 ℃ and the pressure is 0.34MPa, 0.35MPa and 0.36MPa in sequence, the material residence time is 0.2-1 hour, preferably 0.5-0.8 hour, and the solid content at the outlet is 13-14%.

The first plug flow reactor R2 is provided with the upper, middle and lower three areas with the temperature of 102.4 ℃, 104.5 ℃, 106.1 ℃ and the pressure of 0.42MPa, the stirring speed of 13R/min and the solid content at the outlet of 45-47 percent.

The second plug flow reactor R3 is provided with the upper, middle and lower three areas with the temperature of 115.2 ℃, 118.5 ℃, 122.5 ℃, the pressure of 0.53MPa, the stirring speed of 3R/min and the solid content at the outlet of 60-62 percent.

The third plug flow reactor R4 is provided with the upper, middle and lower three areas with the temperature of 130.3 ℃, 133.8 ℃, 138.8 ℃, the pressure of 0.65MPa, the stirring speed of 0.3R/min and the solid content at the outlet of 71-73 percent.

The temperature of the upper and middle sections of the static mixing reactor R5 which are independently connected is removed, explosion polymerization is prevented, the temperature of the lower section is set to 148.5 ℃, stirring is not carried out, the pressure is 0.68MPa, and the solid content at the outlet is 83-85%.

By controlling the stirring speed of the internal circulation mixer R1 and controlling the solid content of the mixture in the internal circulation mixer R1, the three-stage plug flow reactor R2R3R4 and the static mixing reactor R5, reasonable rubber particle size and distribution of rubber particles are obtained, so that the impact performance of the ABS resin product prepared by the bulk method is effectively improved, and the test results are shown in Table 3.

Table 3 test results

Remarks:

Example 5

The high performance ABS resin manufactured by example 1 was used. The weight percentages of the components entering the internal circulation reactor R1 are as follows: the soluble amino functionalized styrene-butadiene-isoprene ternary integrated rubber accounts for 8.4% of the mixed glue solution weight ratio of styrene, acrylonitrile, an initiator, a chain transfer agent and a solvent, the styrene accounts for 63.6% of the glue solution weight ratio, the acrylonitrile accounts for 14% of the glue solution weight ratio, and the ethylbenzene accounts for 14% of the glue solution weight ratio. The initiator was 70ppm based on the styrene and acrylonitrile solution and the flow was controlled to 0.7g/h. The chain transfer agent accounts for 35ppm of the solution of styrene and acrylonitrile, and the flow rate is controlled to be 0.5g/h.

The internal circulation reactor R1 is set for a residence time of 0.2 to 1 hour, preferably 0.5 to 0.8 hour, and the solid content at the outlet is 13 to 14%.

The temperature of the upper, middle and lower three areas of the first plug flow reactor R2 is 103.2 ℃, 104.5 ℃, 105.8 ℃, the pressure is 0.42MPa, the stirring speed is 16R/min, and the solid content at the outlet is 47-49%.

The second plug flow reactor R3 is provided with the upper, middle and lower three areas with the temperature of 115.5 ℃, 118.6 ℃, 122.5 ℃, the pressure of 0.53MPa, the stirring speed of 4R/min and the solid content at the outlet of 60-62 percent.

The third plug flow reactor R4 is provided with the upper, middle and lower three areas with the temperature of 130.3 ℃, 132.6 ℃, 135.7 ℃, the pressure of 0.65MPa, the stirring speed of 0.3R/min and the solid content at the outlet of 68-75 percent.

The temperature of the upper and middle sections of the static mixing reactor R5 is removed, explosion polymerization is prevented, the temperature of the lower section is 150 ℃, stirring is not carried out, the pressure is 0.68MPa, and the solid content at the outlet is 84-86%.

By controlling the narrow molecular weight distribution of rubber particles in the internal circulation reactor R1, the solid content of the mixture in the three-stage plug flow reactors R2-4 and the independently connected static mixing reactor R5 obtains reasonable rubber particle size and distribution of rubber particles, thereby effectively improving the impact performance of the ABS resin product prepared by the bulk method, and the test results are shown in Table 4.

Table 4 test results

Remarks:

The above-mentioned preferable conditions can be combined with each other to obtain a specific embodiment on the basis of common knowledge in the art.

The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown and described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An ABS resin production process system containing an internal circulation device is characterized by comprising an internal circulation reactor, a primary plug flow reactor, a secondary plug flow reactor, a tertiary plug flow reactor and a static mixing reactor which are sequentially connected in series through pipelines;

The internal circulation reactor is a series loop consisting of a first-stage static mixer, a second-stage static mixer, a third-stage static mixer and a circulating pump which are sequentially communicated through pipelines; the feed inlet is connected with the filter in series and then is communicated with a circulating loop pipeline between the first-stage static mixing reactor and the circulating pump through a feed pipe, a discharge port is arranged between the third-stage static mixer and the circulating pump, and the discharge port is communicated with the inlet of the first-stage plug flow reactor through a branch pipe;

the primary plug flow reactor, the secondary plug flow reactor and the tertiary plug flow reactor are tubular reactors, each plug flow reactor is divided into an upper region, a middle region and a lower region, and each region is provided with a guide plate and a stirring shaft with a flat paddle; the stirring shaft is in transmission connection with a stirring motor arranged at the bottom of the plug flow reactor;

the upper, middle and lower three areas of the plug flow reactor are independent heat conduction pipe systems, temperature control systems and pressure control systems;

the stirring speed of the primary plug flow reactor, the secondary plug flow reactor and the tertiary plug flow reactor is reduced in sequence; the temperature and the pressure in the first-stage plug flow reactor, the second-stage plug flow reactor, the third-stage plug flow reactor and the static mixing reactor are gradually increased; the temperature settings in the upper, middle and lower three areas of the primary plug flow reactor, the secondary plug flow reactor and the tertiary plug flow reactor are gradually increased; the upper and middle regions of the static mixing reactor are heat-removed, and the lower region is heated.

2. The process system for producing ABS resin with an internal circulation device according to claim 1, wherein the inside of the first-stage static mixer, the inside of the second-stage static mixer and the inside of the third-stage static mixer are respectively provided with a deflector;

the temperature and pressure in the first, second and third static mixers of the internal circulation reactor are gradually increased.

3. The process system for producing an ABS resin comprising an internal circulation device according to claim 1, wherein the static mixing reactor is divided into upper, middle and lower three regions, each region being provided with a baffle.

4. The ABS resin production process system comprising the internal circulation device according to any one of claims 1 or 2 wherein the static mixer, the plug flow reactor and the static mixing reactor are each provided with a jacket, and heat conduction oil pipes are laid in the jackets and in the interlayer of the deflector; and the heat conduction oil pipe is communicated with the heat conduction oil pump.

5. The process system for producing ABS resin with internal circulation device according to claim 4, wherein at least a part of the static mixer, the primary plug flow reactor, the secondary plug flow reactor, the tertiary plug flow reactor and the independent series static mixing reactor and the pipeline is made of carbon steel and stainless steel materials, and the inner surface is provided with an antirust coating.

6. A method for preparing high-performance ABS resin by using the production process system according to any one of claims 1 to 3, characterized by comprising the steps of:

step one, conveying styrene, acrylonitrile monomers, antioxidants and toughening rubber particles which are prepared in proportion to a feed inlet by a feed pump, and simultaneously continuously adding an initiator solution, a chain transfer agent solution and a dilution circulating solution which are dissolved in proportion to a formula to the feed inlet by respective metering pumps and feed pumps; sequentially entering a first-stage static mixer, a second-stage static mixer and a third-stage static mixer in the internal circulation reactor to carry out prepolymerization reaction after passing through a filter, wherein the first-stage static mixer, the second-stage static mixer and the third-stage static mixer in the internal circulation reactor control the reaction temperature to be 100-110 ℃, and the pressure is set to be 0.25-0.45MPa; the prepolymerization residence time is 0.2 to 1 hour, and the solid content at the outlet is controlled to be 12 to 15 percent;

step two, pumping smaller-sized rubber particles and unreacted monomers in the prepolymerized materials in the internal circulation reactor back to an internal system by a circulation pump to continue the reaction, pumping the materials reaching the size requirement into the primary plug flow reactor, controlling the reaction temperature to be 100-110 ℃, controlling the pressure to be 0.25-0.45MPa, and stirring at the speed of 10-25r/min; the residence time is 0.5-2.0 hours, and the solid content of the material at the outlet is 45-50%;

Pumping materials from the first-stage plug flow reactor into the second-stage plug flow reactor, controlling the reaction temperature to be 110-130 ℃, controlling the pressure to be 0.45-0.55MPa, and controlling the stirring speed to be 2-8r/min; the retention time of the materials is 0.5 to 2.0 hours, and the solid content of the materials at the outlet is 58 to 62 percent;

step four, pumping materials from a secondary plug flow reactor to a tertiary plug flow reactor, controlling the reaction temperature to be 130-150 ℃, controlling the pressure to be 0.55-0.7MPa and controlling the stirring speed to be 0.3-1r/min; the retention time of the materials is 0.5 to 2.0 hours, and the solid content of the materials at the outlet is 68 to 75 percent;

step five, pumping the materials from the three-stage plug flow reactor to the static mixing reactor, wherein the upper and middle regions do not need to be heated, and the lower region controls the reaction temperature to be 130-190 ℃ and the pressure to be 0.6-0.7MPa; the retention time of the materials is 0.5 to 2.0 hours, and the solid content of the materials at the outlet is 82 to 86 percent; and after the material reaches the conversion rate, carrying out post-treatment and granulation to obtain an ABS resin finished product.

7. The method for preparing high-performance ABS resin according to claim 6, wherein the toughening rubber is at least 1 of polybutadiene rubber, styrene-butadiene binary copolymer rubber, styrene-isoprene-butadiene ternary integrated rubber, amino/siloxy/silaxy functional styrene-butadiene copolymer rubber, amino/siloxy/silaxy functional styrene-isoprene-butadiene copolymer integrated rubber.

8. The method for preparing high-performance ABS resin according to claim 6, wherein the solvent is toluene or ethylbenzene;

the initiator is 1, 1-di-tert-butyl cyclohexane peroxide;

the chain transfer agent is n-dodecyl mercaptan;

the antioxidant is 1-octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the diluted circulation liquid is selected from at least 1 of propane, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, cyclohexane, n-heptane, methylcyclohexane and ethylbenzene.

9. The method for preparing high-performance ABS resin according to claim 7, wherein the toughened rubber accounts for 5-15% of the mixed glue solution containing styrene, acrylonitrile, initiator, chain transfer agent and solvent, the styrene accounts for 40-75% of the total glue solution, the solvent accounts for 10-20% of the total glue solution, and the acrylonitrile accounts for 5-20% of the total glue solution; the chain transfer agent is used in an amount of 0.10 to 0.40 percent of the sum of the mass of the acrylonitrile and the mass of the styrene; the antioxidant is used in an amount of 0.30-0.3% based on the total mass of acrylonitrile and styrene.