CN114870750B - HIPS resin production process system containing internal circulation device and high-performance HIPS resin preparation method - Google Patents
HIPS resin production process system containing internal circulation device and high-performance HIPS resin preparation method Download PDFInfo
- Publication number
- CN114870750B CN114870750B CN202210650569.7A CN202210650569A CN114870750B CN 114870750 B CN114870750 B CN 114870750B CN 202210650569 A CN202210650569 A CN 202210650569A CN 114870750 B CN114870750 B CN 114870750B
- Authority
- CN
- China
- Prior art keywords
- reactor
- plug flow
- flow reactor
- internal circulation
- stage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/006—Processes utilising sub-atmospheric pressure; Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a HIPS resin production process system with an internal circulation device and a body preparation method. 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 2. 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 HIPS resin product has the characteristics of narrow molecular weight distribution, uniform dispersion, high impact strength, good industrial production prospect and remarkable economic benefit.
Description
Technical Field
The invention belongs to the field of high polymer material synthesis and preparation processes, and particularly relates to a HIPS resin production process system with an internal circulation device and a preparation method of high-performance HIPS resin.
Background
The general polystyrene (GPPS) resin, namely styrene homopolymer, is one of the earliest industrialized synthetic resins, has good transparency, rigidity, dimensional stability, processing fluidity, chemical corrosion resistance, electrical insulation and the like, and is widely applied to the fields of engineering, automobile industry, household appliances and the like. However, further applications of GPPS are limited due to their deficiencies in fracture toughness, environmental stress cracking resistance, solvent resistance, and heat resistance. In recent years, toughening resins have been widely developed and used, and among them, high Impact Polystyrene (HIPS) is a typical rubber toughening resin material. HIPS resins are typically two-phase structured white opaque beaded or pelletized thermoplastic resins composed of a GPPS continuous phase and a rubber dispersed phase. Because of the presence of the toughening rubber particles, HIPS has the advantages of rigidity, excellent processability, good dimensional stability and the like of styrene-like resin, and meanwhile, compared with GPPS matrix resin, the HIPS has obviously improved impact resistance, is widely applied to the electronic and electrical industry, the automobile manufacturing industry, the household appliance industry and the like, and has been developed into one of the most successful styrene-like toughening resins.
The simple and convenient method for producing HIPS by using rubber modified GPPS resin is a mechanical blending method, the process is simple, the implementation is easy, the rubber addition amount is accurate, but the rubber particle size of the HIPS production process by mechanical blending is relatively coarse, and the toughening efficiency is relatively low. The HIPS is prepared by graft copolymerization of a toughening rubber component in a certain proportion in styrene and a small amount of solvent, and the dissolved glue solution, an initiator and a molecular weight regulator are subjected to a free radical reaction to carry out graft polymerization process at a certain temperature, and the HIPS resin product is obtained through a devolatilization and granulation process. As rubber phase particles are grafted with part of styrene monomer, chemical bonds formed by rubber and styrene are increased, and the formed rubber dispersed phase contains polystyrene units, the interaction between the rubber phase and non-grafted GPPS phase is enhanced, the bonding energy between phase interfaces is enhanced, the rubber particles are uniformly dispersed in the GPPS matrix, the toughening effect is improved, and the physical properties such as impact strength of the material are obviously improved. In addition, the method has the advantages of compact process flow, low energy consumption, pure product, low odor, less wastewater discharge, little pollution, low operation cost, environmental protection, easy serialization and automation and the like, is a production process which is important to develop in the current country, and has a very strong application prospect. However, HIPS resin technology prepared by continuous bulk polymerization has high requirements on rubber types, reactor control, enhanced mass transfer and heat transfer processes. The continuous mass method HIPS resin production device introduced in China is the most representative multistage plug flow tube type reactor series device developed by the American Dow chemistry (DOW), the device is formed by connecting 3 plug flow reactors in series, a plurality of layers of partition plates are arranged in each reactor to reduce back mixing, the stirring paddles of each plug flow tube type reactor can be independently controlled, the stirring effect is good, the problem of material wall hanging is avoided, and the product performance and the color are good. However, the device has high requirements on mass transfer and heat transfer, the process fluctuation of each stage of reactor is large, the system stability is poor, the rubber particle size is uneven, and the problems of explosion aggregation and the like exist.
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 HIPS production process, development of brand-new production process equipment of high-performance HIPS 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 a HIPS production process system in the prior art, the prepared rubber particles are wide in molecular weight distribution, poor in dispersibility and the like, the invention provides a production process system of high-performance HIPS 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:
a HIPS resin production process system comprising an internal circulation device comprises an internal circulation reactor, a primary plug flow reactor, a secondary 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 feeding pipe 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, a discharge hole is arranged between the third-stage static mixer and the circulating pump, and the discharge hole is connected 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, then are input into a feed inlet by the feed pump through a filter, and are connected with an internal circulation reactor through a pipeline; 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 and the secondary 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 inside 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 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 independent heat conducting pipe systems, temperature control systems and pressure control systems.
Further, the stirring speeds of the primary plug flow reactor and the secondary plug flow reactor are sequentially reduced; the temperature and the pressure in the primary plug flow reactor, the secondary 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 and secondary plug flow reactors are gradually increased; the upper and middle regions of the static mixing reactor are heat-removed, and the lower region is heated.
Further, the three-stage static mixer, the two-stage plug flow reactor and the static mixing reactor of the internal circulation reactor are all provided with jackets, and a guide plate is arranged in each jacket; and heat conduction oil pipes are respectively laid in the jackets and the interlayer of the guide plate and are communicated with the heat conduction oil pump, and heat conduction oil circulation is utilized for heat conduction and heat removal.
Further, at least one part of the static mixer, the primary plug flow reactor, the secondary plug flow reactor, the 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.
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 13-18%, 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 48-55%, 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 and the secondary plug flow reactor are gradually increased from top to bottom, wherein,
the temperature of the primary plug flow reactor ranges from 105 ℃ to 120 ℃;
the temperature of the secondary plug flow reactor ranges from 120 ℃ to 150 ℃.
Further, the pressure of the primary plug flow reactor and the secondary plug flow reactor is between 0.25 and 0.5MPa, the pressure is gradually increased, and the preferable pressure is 0.32MPa and 0.43MPa in sequence; the stirring speed of the primary plug flow reactor and the secondary 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 12-25r/min and 2-10r/min in sequence.
Further, the static mixing reactor is not required to be heated in the upper and middle sections from top to bottom, the temperature of the lower section is controlled to be 100-190 ℃ and preferably 150-190 ℃ or 145-150 ℃ without stirring paddles, the pressure is 0.25-0.5MPa and preferably 0.45-0.5MPa, and the upper and middle sections are not required to be heated.
The solid content of the mixture at the inlet of the upper section of the static mixing reactor is 67-75%, 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 reactor, 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. And the devolatilizer flashes out unreacted styrene and solvent, recycles the unreacted styrene and the solvent, and the melted material passes through a granulator to obtain HIPS resin finished products.
Further, the internal circulation reactor, 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 HIPS resin by using the production process system, which mainly comprises the following steps:
step one, conveying styrene, an antioxidant and toughening rubber particles which are prepared in proportion to a feed pipe, simultaneously continuously adding an initiator solution, a chain transfer agent solution and a dilution circulating solution which are dissolved according to the formula proportion to the feed pipe through 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 reaction, wherein the pressures of the first-stage static mixer, the second-stage static mixer and the third-stage static mixer in the internal circulation reactor are set to be 0.25-0.5MPa, preferably 0.25-0.35MPa, the reaction pressure is preferably 0.28MPa, the reaction temperature is 100-115 ℃, preferably 105.2 ℃, the solid content at an outlet is controlled to be 13-18%, and the prepolymerization time is controlled to be 0.2-1 h, preferably 0.5-0.8 h;
step two, pumping the rubber particles with smaller sizes and unreacted monomers in the materials prepolymerized by 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, and controlling the reaction temperature to be 105-120 ℃ and the pressure to be 0.25-0.5MPa, preferably 0.25-0.35MPa; the stirring speed is 12-25r/min, the residence time is 0.5-2.0 hours, the solid content of the materials at the outlet is 48-55%, the three areas of the primary plug flow reactor from top to bottom are sequentially set to be 106.2 ℃, 113.2 ℃, 116.8 ℃ and the reactor pressure is preferably 0.32MPa;
step three, pumping materials from a first-stage plug flow reactor into a second-stage plug flow reactor, controlling the reaction temperature to be 120-150 ℃ and controlling the pressure to be 0.25-0.5MPa; preferably between 0.35 and 0.45 MPa; the stirring speed is 2-10r/min, the material residence time is 0.5-2.0 hours, the solid content of the material at the outlet is 65-75%, preferably 67-75%, more preferably 68-70%, the temperature of the first-stage plug flow reactor is 128.1 ℃, 141.2 ℃, 148.2 ℃ and the reactor pressure is preferably 0.43MPa in sequence from top to bottom;
pumping the materials from the three-stage plug flow reactor to the static mixing reactor, wherein the upper and middle regions need to be heat-removed to below 100 ℃, and the lower region controls the reaction temperature to be 150-190 ℃, preferably 170 ℃, and the pressure range to be 0.25-0.5MPa, preferably 0.4-0.5MPa; the residence time of the material is 0.5-2.0 hours, the solid content of the material at the outlet is 80-86%, preferably 82-86%, more preferably 84-85%, and the pressure of the reactor is preferably 0.48MPa; and after the material reaches the conversion rate, the material is sent to a devolatilizer to flash off unreacted styrene and solvent and recycle the unreacted styrene and the solvent, and the melted material is pelletized to obtain a HIPS 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 3-12% of the mixed glue solution containing styrene, an initiator, a chain transfer agent and a solvent, the styrene accounts for 45-85% of the total glue solution, and the solvent accounts for 10-20% of the total glue solution; the chain transfer agent is used in an amount of 0.10 to 0.40 percent based on the mass of the styrene; the antioxidant is used in an amount of 0.30-0.3% by mass of styrene.
The HIPS resin is a rubber toughened polystyrene 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 dispersed phase is rubber particles grafted with styrene homopolymer, and the continuous phase is macromolecular styrene homopolymer GPPS. 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 HIPS resin 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 HIPS resin product has the characteristics of narrow molecular weight distribution 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 a HIPS resin production process system including an internal circulation device.
Reference numerals illustrate: r1-an internal circulation reactor; r2-primary plug flow reactor; r3-secondary plug flow reactor; r4-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: microscopic morphology observation of HIPS resin is carried out by adopting the American FEI company, namely, firstly, ultrathin slicing is carried out, then, after 24 hours of oxidation by osmium tetroxide, TEM observation is carried out, and the test pressure is 200kV; scanning Electron Microscope (SEM) analysis: spraying gold on the section of the HIPS sample after impact fracture by using a gold spraying instrument K550X produced by EMITECH company in England, and placing the HIPS sample under a QUANTA200 scanning electron microscope produced by FEI company in America to observe the section morphology at an accelerating voltage of 20kV; polymer solids (X) test: the clean crucible was pre-weighed 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, a HIPS resin production process system with an internal circulation device comprises an internal circulation reactor R1, a first plug flow reactor R2, a second plug flow reactor R3 and a static mixing reactor R4 which are sequentially connected in series through pipelines; the material output end of the static mixing reactor R4 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 monomer and solvent and recycling, and the melted materials pass through a granulator to obtain HIPS resin finished products.
The internal circulation reactor R1 is a series loop formed by a first-stage static mixer a, a second-stage static mixer b, a third-stage static mixer c and a circulating pump which are sequentially communicated through pipelines; the feeding pipe is connected with the filter D in series and then is communicated with a circulating loop pipeline between the first-stage static mixer a and the circulating pump, a discharge port is arranged between the third-stage static mixer c and the circulating pump, and the discharge port is connected with an inlet of the first-stage plug flow reactor R2 through a branch pipe;
all the raw materials which are configured in proportion are input into a feed pipe for mixing, and then are input into a circulation loop of the internal circulation reactor R1 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, 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 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 100-115 ℃, the pressure range is 0.25-0.5MPa, and the pressure range is preferably 0.25-0.35MPa;
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 13-18%.
The primary plug flow reactor R2 and the secondary plug flow reactor R3 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 primary plug flow reactor R2 and the secondary plug flow reactor R3 are respectively an independent heat conduction pipe system, a temperature control system and a pressure control system.
The stirring shaft inside 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 speed of the primary plug flow reactor R2 and the secondary plug flow reactor R3 is reduced in sequence; the temperature and the pressure in the primary plug flow reactor R2, the secondary plug flow reactor R3 and the static mixing reactor R4 are gradually increased; the temperature settings in the upper, middle and lower three areas of the first-stage plug flow reactor R2 and the second-stage plug flow reactor R3 are gradually increased; the upper and middle regions of the static mixing reactor R4 are heat-removed, and the lower region is heated.
The internal circulation reactor R1, the plug flow reactor R2-3 and the static mixing reactor R4 are all provided with jackets, guide plates are arranged in the jackets, heat conduction oil pipes are laid in the jackets and the guide plate interlayers, and are 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 R2-3 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 temperature of the primary and secondary plug flow reactors is gradually increased, the preferable temperature range is sequentially 105-120 ℃, the temperature range is 120-150 ℃, the pressure is set to be adjustable within the range of 0.25-0.5MPa, and the preferable pressure range is sequentially 0.25-0.35MPa and the pressure range is 0.35-0.45MPa.
The upper, middle and lower three sections of guide plates of the static mixing reactor R4 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, the heat is required to be removed to be lower than 100 ℃, the temperature is controlled to prevent the explosion polymerization 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 150-190 ℃, the monomer conversion rate is improved, and the pressure is 0.25-0.5MPa, preferably 0.4-0.5MPa; 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 independently connected static mixing reactor R4 and at least one part of the pipeline are made of carbon steel and stainless steel materials, and the internal surface is provided with an antirust coating.
And sampling ports are arranged at the outlets of the internal circulation reactor R1, the secondary plug flow reactor R2-3 and the independently connected static mixing reactor R5 and are used for monitoring the solid content.
Example 2
The high performance HIPS resin produced in example 1 was used. The weight percentages of the components entering the full mixed flow reactor R1 are as follows: the polystyrene-butadiene-isoprene ternary integrated rubber accounts for 8.4% of the mixed glue solution containing styrene, an initiator, a chain transfer agent and a solvent, the styrene accounts for 77.6% of the glue solution, and the ethylbenzene accounts for 14% of the glue solution. The initiator was 70ppm based on the styrene solution and the flow was controlled to 0.7g/h. The chain transfer agent was 35ppm based on the styrene concentration and the controlled flow was 0.5g/h.
The setting temperature of the internal circulation reactor is 100-115 ℃, the preferable temperature of a first static mixer R1-abc, a second static mixer R2-abc and a third static mixer R3-abc in the internal circulation reactor are 105.1 ℃, 105.4 ℃, 105.8 ℃ and the pressure of the internal circulation reactor are 0.26MPa, 0.27MPa and 0.28MPa in sequence, the plug flow reactor R2-3 is a tubular reactor, the R2-3 three-level plug flow reactor is divided into an upper region, a middle region and a lower region, and a guide plate and a stirring shaft with a flat paddle are respectively arranged in the upper region, the middle region and the lower region; the upper, middle and lower three sections of guide plates of the R2-3 secondary piston 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 0.25-0.5MPa, the pressure of the primary and secondary piston flow reactors is gradually increased, and the preferable pressure is 0.32MPa and 0.43MPa in sequence; the stirring speed of the R2-3 secondary 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 regulated and controlled in the later reaction stage, and the stirring speed is preferably 12-25R/min and 2-10R/min in sequence; the residence time of the R2-3 secondary plug flow reactor is 0.5-2.0 hours, and the solid content at the outlet of the lower section area is 48-55% and 67-75% 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 15 to 17%.
The temperature of the upper, middle and lower three areas of the first plug flow reactor R2 is 106.2 ℃, 113.2 ℃, 116.8 ℃ and the pressure is 0.32MPa, the stirring speed is 18R/min, and the solid content at the outlet is 52-54%.
The second plug flow reactor R3 is provided with the upper, middle and lower three areas with the temperature of 128.1 ℃, 141.2 ℃, 148.2 ℃, the pressure of 0.43MPa, the stirring speed of 5R/min and the solid content at the outlet of 71-74 percent.
The temperature of the upper and middle sections of the static mixing reactor R4 is removed, explosion polymerization is prevented, the temperature of the lower section is 170 ℃, the pressure is 0.48MPa, 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 reactor R2-3 and the independently connected static mixing reactor R4 obtains reasonable rubber particle size and distribution of rubber particles, thereby effectively improving the impact performance of HIPS resin products 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 3 hours to test the solids content and average rubber particle size of the polymer at the outlet of the static mixing reactor R4.
3. HIPS products were injection molded every 3 hours, and the impact strength and elongation at break of the products were tested once.
Example 3
The high performance HIPS resin produced in example 1 was used. The internal circulation reactor R1 is a prepolymerization reactor, the continuous rubber phase is subjected to a prepolymerization process of grafting GPPS in the reactor, and 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, so that the grafting rate and the monomer conversion rate of the rubber are improved, the product quality is stabilized, and the internal circulation reactor R1 is favorable for obtaining rubber particles with narrower molecular weight molecules. Materials sequentially enter a first-stage plug flow reactor and a second-stage plug flow reactor and a static mixing reactor R4 which are independently connected, so that GPPS grafting reaction process further occurs. 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, an initiator, a chain transfer agent and a solvent, the styrene accounts for 77.6% of the glue solution, and the ethylbenzene accounts for 14% of the glue solution. The initiator was 70ppm based on the styrene solution and the flow was controlled to 0.7g/h. The chain transfer agent was 35ppm based on the styrene concentration and the controlled flow was 0.5g/h.
The setting temperature of the first, second and third stage static mixers R1-abc in the internal circulation reactor R1 is 102.8 ℃, 103.4 ℃, 103.6 ℃ and the pressure is 0.28MPa, 0.29MPa and 0.30MPa 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 13-15%.
The first plug flow reactor R2 is provided with the upper, middle and lower three areas with the temperature of 105.2 ℃, 112.1 ℃, 114.8 ℃ and the pressure of 0.31MPa, the stirring speed of 18R/min and the solid content at the outlet of 49-51 percent.
The second plug flow reactor R3 is provided with the upper, middle and lower three areas with the temperature of 126.1 ℃, 140.5 ℃, 146.2 ℃, the pressure of 0.40MPa, the stirring speed of 5R/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 R4 is removed, explosion is prevented, the temperature of the lower section area is set to 168 ℃, the pressure is 0.46MPa, 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 reactor R2-3 and the independently connected static mixing reactor R4 obtains reasonable rubber particle size and distribution of rubber particles, thereby effectively improving the impact performance of HIPS resin products 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 reactor R1.
2. Samples were taken every 3 hours to test the solids content and average rubber particle size of the polymer at the outlet of the static mixing reactor R4.
3. HIPS products were injection molded every 3 hours, and the impact strength and elongation at break of the products were tested once.
Example 4
The high performance HIPS resin produced in example 1 was used. The internal circulation reactor R1 is a prepolymerization reactor, the continuous rubber phase is subjected to a prepolymerization process of grafting GPPS in the reactor, and 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, so that the grafting rate and the monomer conversion rate of the rubber are improved, the product quality is stabilized, and the internal circulation reactor R1 is favorable for obtaining rubber particles with narrower molecular weight molecules. Materials sequentially enter a first-stage plug flow reactor and a second-stage plug flow reactor and a static mixing reactor R4 which are independently connected, so that GPPS grafting reaction process further occurs. 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, an initiator, a chain transfer agent and a solvent, the styrene accounts for 77.6% of the glue solution, and the ethylbenzene accounts for 14% of the glue solution. The initiator was 70ppm based on the styrene solution and the flow was controlled to 0.7g/h. The chain transfer agent was 35ppm based on the styrene solution and the flow was 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 104.0 ℃, 104.2 ℃, 104.4 ℃ and the pressure is 0.30MPa, 0.31MPa and 0.32MPa 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 14-16%.
The first plug flow reactor R2 is provided with the upper, middle and lower three areas with the temperature of 106.2 ℃, 113.2 ℃, 116.8 ℃ and the pressure of 0.32MPa, the stirring speed of 16R/min and the solid content at the outlet of 51-53 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 ℃ and the pressure of 0.43MPa, the stirring speed of 3R/min and the solid content at the outlet of 69-72 percent.
The temperature of the upper and middle sections of the static mixing reactor R4 which are independently connected is removed, explosion is prevented, the temperature of the lower section is 170 ℃, the pressure is 0.48MPa, the solid content at the outlet is 82-84%, and the solid content at the outlet is 83-85%.
By controlling the stirring speed of the internal circulation reactor R1 and controlling the solid content of the mixture in the internal circulation reactor 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 HIPS resin products prepared by the bulk method is effectively improved, and the test results are shown in Table 3.
Table 3 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 3 hours to test the solids content and average rubber particle size of the polymer at the outlet of the static mixing reactor R4.
3. HIPS products were injection molded every 3 hours, and the impact strength and elongation at break of the products were tested once.
Example 5
The high performance HIPS resin produced in example 1 was used. The weight percentages of the components entering the full mixed flow reactor R1 are as follows: the soluble amino functionalized styrene-butadiene-isoprene ternary integrated rubber accounts for 8.4% of the mixed glue solution containing styrene, an initiator, a chain transfer agent and a solvent, the styrene accounts for 77.6% of the glue solution, and the ethylbenzene accounts for 14% of the glue solution. The initiator was 70ppm based on the styrene solution and the flow was controlled to 0.7g/h. The chain transfer agent was 35ppm based on the styrene concentration and the controlled flow was 0.5g/h.
The setting temperature of the internal circulation reactor is 100-115 ℃, the preferable temperature of a first static mixer R1-abc, a second static mixer R2-abc and a third static mixer R3-abc in the internal circulation reactor are 105.1 ℃, 105.4 ℃, 105.8 ℃ and the pressure of the internal circulation reactor are 0.26MPa, 0.27MPa and 0.28MPa in sequence, the plug flow reactor R2-3 is a tubular reactor, the R2-3 three-level plug flow reactor is divided into an upper region, a middle region and a lower region, and a guide plate and a stirring shaft with a flat paddle are respectively arranged in the upper region, the middle region and the lower region; the upper, middle and lower three sections of guide plates of the R2-3 secondary piston 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 0.25-0.5MPa, the pressure of the primary and secondary piston flow reactors is gradually increased, and the preferable pressure is 0.32MPa and 0.43MPa in sequence; the stirring speed of the R2-3 secondary 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 regulated and controlled in the later reaction stage, and the stirring speed is preferably 12-25R/min and 2-10R/min in sequence; the residence time of the R2-3 secondary plug flow reactor is 0.5-2.0 hours, and the solid content at the outlet of the lower section area is 48-55% and 67-75% 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 17%.
The first plug flow reactor R2 is provided with the upper, middle and lower three areas with the temperature of 106.2 ℃, 113.2 ℃, 116.8 ℃ and the pressure of 0.32MPa, the stirring speed of 18R/min and the solid content at the outlet of 50-53 percent.
The second plug flow reactor R3 is provided with the upper, middle and lower three areas with the temperature of 128.1 ℃, 141.2 ℃, 148.2 ℃ and the pressure of 0.43MPa, the stirring speed of 4R/min and the solid content at the outlet of 70-73 percent.
The temperature of the upper and middle sections of the static mixing reactor R4 is removed, explosion polymerization is prevented, the temperature of the lower section is set at 171 ℃, the pressure is 0.48MPa, 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 reactor R2-3 and the independently connected static mixing reactor R4 obtains reasonable rubber particle size and distribution of rubber particles, thereby effectively improving the impact performance of HIPS resin products prepared by the bulk method, and the test results are shown in Table 4.
Table 4 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 3 hours to test the solids content and average rubber particle size of the polymer at the outlet of the static mixing reactor R4.
3. HIPS products were injection molded every 3 hours, and the impact strength and elongation at break of the products were tested once.
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 (7)
1. The HIPS resin production process system with the internal circulation device is characterized by comprising an internal circulation reactor, a primary plug flow reactor, a secondary 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 feeding pipe is connected with the filter in series and then is communicated with a pipeline between the first-stage static mixer and the circulating pump, a discharge hole is arranged between the third-stage static mixer and the circulating pump, and the discharge hole is communicated with the inlet of the first-stage plug flow reactor through a branch pipe;
the primary plug flow reactor and the secondary 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 inside the plug flow reactor 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 and the secondary plug flow reactor is reduced in sequence; the pressure in the primary plug flow reactor, the secondary plug flow reactor and the static mixing reactor is gradually increased; the reaction temperature in the primary plug flow reactor is 105-120 ℃; the reaction temperature in the secondary plug flow reactor is 120-150 ℃; the static mixing reactor is divided into an upper region, a middle region and a lower region, and each region is provided with a guide plate; the upper and middle regions of the static mixing reactor are heat-removed to below 100 ℃, and the lower region controls the reaction temperature to 150-190 ℃.
2. The HIPS resin production process system with an internal circulation device according to claim 1, wherein the first-stage static mixer, the second-stage static mixer and the third-stage static mixer are internally provided with guide plates;
the first, second and third static mixers are independent heat conducting pipe systems, temperature control systems and pressure control systems;
the temperature and pressure in the first, second and third stage static mixers gradually increase.
3. The HIPS resin production process system with the internal circulation device according to any one of claims 1 or 2, wherein a three-stage static mixer, a plug flow reactor and a static mixing reactor of the internal circulation reactor are all provided with jackets, and a guide plate is arranged in each jacket; and heat conduction oil pipes are laid in the jackets and the interlayer of the guide plate, and are communicated with the heat conduction oil pump.
4. The HIPS resin production process system with internal circulation device according to claim 3, wherein at least one part of the static mixer, the primary plug flow reactor, the secondary plug flow reactor, the 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.
5. A method for preparing high performance HIPS resin using the HIPS resin production process system comprising an internal circulation device of any one of claims 1 to 2, comprising the steps of:
step one, conveying styrene, an antioxidant and toughening rubber particles which are prepared in proportion to a feed pipe through a feed inlet, simultaneously continuously adding an initiator solution, a chain transfer agent solution and a dilution circulating solution which are dissolved according to the formula proportion to the feed pipe through 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 an internal circulation reactor for prepolymerization reaction after passing through a filter, wherein the reaction temperature of the first-stage static mixer, the second-stage static mixer and the third-stage static mixer in the internal circulation reactor is controlled to be between 100 ℃ and 115 ℃, and the pressure is set to be between 0.25 MPa and 0.35MPa; the prepolymerization residence time is 0.2 to 1 hour, and the solid content at the outlet is controlled to be 13 to 18 percent;
step two, pumping the rubber particles with smaller sizes and unreacted monomers in the materials prepolymerized by the internal circulation reactor back to the internal circulation reactor by a circulating pump for continuous reaction, pumping the materials reaching the size requirement into the primary plug flow reactor, controlling the reaction temperature to be 105-120 ℃, controlling the pressure to be 0.25-0.35MPa, and stirring at a speed of 12-25r/min; the residence time is 0.5-2.0 hours, and the solid content of the material at the outlet is 48-55%;
pumping materials from the first-stage plug flow reactor into the second-stage plug flow reactor, controlling the reaction temperature to be 120-150 ℃, controlling the pressure to be 0.35-0.45MPa, and stirring at a speed of 2-10r/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 67 to 75 percent;
pumping the materials from the secondary plug flow reactor to the static mixing reactor, wherein the upper and middle regions are heat-removed to below 100 ℃, and the lower region controls the reaction temperature to be 150-190 ℃ and the pressure to be 0.4-0.5MPa; 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 (5) after the material reaches the conversion rate, carrying out post-treatment and pelleting to obtain the HIPS resin finished product.
6. The method of making a high performance HIPS resin of claim 5, wherein the toughening rubber is at least 1 of polybutadiene rubber, styrene-butadiene copolymer rubber, styrene-isoprene-butadiene terpolymer rubber, amino/siloxy/silahyde functionalized styrene-butadiene copolymer rubber, amino/siloxy/silahyde functionalized styrene-isoprene-butadiene copolymer rubber.
7. The method for producing a high performance HIPS resin according to claim 5, wherein,
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210650569.7A CN114870750B (en) | 2022-06-10 | 2022-06-10 | HIPS resin production process system containing internal circulation device and high-performance HIPS resin preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210650569.7A CN114870750B (en) | 2022-06-10 | 2022-06-10 | HIPS resin production process system containing internal circulation device and high-performance HIPS resin preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114870750A CN114870750A (en) | 2022-08-09 |
| CN114870750B true CN114870750B (en) | 2023-09-15 |
Family
ID=82681015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210650569.7A Active CN114870750B (en) | 2022-06-10 | 2022-06-10 | HIPS resin production process system containing internal circulation device and high-performance HIPS resin preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114870750B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1044565A (en) * | 1963-01-28 | 1966-10-05 | Cosden Oil And Chemical Compan | High impact polystyrene and method of making same |
| CN1274372A (en) * | 1998-07-30 | 2000-11-22 | 大日本油墨化学工业株式会社 | Styrene resin compsn. and process for producing same |
| CN1289346A (en) * | 1998-02-07 | 2001-03-28 | 巴斯福股份公司 | Method for the continuous production of thermoplastic moulding materials |
| CN1307604A (en) * | 1998-06-04 | 2001-08-08 | 旭化成株式会社 | Process for preparation of rubber-reinforced styrene resin |
| CN1429852A (en) * | 2001-12-31 | 2003-07-16 | 中国石化集团齐鲁石油化工公司 | Method of producing HIPS using high cis. butadiene rubber by PS equipment |
| US20070142549A1 (en) * | 2005-12-21 | 2007-06-21 | Fina Technology, Inc. | Reactor system for the production of high impact polystyrene |
| CN102046664A (en) * | 2008-07-08 | 2011-05-04 | 东丽株式会社 | Method for manufacturing thermoplastic copolymers |
| CN103172765A (en) * | 2013-03-22 | 2013-06-26 | 上海领智化工科技有限公司 | Device and method for preparing styrene series resin outside kettle by using static hybrid continuous bulk polymerization method |
| CN109180871A (en) * | 2018-01-01 | 2019-01-11 | 杨青岚 | Rubber-modified styrene continuous bulk polymerization process |
| CN113583186A (en) * | 2021-09-09 | 2021-11-02 | 科元控股集团有限公司 | Production method of continuous bulk ABS resin |
| CN216473003U (en) * | 2020-12-28 | 2022-05-10 | 江苏可立特工程设计研究有限公司 | Production equipment for high impact polystyrene with capacity of more than 5 ten thousand tons and capacity scale |
-
2022
- 2022-06-10 CN CN202210650569.7A patent/CN114870750B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1044565A (en) * | 1963-01-28 | 1966-10-05 | Cosden Oil And Chemical Compan | High impact polystyrene and method of making same |
| CN1289346A (en) * | 1998-02-07 | 2001-03-28 | 巴斯福股份公司 | Method for the continuous production of thermoplastic moulding materials |
| CN1307604A (en) * | 1998-06-04 | 2001-08-08 | 旭化成株式会社 | Process for preparation of rubber-reinforced styrene resin |
| CN1274372A (en) * | 1998-07-30 | 2000-11-22 | 大日本油墨化学工业株式会社 | Styrene resin compsn. and process for producing same |
| CN1429852A (en) * | 2001-12-31 | 2003-07-16 | 中国石化集团齐鲁石油化工公司 | Method of producing HIPS using high cis. butadiene rubber by PS equipment |
| US20070142549A1 (en) * | 2005-12-21 | 2007-06-21 | Fina Technology, Inc. | Reactor system for the production of high impact polystyrene |
| CN102046664A (en) * | 2008-07-08 | 2011-05-04 | 东丽株式会社 | Method for manufacturing thermoplastic copolymers |
| CN103172765A (en) * | 2013-03-22 | 2013-06-26 | 上海领智化工科技有限公司 | Device and method for preparing styrene series resin outside kettle by using static hybrid continuous bulk polymerization method |
| CN109180871A (en) * | 2018-01-01 | 2019-01-11 | 杨青岚 | Rubber-modified styrene continuous bulk polymerization process |
| CN216473003U (en) * | 2020-12-28 | 2022-05-10 | 江苏可立特工程设计研究有限公司 | Production equipment for high impact polystyrene with capacity of more than 5 ten thousand tons and capacity scale |
| CN113583186A (en) * | 2021-09-09 | 2021-11-02 | 科元控股集团有限公司 | Production method of continuous bulk ABS resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114870750A (en) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4659790A (en) | Heat-resistant copolymer of alpha-methylstyrene and acrylonitrile, process for preparing the same, and thermoplastic resin composition containing the same | |
| US3903200A (en) | Continuous mass polymerization process for ABS polymeric polyblends | |
| JP3447378B2 (en) | Granulation equipment | |
| US3851014A (en) | Method for making rubber modified resins | |
| CN110746544B (en) | High-gloss high-impact polystyrene material and preparation method thereof | |
| CN106632867B (en) | Method for preparing high-impact AES resin by adopting continuous body device | |
| CN105418835A (en) | Preparing method for core-shell structure functionality acrylate polymer particles for toughening polycarbonate | |
| CN101058621B (en) | Method of preparing ACS polymer based on continuous noumenon method | |
| US5550186A (en) | Particle sizing | |
| CN113877498A (en) | Device and method for preparing SAN resin with stable composition and low volatile component | |
| US4167543A (en) | Thermoplastic molding compositions | |
| US3903199A (en) | Continuous mass polymerization process for ABS polymeric polyblends | |
| CN114870750B (en) | HIPS resin production process system containing internal circulation device and high-performance HIPS resin preparation method | |
| CN115055145B (en) | HIPS resin production process system and preparation method thereof | |
| CN114870781B (en) | ABS resin production process system containing internal circulation device and preparation method thereof | |
| WO2024046494A1 (en) | Breathable polytetrafluoroethylene stretch film and preparation method therefor | |
| CN102633950B (en) | Synthetic method of ABS graft copolymer with multimodal distribution | |
| CA1109582A (en) | Thermoplastic moulding compositions | |
| US5514750A (en) | Particulation of a metastable syrup | |
| CN115057972A (en) | Production process system of high-performance ABS resin and preparation method thereof | |
| CN115703904A (en) | High-heat-resistance polyethylene pipe composition and preparation method thereof | |
| US5973079A (en) | Large particle generation | |
| CN114917852B (en) | Method for continuously producing graphite expandable polystyrene by bulk method | |
| CN1150232C (en) | Making method of impact resistance resin composition | |
| CN217398798U (en) | Device for preparing ABS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |