CN114685721A - Device and method for preparing ABS - Google Patents
Device and method for preparing ABS Download PDFInfo
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- CN114685721A CN114685721A CN202210401999.5A CN202210401999A CN114685721A CN 114685721 A CN114685721 A CN 114685721A CN 202210401999 A CN202210401999 A CN 202210401999A CN 114685721 A CN114685721 A CN 114685721A
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- precontactor
- multistage
- acrylonitrile
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- 238000000034 method Methods 0.000 title claims abstract description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 76
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 49
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 39
- 239000003292 glue Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 24
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract description 8
- 229920001971 elastomer Polymers 0.000 claims description 60
- 239000005060 rubber Substances 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 54
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 21
- 239000012986 chain transfer agent Substances 0.000 claims description 20
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 230000009466 transformation Effects 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 238000004134 energy conservation Methods 0.000 claims 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 43
- 230000008569 process Effects 0.000 abstract description 10
- 238000010924 continuous production Methods 0.000 abstract description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 abstract 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 abstract 2
- 239000002994 raw material Substances 0.000 description 13
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 4
- -1 3, 5-di-t-butyl-4-hydroxyphenyl Chemical group 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to a device and a method for preparing ABS (acrylonitrile-butadiene-styrene), which comprises a pre-contactor 1, a pre-contactor 2, a multi-stage polymerizer and a tube array post-polymerizer, wherein the contactor 1 is connected with the pre-contactor 2, the pre-contactor 2 is connected with the multi-stage polymerizer, and the multi-stage polymerizer is connected with the tube array post-polymerizer; the precontactor 1 is used for mixing and contacting glue solution formed by mixing polybutadiene rubber and styrene with acrylonitrile and chemical auxiliaries to generate polymerization reaction; the precontactor 2 is used for mixing and contacting the discharge of the precontactor 1 with acrylonitrile and chemical additives to continuously generate polymerization reaction, or directly mixing and contacting the discharge of the precontactor 1 with the chemical additives to continuously generate polymerization reaction in the precontactor 2; the multistage polymerizer is used for continuously carrying out graft polymerization on the discharged material of the precontactor 2; the ABS resin produced by the invention has high impact strength, reduces the equipment investment amount, improves the process problems of unstable continuous production operation and the like, and has higher practical value.
Description
Technical Field
The invention belongs to the technical field of high polymer material resin, and particularly relates to a device and a method for preparing ABS.
Background
The ABS resin is styrene (C)8H8) Butadiene (C)4H6) And acrylonitrile (C)3H3N) is a thermoplastic polymer material with high strength, good toughness and easy processing and forming, and is widely applied to the fields of electronic appliances, automobile parts, toy consumables and the like. At present, the industrial production method of the ABS resin mainly comprises the following steps: emulsion graft-bulk SAN blending processes and continuous bulk polymerization processes. The products of the emulsion grafting-bulk SAN blending method have rich types and excellent performance, but the products have higher residual monomer content and large water consumption in the production process, and the subsequent addition of water treatment cost has great environmental pollution; the continuous body method is environment-friendly in process, high in product cleanliness, few in product types and low in impact strength. With the national requirement on enterprise environmental protection increasing, the industrialization of the emulsion grafting-bulk SAN blending method is increasingly limited, and the continuous bulk method gradually becomes the preferred process technology of a newly built device in China. Meanwhile, the research on the performances of raw material feeding, process operation parameter optimization, product impact strength improvement and the like is always a hot point for the research on the preparation of the ABS resin by a bulk method.
At present, domestic enterprises using a continuous bulk method to produce ABS resin comprise Shanghai Gaoqiao petrochemical industry, northern Huajin group and the like, most of the brands are general ABS products, the impact strength is low, and the requirements of high impact resistance and high glossiness of the ABS products in downstream high-end consumer markets are difficult to meet.
US2727884 and US3600535 disclose a process for the preparation of ABS using four plug flow reactors in series. The heat released by the polymerization reaction is taken away through a large amount of heat conducting oil circulation, the polybutadiene rubber, the styrene and the acrylonitrile monomer are preheated to the reaction temperature for reaction, the polymer after the reaction is sent to a devolatilization device, unreacted styrene and acrylonitrile monomer are flashed out, and the melted material is subjected to bracing and dicing to obtain an ABS resin finished product. The disadvantages of the plug flow reactor are complex structure, large processing difficulty and high equipment investment.
The invention patent CN1121443C of Japan Mitsui proposes a method for preparing a rubber-modified styrene resin composition, which adopts a continuous bulk polymerization device with four groups of complete mixing type reactors to prepare the rubber-modified styrene resin, and the technology is introduced in 1986 by the organic synthesis factory of China GmbH company to produce the continuous bulk ABS, non-crosslinked rubber is dissolved in styrene and acrylonitrile monomers, and is continuously added into four full mixing kettle reactors, prepolymerization is carried out in the first reactor to phase transformation, and then bulk polymerization is continuously carried out in the second, third and fourth reactors. The original design can produce 8 ABS product brands. However, since the technology is not mature, the product can only reach medium impact strength, the number of the brands is small, some auxiliary raw materials are required to be imported, and the device is basically only used for producing HIPS resin.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a device and a method for preparing ABS, which ensure that enough monomer copolymer is attached to rubber particles in the phase transition process in a mode of rubber, styrene and acrylonitrile split polymerization, are favorable for bimodal or multimodal distribution of rubber granularity, and improve higher surface gloss and higher toughness of ABS products; the ABS resin produced by the invention has high impact strength, reduces the equipment investment amount, improves the process problems of unstable continuous production operation and the like, and has higher practical value.
(II) technical scheme
The invention relates to a device for preparing ABS, which comprises a precontactor 1, a precontactor 2, a multistage polymerizer and a tubular postpolymerizer, wherein the contactor 1 is connected with the precontactor 2, the precontactor 2 is connected with the multistage polymerizer, and the multistage polymerizer is connected with the tubular postpolymerizer; the precontactor 1 is used for mixing and contacting glue solution formed by mixing polybutadiene rubber and styrene with acrylonitrile and chemical auxiliaries to generate polymerization reaction; the precontactor 2 is used for mixing and contacting the discharge of the precontactor 1 with acrylonitrile and chemical additives to continuously generate polymerization reaction, or directly mixing and contacting the discharge of the precontactor 1 with the chemical additives to continuously generate polymerization reaction in the precontactor 2; the multistage polymerizer is used for continuously carrying out graft polymerization on the discharged material of the precontactor 2; the tubular post-polymerizer can ensure that the conversion rate of the ABS reaches the expected requirement, and simultaneously ensures that the quality of the generated ABS product is stable.
According to the method for preparing ABS, the range values of all the fed components account for the total feeding amount and are respectively as follows: 15-20% of ethyl benzene, 8-13% of rubber, 5-20% of acrylonitrile and 50-65% of styrene, and chemical auxiliary agents: 0.01 to 0.03 percent of initiator, 0.05 to 0.3 percent of chain transfer agent and 0.15 to 0.3 percent of antioxidant; the rubber is polybutadiene rubber.
Wherein, acrylonitrile is divided into two parts and respectively enters the precontactor 1 and the precontactor 2;
the method comprises the following specific steps:
1) the polybutadiene rubber is crushed into rubber pieces, the rubber pieces, styrene and a diluent are mixed into a glue solution, the glue solution enters the precontactor 1 after being heated, and the heated glue solution is in mixed contact with the first strand of acrylonitrile, an initiator and an antioxidant; controlling the operating pressure of the precontactor 1 to be 0.8MPag and the stirring speed to be 20 rpm; the precontactor 1 is a full-mixing kettle reactor with a stirrer inside, the height-diameter ratio of the reactor is 2-3, the outer wall of the precontactor 1 adopts a jacket structure, the medium of a jacket layer is heat-conducting oil, and the heat emitted by the reaction is continuously taken away through the circulation of the heat-conducting oil; the polymerization conversion rate of the styrene and acrylonitrile monomers does not exceed the rubber content percentage, so that the rubber phase is still a continuous phase in the precontactor 1 and does not generate phase transition, meanwhile, the temperature of the reactor of the precontactor 1 is controlled to be constant, the heat released by the polymerization of the monomers just raises the temperature of the fed materials to the temperature required by the polymerization reaction, the balance of reaction heat release and feeding temperature rise and heat absorption is realized, and the medium in the jacket structure only plays a role in maintaining stability and finely adjusting the temperature of the reactor;
2) the glue solution from the pre-contactor 1 enters a pre-contactor 2, is mixed and contacted with another strand of acrylonitrile and a chain transfer agent, the reaction temperature is controlled at 110 ℃, the operation pressure is 0.78MPag, and the stirring speed is 30 rpm; the structural form of the precontactor 2 is the same as that of the precontactor 1, the height-diameter ratio of the precontactor 2 is 2.5-3.5, the outer wall of the precontactor adopts a jacket structure, the medium of a jacket layer is heat-conducting oil, and styrene continues to perform polymerization reaction with acrylonitrile monomers until phase transformation is completed; wherein, the acrylonitrile entering the precontactor 1 accounts for 80 percent of the total acrylonitrile flow, and the acrylonitrile entering the precontactor 2 accounts for 20 percent of the total acrylonitrile flow;
3) the precontactor 2 is connected with the multistage polymerizers 1 and the multistage polymerizers 2, the multistage polymerizers 1 and the multistage polymerizers 2 are plug flow reactors with stirrers inside, the outer walls of the multistage polymerizers 1 and the multistage polymerizers 2 adopt jacket structures, jacket media are heat conducting oil, and the two multistage polymerizers can be connected in series or in parallel; the reaction material which has completed the phase transition in the precontactor 2 enters a multistage polymerizer 1, the reaction material is mixed with a chain transfer agent and enters the multistage polymerizer 2, the operating temperature of the multistage polymerizer is 125-150 ℃, the operating pressure is 0.75MPag, and the stirring speed is 10 rpm; at the moment, rubber serving as a disperse phase is fully grafted, a large amount of monomer copolymer is grafted on the surface of rubber particles so as to improve the interface bonding force between the two phases, the internal temperature of the multistage polymerizer is in gradient distribution along the axial direction, and the heat released by the polymerization reaction is timely removed in a jacket cooling mode, so that the problems of insufficient power of stirring equipment and even damage to the reactor equipment caused by polymer implosion due to local excessive reaction are solved;
4) the materials from the multistage polymerizer enter a tubular postpolymerizer, the tubular postpolymerizer adopts the structural form of a tubular reactor, the materials are dispersed in each tubular at the tubular inlet, the contact area of the materials and the medium between the tubular pipes is better increased, the reaction heat is timely removed by the medium heat conducting oil between the tubular pipes, the temperature of the tubular postpolymerizer is controlled at 165-180 ℃, and the operating pressure is 0.62 Mpag; deepening the graft crosslinking of the rubber particles and the monomer copolymer; the post-polymerization device of the tube array can ensure that the conversion rate of the ABS reaches the expected requirement and ensure the stable quality of the produced ABS product.
The shell and tube reactor is also called tube bundle reactor; the device consists of a plurality of reaction tubes, and is a fixed bed reactor in which a catalyst can be filled; the structure of the device consists of a tube bundle, a shell and two end sockets; the heat required by the reaction is provided by flue gas and high-temperature steam outside the tube, or the heat released by the reaction is removed by molten salt heat conduction oil and water, so that the reaction temperature is maintained.
According to the method for preparing ABS, the range values of all the fed components account for the total feeding amount and are respectively as follows: 15-20% ethylbenzene, 8-13% rubber, 5-20% acrylonitrile and 50-65% styrene; chemical auxiliary agents: 0.01 to 0.03 percent of initiator, 0.05 to 0.3 percent of chain transfer agent and 0.15 to 0.3 percent of antioxidant;
wherein, acrylonitrile is added into the precontactor 1 at one time;
the method comprises the following specific steps:
1) polybutadiene rubber is crushed into rubber pieces, the rubber pieces, styrene and a diluent are mixed into a glue solution, the glue solution enters the precontactor 1 after being heated, and the heated glue solution is mixed and contacted with acrylonitrile, an initiator and an antioxidant; controlling the operating pressure of the precontactor 1 to be 0.8MPag and the stirring speed to be 20 rpm; the precontactor 1 is a full-mixing kettle reactor with a stirrer inside, the height-diameter ratio of the reactor is 2-3, the outer wall of the precontactor 1 adopts a jacket structure, the medium of a jacket layer is heat-conducting oil, and the heat emitted by the reaction is continuously taken away through the circulation of the heat-conducting oil; the polymerization conversion rate of styrene and acrylonitrile monomers does not exceed the rubber content percentage, so that a rubber phase is still a continuous phase in the precontactor 1 and does not generate phase transition, meanwhile, the temperature of the reactor of the precontactor 1 is controlled to be constant, the temperature of a fed material is just raised to the temperature required by polymerization reaction by heat released by monomer polymerization, the balance of reaction heat release and feeding temperature rise heat absorption is realized, and a medium in a jacket structure only plays a role in maintaining stability and finely adjusting the temperature of the reactor;
2) the glue solution from the pre-contactor 1 enters a pre-contactor 2 and is mixed and contacted with a chain transfer agent, the reaction temperature is controlled at 110 ℃, the operation pressure is 0.78MPag, and the stirring speed is 30 rpm; the structural form of the precontactor 2 is the same as that of the precontactor 1, the height-diameter ratio of the precontactor 2 is 2.5-3.5, the outer wall of the precontactor adopts a jacket structure, the medium of a jacket layer is heat-conducting oil, and styrene continues to perform polymerization reaction with acrylonitrile monomers until phase transformation is completed;
3) the precontactor 2 is connected with the multistage polymerizers 1 and the multistage polymerizers 2, the multistage polymerizers 1 and the multistage polymerizers 2 are plug flow reactors with stirrers inside, the outer walls of the multistage polymerizers 1 and the multistage polymerizers 2 adopt jacket structures, jacket media are heat conducting oil, and the two multistage polymerizers can be connected in series or in parallel; the reaction material which has completed the phase transition in the precontactor 2 enters a multistage polymerizer 1, the reaction material is mixed with a chain transfer agent and enters the multistage polymerizer 2, the operating temperature of the multistage polymerizer is 125-150 ℃, the operating pressure is 0.75MPag, and the stirring speed is 10 rpm; at the moment, rubber serving as a disperse phase is fully grafted, a large amount of monomer copolymer is grafted on the surface of rubber particles so as to improve the interface bonding force between the two phases, the internal temperature of the multistage polymerizer is in gradient distribution along the axial direction, and the heat released by the polymerization reaction is timely removed in a jacket cooling mode, so that the problems of insufficient power of stirring equipment and even damage to the reactor equipment caused by polymer implosion due to local excessive reaction are solved;
4) the materials from the multistage polymerizer enter a tubular postpolymerizer which adopts the structural form of a tubular reactor, the materials are dispersed in each tubular at the tubular inlet, the contact area of the materials and the media between the tubular pipes is better increased, the reaction heat is timely removed by the media heat transfer oil between the tubular pipes, the temperature of the tubular postpolymerizer is controlled at 165-180 ℃, and the operating pressure is 0.62 Mpag; deepening the graft crosslinking of the rubber particles and the monomer copolymer; the post-polymerization device of the tube array can ensure that the conversion rate of the ABS reaches the expected requirement and ensure the stable quality of the produced ABS product.
(III) advantageous effects
The invention has the advantages that:
1. according to the invention, by means of the stranded polymerization reaction of rubber, styrene and acrylonitrile, sufficient monomer copolymer is ensured to be attached to rubber particles in the phase transformation process, which is beneficial to the rubber particle size to be in bimodal or multimodal distribution, and the higher surface gloss and higher toughness of an ABS product are improved;
2. the invention controls the size and the distribution of the rubber particle diameter by setting the power stirring equipment in a grading way, and improves the shock resistance of the ABS product;
3. the invention reduces the circulation quantity of heat conducting oil of the device;
4. the invention optimizes the process flow and saves the investment.
Drawings
FIG. 1 is a schematic view of the overall structure of the present invention;
in the figure, 1, a precontactor 1; 2. a precontactor 2; 3. a multistage polymerizer 1; 4. a multistage polymerizer 2; 5. a tube array postpolymerizer;
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
As shown in figure 1:
the invention discloses a device for preparing ABS, which comprises a pre-contactor 1, a pre-contactor 2, a multi-stage polymerizer and a tube array post-polymerizer, wherein the contactor 1 is connected with the pre-contactor 2, the pre-contactor 2 is connected with the multi-stage polymerizer, and the multi-stage polymerizer is connected with the tube array post-polymerizer; the precontactor 1 is used for mixing and contacting a glue solution formed by mixing polybutadiene rubber and styrene with acrylonitrile and a chemical auxiliary agent to generate a polymerization reaction; the precontactor 2 is used for mixing and contacting the discharged material of the precontactor 1 with acrylonitrile and chemical additives to continuously generate polymerization reaction, or directly mixing and contacting the discharged material of the precontactor 1 with the chemical additives to continuously generate polymerization reaction; the multistage polymerizer is used for continuously carrying out graft polymerization on the discharged material of the precontactor 2; the tubular post-polymerizer can ensure that the conversion rate of the ABS reaches the expected requirement, and simultaneously ensure that the quality of the produced ABS product is stable.
Example 1
The acrylonitrile is divided into two parts and respectively enters a precontactor 1 and a precontactor 2;
raw materials (glue solution): rubber, styrene, acrylonitrile and ethylbenzene are used as diluents, and the content of each raw material in the glue solution is as follows: 10% of rubber, 65% of styrene, 9.37% of ethylbenzene and 15% of acrylonitrile; the total flow of the starting materials was 9000kg/h, the acrylonitrile being added twice in a ratio of 4: 1 is added into a pre-contactor 1 and a pre-contactor 2 respectively;
the amount of each auxiliary agent is as follows: an initiator (trade name: Trigonox 22-E-50) was contained in an amount of 0.03%, a chain transfer agent (chemical name: n-dodecylmercaptan) was contained in an amount of 0.3%, and an antioxidant (chemical name: 1-octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl)) was contained in an amount of 0.3%;
the raw materials and the auxiliary agent account for the percentage value of the total feeding amount;
feeding a glue solution containing rubber fragments with the particle size of 2-3mm, styrene and ethylbenzene into a precontactor 1, adding a first strand of acrylonitrile, an initiator and an antioxidant into the precontactor 1, controlling the temperature of the precontactor 1 at 100 ℃, the operating pressure at 0.8MPag, and the stirring speed at 20 rpm; discharging the materials into a precontactor 2, continuously adding a second strand of acrylonitrile and a chain transfer agent into the precontactor 2, controlling the reaction temperature at 110 ℃, the operation pressure at 0.78MPag and the stirring speed at 30 rpm; the discharge of the pre-contactor 2 enters a multi-stage polymerizer for continuous graft polymerization, the operating temperature of the multi-stage polymerizer is 125-150 ℃, the operating pressure is 0.75MPag, and the stirring speed is 10 rpm; feeding the material from the multistage polymerizer into a tubular post-polymerizer, wherein the operation temperature is 165 ℃ and the operation pressure is 0.62 MPag; the material enters the top of the tubular post-polymerizer, is uniformly dispersed in each tubular, and then the reaction material comes out from the bottom of the tubular post-polymerizer to obtain the ABS product.
The performance of the ABS resin obtained in example 1 was tested, and the rubber particle size was 1163nm, and the impact strength was 179.3J/m.
Example 2
Acrylonitrile is added to precontactor 1 in one portion without splitting.
Raw materials (glue solution): rubber, styrene, acrylonitrile and ethylbenzene are used as diluents, and the content of each raw material in the glue solution is as follows: 10% of rubber, 65% of styrene, 9.37% of ethylbenzene and 15% of acrylonitrile. The total flow rate of the raw materials is 9000 kg/h;
the amount of each auxiliary agent is as follows: an initiator (trade name: Trigonox 22-E-50) was contained in an amount of 0.03%, a chain transfer agent (chemical name: n-dodecylmercaptan) was contained in an amount of 0.3%, and an antioxidant (chemical name: 1-octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl)) was contained in an amount of 0.3%;
feeding a glue solution containing rubber fragments with the particle size of 2-3mm, styrene and ethylbenzene into a precontactor 1, adding acrylonitrile, an initiator and an antioxidant into the precontactor 1, controlling the temperature of the precontactor 1 at 100 ℃, the operating pressure at 0.8MPag and the stirring speed at 20 rpm; discharging the materials into a pre-contactor 2, continuously adding a chain transfer agent into the pre-contactor 2, controlling the reaction temperature at 110 ℃, controlling the operation pressure at 0.78MPag and controlling the stirring speed at 30 rpm; the discharged material of the precontactor 2 enters a multistage polymerizer for continuous graft polymerization, the operating temperature of the multistage polymerizer is 125-150 ℃, the operating pressure is 0.75MPag, and the stirring speed is 10 rpm; feeding the material from the multistage polymerizer into a tubular post-polymerizer, wherein the operation temperature is 165 ℃ and the operation pressure is 0.62 MPag; the materials enter the top of the tubular post-polymerizer, are uniformly dispersed in each tubular, and then are discharged from the bottom of the tubular post-polymerizer; obtaining the ABS product.
The ABS resin obtained in example 2 was tested for properties, and the rubber particle size was 1296nm and the impact strength was 148.1J/m.
Example 3
Acrylonitrile is divided into two parts and enters the precontactor 1 and the precontactor 2 respectively.
Raw materials (glue solution): rubber, styrene, acrylonitrile and ethylbenzene are used as diluents, and the content of each raw material in the glue solution is as follows: 13% of rubber, 65% of styrene, 11.37% of ethylbenzene and 10% of acrylonitrile. The total feed rate was 9000kg/h, where acrylonitrile was added twice in 4: 1 is added into a pre-contactor 1 and a pre-contactor 2 respectively;
the amount of each auxiliary agent is as follows: an initiator (trade name: Trigonox 22-E-50) was contained in an amount of 0.03%, a chain transfer agent (chemical name: n-dodecylmercaptan) was contained in an amount of 0.3%, and an antioxidant (chemical name: 1-octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl)) was contained in an amount of 0.3%;
feeding a glue solution containing rubber fragments with the particle size of 2-3mm, styrene and ethylbenzene into a precontactor 1, adding a first strand of acrylonitrile, an initiator and an antioxidant into the precontactor 1, controlling the temperature of the precontactor 1 at 100 ℃, the operating pressure at 0.8MPag, and the stirring speed at 20 rpm; discharging the materials into a precontactor 2, continuously adding a second strand of acrylonitrile and a chain transfer agent into the precontactor 2, controlling the reaction temperature at 110 ℃, the operation pressure at 0.78MPag and the stirring speed at 30 rpm; the discharged material of the precontactor 2 enters a multistage polymerizer for continuous graft polymerization, the operating temperature of the multistage polymerizer is 125-150 ℃, the operating pressure is 0.75MPag, and the stirring speed is 10 rpm; feeding the material from the multistage polymerizer into a tubular post-polymerizer, wherein the operation temperature is 165 ℃ and the operation pressure is 0.62 MPag; the material enters the top of the tubular post-polymerizer, is uniformly dispersed in each tubular, and then the ABS product is obtained from the reaction material coming out of the bottom of the tubular post-polymerizer.
The ABS resin obtained in the above example 3 was tested for properties, and the rubber particle size was 1198nm, and the impact strength was 186.2J/m.
Example 4
Acrylonitrile is added to precontactor 1 in one portion without splitting.
Raw materials (glue solution): rubber, styrene, acrylonitrile and ethylbenzene are used as diluents, and the content of each raw material in the glue solution is as follows: 13% of rubber, 65% of styrene, 11.37% of ethylbenzene and 10% of acrylonitrile. The total feed flow was 9000 kg/h;
the amount of each auxiliary agent is as follows: an initiator (trade name: Trigonox 22-E-50) was contained in an amount of 0.03%, a chain transfer agent (chemical name: n-dodecylmercaptan) was contained in an amount of 0.3%, and an antioxidant (chemical name: 1-octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl)) was contained in an amount of 0.3%;
feeding a glue solution containing rubber fragments with the particle size of 2-3mm, styrene and ethylbenzene into a precontactor 1, adding a first strand of acrylonitrile, an initiator and an antioxidant into the precontactor 1, controlling the temperature of the precontactor 1 at 100 ℃, the operating pressure at 0.8MPag, and the stirring speed at 20 rpm; discharging the materials into a precontactor 2, continuously adding a second strand of acrylonitrile and a chain transfer agent into the precontactor 2, controlling the reaction temperature at 110 ℃, the operation pressure at 0.78MPag and the stirring speed at 30 rpm; the discharge of the pre-contactor 2 enters a multi-stage polymerizer for continuous graft polymerization, the operating temperature of the multi-stage polymerizer is 125-150 ℃, the operating pressure is 0.75MPag, and the stirring speed is 10 rpm; feeding the material from the multistage polymerizer into a tubular post-polymerizer, wherein the operation temperature is 165 ℃ and the operation pressure is 0.62 MPag; the material enters the top of the tubular post-polymerizer, is uniformly dispersed in each tubular, and then the ABS product is obtained from the reaction material coming out of the bottom of the tubular post-polymerizer.
The ABS resin obtained in example 4 was tested for properties, and the rubber particle size was 1301nm, and the impact strength was 156.3J/m.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Rubber particle size nm | 1163 | 1296 | 1198 | 1301 |
| Impact strength J/m | 179.3 | 148.1 | 181.2 | 150.3 |
By combining the comparison of the examples, see table 1, the ABS resin prepared by adding acrylonitrile in a strand manner is superior to that prepared by adding acrylonitrile in a strand manner, and the performance of the ABS product is obviously improved, and on the basis of increasing the rubber content in examples 3 and 4, comparative examples 1 and 2 find that the impact strength in the product is increased but is not obvious, but the power consumption of equipment is increased along with the increase of the viscosity of the material, so that the device is more suitable for raw materials with about 10% of rubber content, and is a method and a system for preparing ABS with higher practical value.
Claims (3)
1. A device for preparing ABS comprises a precontactor 1, a precontactor 2, a multistage polymerizer and a tubular postpolymerizer, wherein the contactor 1 is connected with the precontactor 2, the precontactor 2 is connected with the multistage polymerizer, and the multistage polymerizer is connected with the tubular postpolymerizer; the precontactor 1 is used for mixing and contacting glue solution formed by mixing polybutadiene rubber and styrene with acrylonitrile and chemical auxiliaries to generate polymerization reaction; the precontactor 2 is used for mixing and contacting the discharge of the precontactor 1 with acrylonitrile and chemical additives to continuously generate polymerization reaction, or directly mixing and contacting the discharge of the precontactor 1 with the chemical additives to continuously generate polymerization reaction in the precontactor 2; the multistage polymerizer is used for continuously carrying out graft polymerization on the discharged material of the precontactor 2; the tubular post-polymerizer can ensure that the conversion rate of the ABS reaches the expected requirement, and simultaneously ensures that the quality of the generated ABS product is stable.
2. The method for preparing ABS according to claim 1, wherein:
the range values of the fed components are the values accounting for the total feeding amount, and are respectively as follows: 15-20% of ethyl benzene, 8-13% of rubber, 5-20% of acrylonitrile and 50-65% of styrene, and chemical auxiliary agents: 0.01 to 0.03 percent of initiator, 0.05 to 0.3 percent of chain transfer agent and 0.15 to 0.3 percent of antioxidant; wherein, acrylonitrile is divided into two parts and respectively enters the precontactor 1 and the precontactor 2; the method comprises the following specific steps:
1) the polybutadiene rubber is crushed into rubber pieces, the rubber pieces, styrene and a diluent are mixed into a glue solution, the glue solution enters the precontactor 1 after being heated, and the heated glue solution is in mixed contact with the first strand of acrylonitrile, an initiator and an antioxidant; controlling the operating pressure of the precontactor 1 to be 0.8MPag and the stirring speed to be 20 rpm; the precontactor 1 is a full-mixing kettle reactor with a stirrer inside, the height-diameter ratio of the reactor is 2-3, the precontactor 1 adopts a jacket structure, the medium in the jacket is heat-conducting oil, and the heat emitted by the reaction is continuously taken away through the circulation of the heat-conducting oil; the polymerization conversion rate of styrene and acrylonitrile monomers does not exceed the rubber content percentage, so that a rubber phase is still a continuous phase in the precontactor 1 and does not generate phase transition, and meanwhile, the reaction temperature of the precontactor 1 is controlled to be constant, the temperature of a fed material is just raised to the temperature required by polymerization reaction by heat released by monomer polymerization, the balance of reaction heat release and feeding temperature rise heat absorption is realized, a medium in a jacket structure only plays a role in maintaining stability and finely adjusting the temperature of the reactor, and the energy conservation is realized;
2) the glue solution from the pre-contactor 1 enters a pre-contactor 2, is mixed and contacted with another strand of acrylonitrile and a chain transfer agent, the reaction temperature is controlled at 110 ℃, the operation pressure is 0.78MPag, and the stirring speed is 30 rpm; the structure type of the precontactor 2 is the same as that of the precontactor 1, the height-diameter ratio of the precontactor 2 is 2.5-3.5, the outer wall of the precontactor adopts a jacket structure, the medium of a jacket layer is heat-conducting oil, and styrene continues to perform polymerization reaction with acrylonitrile monomers until phase transformation is completed; wherein, the acrylonitrile entering the precontactor 1 accounts for 80 percent of the total acrylonitrile flow, and the acrylonitrile entering the precontactor 2 accounts for 20 percent of the total acrylonitrile flow;
3) the precontactor 2 is connected with the multistage polymerizers 1 and the multistage polymerizers 2, the multistage polymerizers 1 and the multistage polymerizers 2 are plug flow reactors with stirrers inside, the outer walls of the multistage polymerizers 1 and the multistage polymerizers 2 adopt jacket structures, the medium in the jackets is heat conducting oil, and the two multistage polymerizers can be connected in series or in parallel; the reaction material which has completed the phase transition in the precontactor 2 enters a multistage polymerizer 1, the reaction material is mixed with a chain transfer agent and enters the multistage polymerizer 2, the operating temperature of the multistage polymerizer is 125-150 ℃, the operating pressure is 0.75MPag, and the stirring speed is 10 rpm; at the moment, rubber serving as a disperse phase is fully grafted, a large amount of monomer copolymer is grafted on the surface of rubber particles so as to improve the interface bonding force between the two phases, the internal temperature of the multistage polymerizer is in gradient distribution along the axial direction, and the heat released by the polymerization reaction is timely removed in a jacket cooling mode, so that the problems of insufficient power of stirring equipment and even damage to the reactor equipment caused by polymer implosion due to local excessive reaction are solved;
4) the materials from the multistage polymerizer enter a tubular postpolymerizer, the tubular postpolymerizer adopts the structural form of a tubular reactor, the materials are dispersed in each tubular at the tubular inlet, the contact area of the materials and the medium between the tubular pipes is better increased, the reaction heat is timely removed by the medium heat conducting oil between the tubular pipes, the temperature of the tubular postpolymerizer is controlled at 165-180 ℃, and the operating pressure is 0.62 MPag; deepening the graft crosslinking of the rubber particles and the monomer copolymer; the post-polymerization device of the tube array can ensure that the conversion rate of the ABS reaches the expected requirement and ensure the stable quality of the produced ABS product.
3. The method for preparing ABS according to claim 1, wherein:
the range values of the fed components are the values accounting for the total feeding amount, and are respectively as follows: 15-20% ethylbenzene, 8-13% rubber, 5-20% acrylonitrile and 50-65% styrene; chemical auxiliary agents: 0.01 to 0.03 percent of initiator, 0.05 to 0.3 percent of chain transfer agent and 0.15 to 0.3 percent of antioxidant; wherein, acrylonitrile is added into the precontactor 1 at one time; the method comprises the following specific steps:
1) polybutadiene rubber is crushed into rubber pieces, the rubber pieces, styrene and a diluent are mixed into a glue solution, the glue solution enters the precontactor 1 after being heated, and the heated glue solution is mixed and contacted with acrylonitrile, an initiator and an antioxidant; controlling the operating pressure of the precontactor 1 to be 0.8MPag and the stirring speed to be 20 rpm; the precontactor 1 is a full-mixing kettle reactor with a stirrer inside, the height-diameter ratio of the reactor is 2-3, the outer wall of the precontactor 1 adopts a jacket structure, the medium of a jacket layer is heat-conducting oil, and heat emitted by the reaction is continuously taken away through the circulation of the heat-conducting oil; the polymerization conversion rate of styrene and acrylonitrile monomers does not exceed the rubber content percentage, so that a rubber phase is still a continuous phase in the precontactor 1 and does not generate phase transition, meanwhile, the temperature of the reactor of the precontactor 1 is controlled to be constant, the temperature of a fed material is just raised to the temperature required by polymerization reaction by heat released by monomer polymerization, the balance of reaction heat release and feeding temperature rise heat absorption is realized, and a medium in a jacket structure only plays a role in maintaining stability and finely adjusting the temperature of the reactor;
2) the glue solution from the pre-contactor 1 enters a pre-contactor 2 and is mixed and contacted with a chain transfer agent, the reaction temperature is controlled at 110 ℃, the operation pressure is 0.78MPag, and the stirring speed is 30 rpm; the structural form of the precontactor 2 is the same as that of the precontactor 1, the height-diameter ratio of the precontactor 2 is 2.5-3.5, the outer wall of the precontactor adopts a jacket structure, the medium of a jacket layer is heat-conducting oil, and styrene continues to perform polymerization reaction with acrylonitrile monomers until phase transformation is completed; wherein, the acrylonitrile entering the precontactor 1 accounts for 80 percent of the total acrylonitrile flow, and the acrylonitrile entering the precontactor 2 accounts for 20 percent of the total acrylonitrile flow;
3) the precontactor 2 is connected with the multistage polymerizers 1 and the multistage polymerizers 2, the multistage polymerizers 1 and the multistage polymerizers 2 are plug flow reactors with stirrers inside, the outer walls of the multistage polymerizers 1 and the multistage polymerizers 2 adopt jacket structures, jacket media are heat conducting oil, and the two multistage polymerizers can be connected in series or in parallel; the reaction material which has completed the phase transition in the precontactor 2 enters a multistage polymerizer 1, the reaction material is mixed with a chain transfer agent and enters the multistage polymerizer 2, the operating temperature of the multistage polymerizer is 125-150 ℃, the operating pressure is 0.75MPag, and the stirring speed is 10 rpm; at the moment, rubber serving as a disperse phase is fully grafted, a large amount of monomer copolymer is grafted on the surface of rubber particles so as to improve the interface bonding force between the two phases, the internal temperature of the multistage polymerizer is in gradient distribution along the axial direction, and the heat released by the polymerization reaction is timely removed in a jacket cooling mode, so that the problems of insufficient power of stirring equipment and even damage to the reactor equipment caused by polymer implosion due to local excessive reaction are solved;
4) the materials from the multistage polymerizer enter a tubular postpolymerizer, the tubular postpolymerizer adopts the structural style of a tubular reactor, the materials are dispersed in each tubular at the tubular inlet, the contact area of the materials and the medium between the tubular pipes is better increased, the reaction heat is timely removed by the medium heat conducting oil between the tubular pipes, the temperature of the tubular postpolymerizer is controlled at 165-180 ℃, and the operating pressure is 0.62 Mpag; deepening the graft crosslinking of the rubber particles and the monomer copolymer; the post-polymerization device of the tube array can ensure that the conversion rate of the ABS reaches the expected requirement and ensure the stable quality of the produced ABS product.
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