CN115869892A - Polymerization system adopting prepolymerization and method for producing ABS resin by using polymerization system - Google Patents
Polymerization system adopting prepolymerization and method for producing ABS resin by using polymerization system Download PDFInfo
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- CN115869892A CN115869892A CN202211721494.3A CN202211721494A CN115869892A CN 115869892 A CN115869892 A CN 115869892A CN 202211721494 A CN202211721494 A CN 202211721494A CN 115869892 A CN115869892 A CN 115869892A
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Abstract
The application relates to a polymerization system adopting prepolymerization and a method for producing ABS resin by applying the polymerization system, belonging to the technical field of resin synthesis. The first to third plug flow reactors are connected in series at one side of the full mixing kettle reactor in sequence, and the discharge end of the fourth plug flow reactor is connected between the first plug flow reactor and the second plug flow reactor. The method for producing the ABS resin comprises the following steps: s1, cutting rubber, dissolving and uniformly mixing to obtain a raw rubber solution; s2, dividing the raw glue solution into two parts which are respectively input into a full-mixing kettle reactor and a fourth plug flow reactor; s3, outputting a final mixture from the third plug flow reactor; and S4, devolatilizing and granulating the final mixture to obtain the ABS resin. The ABS resin has the effects of improving the system stability and the single line production capacity, and simultaneously obtains the ABS resin with higher impact strength.
Description
Technical Field
The application relates to the technical field of resin synthesis, in particular to a prepolymerization polymerization system and a method for producing ABS resin by using the same.
Background
The ABS resin is a terpolymer of acrylonitrile, butadiene and styrene, and is a thermoplastic high polymer material with high strength, good toughness and easy processing and molding. ABS can be obtained by various polymerization methods such as emulsion grafting, emulsion blending, emulsion bulk polymerization, and continuous bulk polymerization. From the viewpoint of environmental protection and investment, the continuous bulk polymerization process is the best ABS production process at present.
Typical continuous bulk polymerization processes are: chemical (Dow) plug flow reactor series process, BASF (BASF) full-mixing kettle reactor series process, three-well east Asia (MTC) full-mixing kettle reactor series process, monsanto (Monsanto) vertical full-mixing kettle reactor and horizontal segmented constant pressure reactor series process, eny (ENI) plug flow reactor series process and 5 internationally neutralized plug flow reactor series-parallel process and the like. At present, the continuous bulk method industrialization device mainly adopts a series process technology of 4 plug flow reactors of a chemical company to produce ABS resin, and the single-line production capacity of the continuous bulk method industrialization device is 7 ten thousand tons/year at most.
U.S. Pat. No. 4,550,863A discloses a polymerization method of acrylonitrile-butadiene-styrene resin, wherein 5 plug flow reactors are arranged in the process flow, and a prepolymerization reactor is composed of 2 plug flow reactors connected in parallel and then connected in series with 3 plug flow reactors. The particle diameters of the rubber in 2 prepolymerization kettles are 0.05-1.50 μm and 0.065-1.95 μm respectively, and when low-cis rubber is adopted, the rubber content is 5%, the ethylbenzene content is 15%, the acrylonitrile content is 15%, and the styrene content is 65%, the prepared ABS resin has bimodal distribution, but the maximum impact strength is only 128J/m.
Compared with the emulsion grafting-bulk SAN blending process, the continuous bulk polymerization process has the main problems that the impact strength of the ABS resin is low, the single-line production capacity is low, and the market competitiveness of the ABS resin is low. In addition, the current continuous bulk polymerization method adopts series-parallel type plug flow reactors for production, the requirement on the mass transfer and heat transfer of the whole device is high, the plug flow reactors are difficult to amplify, the process fluctuation of each stage of plug flow reactors is large, the system stability of the whole device is poor, and potential safety hazards such as implosion exist.
Based on the current situation of an industrial device applied to the continuous bulk polymerization method for producing the ABS resin, the invention provides a production process for carrying out the continuous bulk polymerization method for the ABS resin by adopting a prepolymerization technology, which can solve the practical problems of poor overall system stability and low single-line production capacity of the device adopted by the current continuous bulk polymerization method.
Disclosure of Invention
In order to improve the system stability and single-line production capacity of a device for producing ABS resin by continuous bulk polymerization, the application provides a polymerization system adopting prepolymerization and a method for producing ABS resin by using the system.
In a first aspect, the present application provides a polymerization system using prepolymerization, using the following technical solution:
a polymerization system using prepolymerization comprising
A full-mixing kettle reactor, a reactor shell,
the first plug flow reactor is connected in series with one side of the full mixing kettle reactor;
the second plug flow reactor is connected in series with one side of the first plug flow reactor;
the third plug flow reactor is connected in series with one side of the second plug flow reactor;
the fourth plug flow reactor is connected in parallel with one side of the first plug flow reactor, and the discharge end of the fourth plug flow reactor is connected between the first plug flow reactor and the second plug flow reactor;
and a reflux pump is connected between the feed end of the fourth plug flow reactor and the fourth plug flow reactor.
Wherein the full-mixing kettle reactor comprises
The body of the machine is provided with a plurality of air holes,
the stirrer is arranged in the machine body and is arranged in a spiral belt manner;
and the outer edge of the stirrer is provided with a scraping blade used for abutting against the inner wall of the machine body.
Wherein, any one of the first plug flow reactor to the fourth plug flow reactor is divided into an upper section area, a middle section area and a lower section area for independent temperature control.
Wherein, any one of the first plug flow reactor to the fourth plug flow reactor adopts a structure of a multilayer heat exchange coil and a flat-pitch stirrer.
In a second aspect, the present application provides a method for producing an ABS resin, which employs the following technical solutions:
comprises the following steps
S1, cutting rubber, dissolving and uniformly mixing to obtain a raw rubber solution;
s2, taking one part of the crude rubber liquid as a first part, inputting the first part into a full-mixing kettle reactor, enabling the first part to sequentially pass through the full-mixing kettle reactor and a first plug flow reactor to form a first pre-polymerization rubber liquid, taking the other part of the crude rubber liquid as a second part, inputting the second part into a fourth plug flow reactor, and outputting a second pre-polymerization rubber liquid;
s3, mixing the first pre-polymerization glue solution and the second pre-polymerization glue solution at the feeding end of the second plug flow reactor, then sequentially entering the second plug flow reactor and the third plug flow reactor, and outputting a final mixture;
and S4, removing unreacted monomers and solvents in the final mixture, and granulating to obtain the ABS resin.
Wherein the rubber is low cis-polybutadiene rubber, the cis content is 35-40%, the gel content is less than or equal to 0.02% (wt), and the solution after the rubber is dissolved contains 8-15% of rubber, 50-65% of styrene, 12-25% of acrylonitrile and 15-25% of ethylbenzene.
In S2, taking required amount of raw rubber solution into a container, inputting the raw rubber solution into a full-mixing kettle reactor and a fourth plug flow reactor at different speeds, wherein the speed of inputting the raw rubber solution into the full-mixing kettle reactor is greater than the speed of inputting the raw rubber solution into the fourth plug flow reactor.
Wherein, in S2, the raw rubber solution is input into a full-mixing kettle reactor or a fourth plug flow reactor, and simultaneously, a chain transfer agent and an initiator are added. The initiator is at least one of a monofunctional organic peroxide initiator and a difunctional organic peroxide initiator.
Wherein the circulation volume of the reflux pump is 30% of the liquid holdup in the fourth plug flow reactor.
Compared with the prior art, the invention has at least one of the following beneficial technical effects:
1. compared with the traditional process which singly adopts a plug flow reactor, the invention has the advantages of good mass and heat transfer effect, high rubber grafting rate, easy amplification of a full-mixing kettle reactor, capability of reducing the wall sticking of a polymerization material, good system stability, long production cycle and the like;
2. the ABS resin obtained by the method disclosed by the invention has the characteristic of bimodal distribution, so that the ABS resin has higher impact strength;
3. because of the combination of the prepolymerization technology and the mono-functional and bifunctional organic peroxide initiators, the molecular weight and the production efficiency of the ABS resin can be improved, and the single-line production capacity can be improved by more than 10 percent.
Drawings
Fig. 1 is a schematic view of the overall structure of the polymerization system of the present application.
In the figure, 1, a full mixing kettle reactor; 2. a first plug flow reactor; 3. a second plug flow reactor; 4. a third plug flow reactor; 5. a fourth plug flow reactor; 51. a reflux pump.
Detailed Description
The present application is described in further detail below with reference to fig. 1.
The embodiment of the application discloses a polymerization system adopting prepolymerization and a method for producing ABS resin by using the polymerization system, wherein the polymerization system adopting prepolymerization comprises a full-mixing kettle reactor and four plug flow reactors, the plug flow reactors are uniformly divided into an upper section area, a middle section area and a lower section area for independent temperature control, and a multi-layer heat exchange coil pipe and a flat slurry stirrer structure are adopted.
The four plug flow reactors are named as a first plug flow reactor to a fourth plug flow reactor respectively.
The first plug flow reactor, the second plug flow reactor and the third plug flow reactor are connected in series in sequence at one side of the full mixing kettle reactor. A reflux pump is connected between the feed end of the fourth plug flow reactor and the fourth plug flow reactor, and the discharge end of the fourth plug flow reactor is connected between the first plug flow reactor and the second plug flow reactor.
Wherein, mix cauldron reactor entirely includes the organism and sets up in the inside agitator of organism, and the agitator is the spiral shell belt setting, and the outer fringe of agitator is provided with the doctor-bar that is used for butt organism inner wall.
Two examples will be given below to give a complete description of the implementation of the process for the production of ABS resins in the present application, the analytical methods in the following examples being as follows: the melt index of an ABS resin product is analyzed according to GB/T3682.1-2018, the impact strength of a simply supported beam is analyzed according to GB/T1043.1-2008, the Vicat softening temperature is analyzed according to GB/T1633-2000, the tensile strength is analyzed according to GB/T1040.2-2022, the Rockwell hardness is analyzed according to GB/T3398.2-2018, the molecular weight is determined by gel permeation chromatography, the solid content of a polymer is determined by an electrothermal drying oven drying method, and the conversion rate is calculated according to the solid content.
Example 1
S1, adding 30.5kg of ethylbenzene and 75.5kg of styrene into a rubber dissolving tank, starting a stirrer, uniformly stirring, adding 15.2kg of chopped Asahi Asaprene TM 720AX low-cis rubber into the rubber dissolving tank, dissolving for 6-8 hours under normal temperature stirring, adding 28.2kg of acrylonitrile and 3.3kg of butyl acrylate, and continuously stirring for 4-6 hours to obtain a crude rubber solution.
N-dodecyl mercaptan (NDM) is selected as a chain transfer agent and diluted by ethylbenzene to prepare a 10% chain transfer solution for later use.
1, 1-di-tert-butyl peroxycyclohexane (TACH) is selected as the only initiator and diluted by ethylbenzene to prepare 12% of initiation liquid for later use.
And S2, preheating the primary rubber solution to 85 ℃, dividing the primary rubber solution into a first part and a second part, inputting the first part into a full-mixing kettle reactor at the speed of 6.5kg/h, and simultaneously adding a chain transfer solution and an initiation solution. The addition rates of the chain transfer solution and the initiation solution were 90ml/h and 100ml/h, respectively, and the first prepolymerization cement solution was outputted from the second plug flow reactor. The temperature of the full mixing kettle reactor is controlled at 90 ℃, the rotating speed of the stirrer is controlled at 60rpm, and the conversion rate is controlled at 20%. The temperature of 3 zones in the first plug flow reactor was controlled at 110 deg.C, 115 deg.C and 121 deg.C, the stirrer speed was controlled at 40rpm, and the conversion was controlled at 40%.
The second part was fed into the fourth plug flow reactor at a rate of 3.5kg/h, while the chain transfer solution and the priming solution were fed at rates of 40ml/h and 45ml/h, respectively, and the second prepolymerized dope solution was output from the fourth plug flow reactor. Grafting and phase transition polymerization are carried out in the fourth plug flow reactor, the temperature of 3 zones is controlled at 112 ℃, 118 ℃ and 125 ℃ respectively, the rotating speed of a stirrer is controlled at 40rpm, and the conversion rate is controlled at 40%.
Wherein the volume of the full mixing kettle reactor is 6.5 liters, and the volume of the other 4 plug flow reactors is 4.5 liters. The circulation amount of the reflux pump was 30% of the liquid hold-up in the fourth plug flow reactor.
And S3, mixing the first pre-polymerization glue solution and the second pre-polymerization glue solution at the feeding end of the second plug flow reactor, sequentially entering the second plug flow reactor and the third plug flow reactor, and outputting a final mixture. The temperature of the 3 zones in the second plug flow reactor was controlled at 131 deg.C, 136 deg.C and 145 deg.C, the stirrer speed was controlled at 20rpm, and the conversion was controlled at 55%. The temperature of 3 zones in the third plug flow reactor was controlled at 153 deg.C, 159 deg.C and 167 deg.C, the stirrer speed was controlled at 5rpm, and the conversion was controlled at 70%.
And S4, removing the unreacted monomers and the solvent in the final mixture through devolatilization, and granulating through an extruder to obtain the ABS resin.
The ABS resin obtained by the above method was analyzed, and the results are shown in the following table.
| Analysis item | Test standard | Test conditions | Unit of | Test values |
| Melt flow rate | GB/T3682.1-2018 | 220℃/10kg | g/10min | 15 |
| Impact strength of simply supported beam | GB/T1043.1-2008 | 23 ℃/A notch | kJ/m2 | 21 |
| Tensile strength | GB/T1040.2-2006 | 50mm/min | MPa | 39 |
| Vicat softening temperature | GB/T1633-2000 | 50N，50℃/h | ℃ | 90 |
| Rockwell hardness | GB/T3398.2-2018 | R scale | 104 |
The test results in a third plug flow reactor with a solids content of 55.6%, a total conversion of approximately 69.5%, an ABS resin weight average molecular weight of 156800 (Mw), and an impact strength of 21kJ/m 2 。
Example 2
S1, 30.5kg of ethylbenzene and 75.5kg of styrene are taken to be put into a rubber dissolving tank, a stirrer is started and stirred uniformly, 15.2kg of chopped Asahi Asaprene TM 720AX low cis rubber is taken to be added into the rubber dissolving tank, after the mixture is stirred at normal temperature and dissolved for 6 to 8 hours, 28.2kg of acrylonitrile and 3.3kg of butyl acrylate are added, and then the mixture is stirred continuously for 4 to 6 hours to obtain a crude rubber solution.
N-dodecyl mercaptan (NDM) is selected as a chain transfer agent and diluted by ethylbenzene to prepare a 10% chain transfer solution for later use.
1, 1-di-tert-butyl peroxycyclohexane (TACH) is selected as a first initiator, diluted by ethylbenzene and prepared into a first 12 percent initiation solution for later use. Selecting the raw materials in a weight ratio of 4:6 mixture of mono-functional initiator tert-amyl peroxypivalate (TAPV) and bifunctional initiator TACH is used as the second initiator, and diluted with ethyl benzene to prepare 12% of second initiation liquid for later use.
And S2, preheating the primary rubber solution to 85 ℃, dividing the primary rubber solution into a first part and a second part, inputting the first part into a full-mixing kettle reactor at the speed of 6.5kg/h, and simultaneously adding a chain transfer solution and a second initiation solution. The feeding rates of the chain transfer liquid and the second initiation liquid are respectively 90ml/h and 110ml/h, and the first prepolymerization glue solution is output from the second plug flow reactor. The temperature of the full mixing kettle reactor is controlled at 92 ℃, the rotating speed of the stirrer is controlled at 60rpm, and the conversion rate is controlled at 22%. The temperature of 3 zones in the first plug flow reactor was controlled at 112 ℃, 118 ℃ and 124 ℃, respectively, the stirrer speed was controlled at 40rpm, and the conversion was controlled at 42%.
The second part was fed into the fourth plug flow reactor at a rate of 3.5kg/h, while feeding a chain transfer solution and a first initiation solution at rates of 40ml/h and 45ml/h, respectively, and a second prepolymerised cement solution was fed out of the fourth plug flow reactor. Grafting and phase transition polymerization are carried out in a fourth plug flow reactor, the temperature of 3 zones is respectively controlled at 113 ℃, 119 ℃ and 126 ℃, the rotating speed of a stirrer is controlled at 40rpm, and the conversion rate is controlled at 42%.
Wherein the volume of the full mixing kettle reactor is 6.5 liters, and the volume of the other 4 plug flow reactors is 4.5 liters. The circulation amount of the reflux pump was 30% of the liquid hold-up in the fourth plug flow reactor.
And S3, mixing the first pre-polymerization glue solution and the second pre-polymerization glue solution at the feeding end of the second plug flow reactor, sequentially entering the second plug flow reactor and the third plug flow reactor, and outputting a final mixture. The temperature of the 3 zones in the second plug flow reactor was controlled at 134 ℃, 139 ℃ and 149 ℃, the stirrer speed was controlled at 20rpm, and the conversion was controlled at 58%. The temperature of 3 zones in the third plug flow reactor was controlled at 156 deg.C, 165 deg.C and 173 deg.C, the stirrer speed was controlled at 4rpm, and the conversion was controlled at 75%.
And S4, removing the unreacted monomers and the solvent in the final mixture through devolatilization, and granulating through an extruder to obtain the ABS resin.
The ABS resin obtained by the above method was analyzed, and the results are shown in the following table.
| Analysis item | Test standard | Test conditions | Unit of | Test values |
| Melt flow rate | GB/T3682.1-2018 | 220℃/10kg | g/10min | 14 |
| Impact strength of simply supported beam | GB/T1043.1-2008 | 23 ℃/A notch | kJ/m2 | 23 |
| Tensile strength | GB/T1040.2-2006 | 50mm/min | MPa | 40 |
| Vicat softening temperature | GB/T1633-2000 | 50N，50℃/h | ℃ | 91 |
| Rockwell hardness | GB/T3398.2-2018 | R scale | 104 |
The test gave a solids content in the third plug flow reactor of 60.8%, an overall conversion of approximately 76%, a weight average molecular weight of the ABS resin product of 161800 (Mw), and an impact strength of 23kJ/m2.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: equivalent changes made according to the structure, shape and principle of the invention shall be covered by the protection scope of the invention.
Claims (9)
1. A polymerization system using prepolymerization, characterized in that: comprises that
A full-mixing kettle reactor, a reactor shell,
the first plug flow reactor is connected in series with one side of the full-mixing kettle reactor;
the second plug flow reactor is connected in series with one side of the first plug flow reactor;
the third plug flow reactor is connected in series with one side of the second plug flow reactor;
the fourth plug flow reactor is connected in parallel with one side of the first plug flow reactor, and the discharge end of the fourth plug flow reactor is connected between the first plug flow reactor and the second plug flow reactor;
and a reflux pump is connected between the feed end of the fourth plug flow reactor and the fourth plug flow reactor.
2. The polymerization system according to claim 1, wherein: the full-mixing kettle reactor comprises
The body of the machine is provided with a plurality of air holes,
the stirrer is arranged inside the machine body and is arranged in a spiral belt manner;
and the outer edge of the stirrer is provided with a scraping blade used for abutting against the inner wall of the machine body.
3. The polymerization system according to claim 1, wherein: and any one of the first plug flow reactor to the fourth plug flow reactor is divided into an upper section area, a middle section area and a lower section area for independent temperature control.
4. The polymerization system according to claim 1, wherein: and any one of the first plug flow reactor to the fourth plug flow reactor adopts a structure of a multilayer heat exchange coil and a slurry stirring device.
5. Use of a polymerization system employing prepolymerization according to any one of claims 1 to 4 and a process for producing an ABS resin using the same, characterized in that: comprises the following steps
S1, cutting rubber, dissolving and uniformly mixing to obtain a raw glue solution;
s2, taking one part of the raw glue solution as a first part, inputting the first part into a full-mixing kettle reactor, allowing the first part to sequentially pass through the full-mixing kettle reactor and a first plug flow reactor to form a first pre-polymerization glue solution, taking the other part of the raw glue solution as a second part, inputting the second part into a fourth plug flow reactor, and outputting a second pre-polymerization glue solution;
s3, mixing the first pre-polymerization glue solution and the second pre-polymerization glue solution at the feeding end of the second plug flow reactor, sequentially entering the second plug flow reactor and the third plug flow reactor, and outputting a final mixture;
and S4, removing unreacted monomers and solvents in the final mixture, and granulating to obtain the ABS resin.
6. The method of producing an ABS resin according to claim 5, characterized in that: the rubber is low cis-polybutadiene rubber, the cis content is 35-40%, and the gel content is less than or equal to 0.02% (wt); the solution after the rubber is dissolved contains 8-15% of rubber, 50-65% of styrene, 12-25% of acrylonitrile and 15-25% of ethylbenzene.
7. The method of producing an ABS resin according to claim 5, characterized in that: in S2, taking a required amount of raw rubber liquid into a container, and simultaneously inputting the raw rubber liquid into a full-mixing kettle reactor and a fourth plug flow reactor at different speeds, wherein the speed of inputting the raw rubber liquid into the full-mixing kettle reactor is greater than the speed of inputting the raw rubber liquid into the fourth plug flow reactor.
8. The method of producing an ABS resin according to claim 5, characterized in that: in S2, the raw glue solution is input into a full-mixing kettle reactor or a fourth plug flow reactor, and a chain transfer agent and an initiator are added at the same time.
9. The method of producing an ABS resin according to claim 8, characterized in that: the initiator is at least one of a monofunctional organic peroxide initiator and a difunctional organic peroxide initiator.
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