CN108948340B - Device and method for preparing aromatic polycarbonate - Google Patents
Device and method for preparing aromatic polycarbonate Download PDFInfo
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- CN108948340B CN108948340B CN201810570523.8A CN201810570523A CN108948340B CN 108948340 B CN108948340 B CN 108948340B CN 201810570523 A CN201810570523 A CN 201810570523A CN 108948340 B CN108948340 B CN 108948340B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
Abstract
The present invention provides an apparatus and a method for preparing an aromatic polycarbonate, comprising: a raw material batching tank; the transesterification reactor is connected with the raw material batching tank; a prepolymerization reactor connected with the transesterification reactor; the polycondensation reactor is characterized in that at least one independent stirring shaft is arranged on the feeding side and the discharging side of the polycondensation reactor respectively, and stirring paddles are arranged on the stirring shafts. The polycondensation reactor is provided with at least one independent stirring shaft on the feeding side and the discharging side respectively, the stirring shafts are provided with stirring paddles, stirring at different rotating speeds can be realized, materials with different viscosities on the feeding side and the discharging side are subjected to differential stirring control, and more accurate reaction control is realized on chain growth and molecular weight.
Description
Technical Field
The invention belongs to the technical field of polycarbonate preparation, and particularly relates to a device and a method for preparing aromatic polycarbonate by an ester exchange polycondensation method.
Background
The polycarbonate is engineering plastic with excellent comprehensive performance and is characterized in that: has transparency, excellent impact strength, heat resistance, cold resistance, dimensional stability, electrical insulation and the like. The method is widely applied to the fields of industry, agriculture, IT and daily necessities.
Polycarbonate (commonly known as PC) is a polymer having a main chain containing carbonate bonds and benzene ring structures, and has a molecular structural formula:
wherein R is an aromatic arylene group or an aliphatic alkylene group.
A common aromatic polycarbonate, bisphenol a polycarbonate, has the formula:
the industrial production methods of aromatic polycarbonates include phosgene interfacial polycondensation and melt transesterification polycondensation. The melt transesterification polycondensation method is further classified into a conventional melt transesterification method and a non-phosgene melt transesterification polycondensation method. Both the phosgene interfacial polycondensation process and the conventional melt transesterification process require the use of highly toxic phosgene as the starting material. Due to the increasing environmental protection pressure and the stricter requirements on occupational safety and sanitation, the research and development and the industrial development of a non-phosgene molten ester exchange method in the industry are rapid in recent years.
According to the published reports at home and abroad, the non-phosgene melt transesterification polycondensation method adopts the transesterification of diphenyl carbonate and bisphenol A. Undoubtedly, the transesterification polycondensation technology used by different manufacturers has basically the same reaction principle, and all have certain differences in certain engineering designs and process conditions.
The reaction for the preparation of polycarbonate using bisphenol A (BPA) and diphenyl carbonate (DPC) is as follows:
first step of
Second step of
The non-phosgene melt transesterification polycondensation process can be divided into two steps. Firstly, bisphenol A (BPA) and diphenyl carbonate (DPC) are subjected to ester exchange reaction to remove phenol to produce oligomers; in the second step, polycondensation is completed at high temperature and under high vacuum. The conventional process route adopts the processing sequence of ester exchange, multistage pre-polycondensation and polycondensation, and simultaneously, the vacuum degree needs to be strictly controlled in the processes of ester exchange, pre-polycondensation and polycondensation, and the generated phenol is removed in time.
The melt material viscosity change is big among the polycondensation process, and traditional technology polycondensation reactor only is provided with a (mixing) shaft, can not satisfy the optimum stirring rate of the different material of polycondensation reactor feed side and play material side viscosity simultaneously, can cause certain influence to the performance of final product, can not carry out the control of high accuracy to the final polymerization reaction.
Disclosure of Invention
The invention aims to provide a device and a process for preparing aromatic polycarbonate by an ester exchange polycondensation method.
Specifically, the invention provides the following technical scheme:
an apparatus for preparing an aromatic polycarbonate, comprising: a raw material batching tank; the ester exchange reactor 3 is connected with the raw material batching tank; a prepolymerization reactor connected to the transesterification reactor 3; and the polycondensation reactor 6 is connected with the prepolymerization reactor, and is characterized in that at least one independent stirring shaft is respectively arranged on the feeding side and the discharging side of the polycondensation reactor 6, and stirring paddles are arranged on the stirring shaft.
Preferably, in the above device, the raw material batching tank is at least two parallel first raw material batching tank 1 and second raw material batching tank 2.
Preferably, in the above apparatus, the raw material batching tank is provided with a diphenyl carbonate feed inlet and a bisphenol a feed inlet, and the bisphenol a feed inlet is connected to the dryer.
Preferably, in the above device, a candle filter 9 is arranged between the transesterification reactor 3 and the prepolymerization reactor, and the filter element precision of the candle filter 9 is preferably 10-100 microns.
Preferably, in the above apparatus, the prepolymerization reactor comprises a first prepolymerization reactor 4 and a first prepolymerization reactor 5 connected in series.
Preferably, in the above apparatus, the raw material batching tank is provided with an exhaust port.
In the above apparatus, it is preferable that the transesterification reactor 3, the prepolymerization reactor and the polycondensation reactor 6 are provided with exhaust ports.
Preferably, in the above apparatus, the polycondensation reactor 6 is connected to a pelletizer 10.
Preferably, in the above device, the discharge port of the granulator 10 is connected to an electrostatic precipitator 11.
Preferably, in the above apparatus, a first dynamic mixer 12 is disposed between the polycondensation reactor 6 and the granulator 10, a side line return line is disposed on a pipeline of the polycondensation reactor 6 connected to the first dynamic mixer 12, and a second dynamic mixer 13 is disposed on the side line return line; the second dynamic mixer 13 is provided with an additive inlet.
A method for producing an aromatic polycarbonate using the apparatus as described in any of the above, comprising the steps of:
a material preparation process: uniformly mixing bisphenol A and molten dimethyl carbonate in a raw material batching tank;
an ester exchange process: performing transesterification on the mixed raw materials in the transesterification reactor 3;
pre-polycondensation: carrying out pre-polycondensation reaction on the product of the transesterification reaction in the pre-polymerization reactor;
a polycondensation step: and carrying out polycondensation reaction on the product of the pre-polycondensation reaction in the polycondensation reactor 6 to obtain a polycarbonate product.
Preferably, in the above method, the bisphenol a is in a powder form, and is dried by the dryer and then enters the raw material batching tank.
In the above method, preferably, a transesterification catalyst is added in the transesterification step, and the transesterification catalyst is a nitrogen-containing basic compound, preferably tetramethylammonium hydroxide.
In another preferred scheme, an exhaust port is arranged on the raw material batching tank, the temperature of the raw material batching tank is maintained at 135-155 ℃, and an ester exchange catalyst is added in the batching process, wherein the ester exchange catalyst is a nitrogen-containing alkaline compound, preferably tetramethyl ammonium hydroxide.
Preferably, in any one of the above methods, a polycondensation catalyst is added in the polycondensation step, and the polycondensation catalyst is an acetylacetonato-based metal complex, preferably a lanthanide metal acetylacetonato compound.
Preferably, in any one of the above methods, the polycondensation reactor 6 is connected to a pelletizer 10, the discharge port of the pelletizer 10 is connected to an electrostatic precipitator 11, and the polycondensation process includes:
a granulation process: the polycarbonate melt obtained in the polycondensation step enters the granulator 10 for granulation, and a polycarbonate product with the required particle size is obtained as required;
a dust removal process: and the polycarbonate product obtained in the granulating procedure enters the electrostatic dust collector 11 for dust removal.
Preferably, in any one of the above methods, a first dynamic mixer 12 is disposed between the polycondensation reactor 6 and the granulator 10, a side line return line is disposed on a pipeline of the polycondensation reactor 6 connected to the first dynamic mixer 12, and a second dynamic mixer 13 is disposed on the side line return line; the second dynamic mixer 13 is provided with an additive inlet, and the polycondensation process and the granulation process comprise:
an additive blending procedure: a part of the polycarbonate product obtained in the polycondensation process directly enters the first dynamic mixer 12, and the other part of the polycarbonate product firstly enters the second dynamic mixer 13 through the side line return line to be mixed with additives and then enters the first dynamic mixer 12.
The invention has the beneficial effects that:
the polycondensation reactor is provided with at least one independent stirring shaft on the feeding side and the discharging side respectively, the stirring shafts are provided with stirring paddles, stirring at different rotating speeds can be realized, materials with different viscosities on the feeding side and the discharging side are subjected to differential stirring control, and more accurate reaction control is realized on chain growth and molecular weight.
Drawings
FIG. 1 is a flow chart of a process for producing an aromatic polycarbonate by an ester interchange polycondensation in example 1.
FIG. 2 is a flow chart of a process for producing an aromatic polycarbonate by an ester interchange polycondensation in example 2.
FIG. 3 is a flow chart of a process for producing an aromatic polycarbonate by an ester interchange polycondensation in example 3.
FIG. 4 is a flow chart of a process for producing an aromatic polycarbonate by an ester interchange polycondensation in example 4.
The designations in the figures illustrate the following: 1-a first raw material batching tank, 2-a second raw material batching tank, 3-an ester exchange reaction kettle, 4-a first pre-polymerization reactor, 5-a second pre-polymerization reactor, 6-a polycondensation reactor, 7-a first dryer, 8-a second dryer, 9-a candle filter, 10-a granulator, 11-an electrostatic precipitator, 12-a first dynamic mixer and 13-a second dynamic mixer.
Detailed Description
The invention aims to provide a device and a method for preparing aromatic polycarbonate by an ester exchange polycondensation method.
In a preferred embodiment of the present invention, the present invention provides an apparatus for producing an aromatic polycarbonate, comprising: a raw material batching tank; the ester exchange reactor 3 is connected with the raw material batching tank; a prepolymerization reactor connected to the transesterification reactor 3; and the polycondensation reactor 6 is connected with the prepolymerization reactor, and is characterized in that at least one independent stirring shaft is respectively arranged on the feeding side and the discharging side of the polycondensation reactor 6, and stirring paddles are arranged on the stirring shaft.
In a preferred embodiment of the invention, the raw material batching tank is at least two parallel-connected primary raw material batching tank 1 and secondary raw material batching tank 2.
The raw materials proportioning tank adopts the multi-thread parallel operation mode, effectively reduces batching trouble probability of stopping, improves device operating stability.
In a preferred embodiment of the present invention, the raw material batching tank is provided with a diphenyl carbonate feeding port and a bisphenol a feeding port, and the bisphenol a feeding port is connected with the dryer.
In a preferred embodiment of the present invention, a candle filter 9 is arranged between the transesterification reactor 3 and the prepolymerization reactor, and the candle filter 9 preferably has a filter element precision of 10-100 microns.
The candle filter is used for filtering impurity particles and agglomerated particles in the materials and preventing the materials from continuously reacting to form high molecular impurities.
In a preferred embodiment of the present invention, the prepolymerization reactor comprises a first prepolymerization reactor 4 and a first prepolymerization reactor 5 connected in series.
In a preferred embodiment of the present invention, the raw material batching tank is provided with an air outlet.
In a preferred embodiment of the present invention, the transesterification reactor 3, the prepolymerization reactor and the polycondensation reactor 6 are provided with exhaust ports.
In a preferred embodiment of the invention, the polycondensation reactor 6 is connected to a pelletizer 10.
In a preferred embodiment of the present invention, the discharge port of the pelletizer 10 is connected to an electrostatic precipitator 11.
In a preferred embodiment of the present invention, a first dynamic mixer 12 is disposed between the polycondensation reactor 6 and the pelletizer 10, a side line return line is disposed on a pipeline of the polycondensation reactor 6 connected to the first dynamic mixer 12, and a second dynamic mixer 13 is disposed on the side line return line; the second dynamic mixer 13 is provided with an additive inlet.
The present invention also provides a preferred method for preparing an aromatic polycarbonate using the apparatus, comprising the steps of:
a material preparation process: uniformly mixing bisphenol A and molten dimethyl carbonate in a raw material batching tank;
an ester exchange process: performing transesterification on the mixed raw materials in the transesterification reactor 3;
pre-polycondensation: carrying out pre-polycondensation reaction on the product of the transesterification reaction in the pre-polymerization reactor;
a polycondensation step: and carrying out polycondensation reaction on the product of the pre-polycondensation reaction in the polycondensation reactor 6 to obtain a polycarbonate product.
In a preferred embodiment of the present invention, the bisphenol a is in a powder form, and is dried by the dryer and then enters the raw material batching tank.
The bisphenol A powder is dried by nitrogen before being fed, the water content is controlled below 150ppm, the moisture carrying rate is effectively reduced, the oxidative discoloration of the material is reduced, and the product quality is improved.
In a preferred embodiment of the present invention, a transesterification catalyst is added to the transesterification step, and the transesterification catalyst is a nitrogen-containing basic compound, preferably tetramethylammonium hydroxide.
In another preferred embodiment of the present invention, the raw material batching tank is provided with an exhaust port, the temperature of the raw material batching tank is maintained at 135-155 ℃, and an ester exchange catalyst is added in the batching process, wherein the ester exchange catalyst is a nitrogen-containing basic compound, preferably tetramethyl ammonium hydroxide.
The transesterification catalyst is added in the batching procedure, meanwhile, the temperature of the raw material batching tank is maintained at 135-155 ℃, the transesterification pre-reaction at low temperature can be realized in the batching procedure, and the generated phenol is discharged through an exhaust port to promote the continuous proceeding of the reaction, thereby reducing the reaction residence time in the transesterification procedure and improving the conversion rate of the transesterification reaction.
In a preferred embodiment of the present invention, a polycondensation catalyst is added in the polycondensation step, and the polycondensation catalyst is an acetylacetone-based metal complex, preferably a lanthanide metal acetylacetone-based compound.
In a preferred embodiment of the present invention, the polycondensation reactor 6 is connected to a pelletizer 10, the discharge port of the pelletizer 10 is connected to an electrostatic precipitator 11, and the polycondensation process includes:
a granulation process: the polycarbonate melt obtained in the polycondensation step enters the granulator 10 for granulation, and a polycarbonate product with the required particle size is obtained as required;
a dust removal process: and the polycarbonate product obtained in the granulating procedure enters the electrostatic dust collector 11 for dust removal.
The granulated product particles can generate static electricity and dust in the conveying process, the electrostatic dust collector is arranged on the conveying pipeline, the static electricity of the product particles can be eliminated firstly, the dust on the surfaces of the product particles is removed through fed-back dry air, the dust content of the product particles is less than or equal to 300ppm, and a high-quality polycarbonate product is obtained.
In a preferred embodiment of the present invention, a first dynamic mixer 12 is disposed between the polycondensation reactor 6 and the pelletizer 10, a side line return line is disposed on a pipeline of the polycondensation reactor 6 connected to the first dynamic mixer 12, and a second dynamic mixer 13 is disposed on the side line return line; the second dynamic mixer 13 is provided with an additive inlet, and the polycondensation process and the granulation process comprise:
an additive blending procedure: a part of the polycarbonate product obtained in the polycondensation process directly enters the first dynamic mixer 12, and the other part of the polycarbonate product firstly enters the second dynamic mixer 13 through the side line return line to be mixed with additives and then enters the first dynamic mixer 12. The polycarbonate melt taken out for mixing with the additives amounts to 3-10% of the total polycarbonate melt.
The invention adopts a mode of firstly partially mixing and then fully mixing, namely a small strand of melt flow is branched from a main polycarbonate melt pipeline and sent to a first dynamic mixer to be mixed with the additive, and then the melt flow is sent back to a main melt pipeline to be fully mixed with the rest melt, so that the pressure drop can be effectively reduced, and the investment and the operation cost of the device can be reduced.
The aromatic bisphenol A polycarbonate prepared by the device and the method has the viscosity average molecular weight Mv of 20000-.
In order to facilitate understanding of the present invention, the apparatus and method for producing an aromatic polycarbonate according to the present invention will be further described with reference to the accompanying drawings and examples.
Example one
Referring to fig. 1, the present invention provides an apparatus for preparing an aromatic polycarbonate, which comprises: the device comprises a first raw material batching tank 1 and a second raw material batching tank 2 which are connected in parallel; the transesterification reactor 3 is connected with the first raw material batching tank 1 and the second raw material batching tank 2; a first prepolymerization reactor 4 and a second prepolymerization reactor 5 which are sequentially connected with the transesterification reactor 3; and the polycondensation reactor 6 is connected with the second prepolymerization reactor 5, wherein an independent stirring shaft is respectively arranged on the feeding side and the discharging side of the polycondensation reactor 6, and stirring paddles are arranged on the stirring shaft.
Wherein, be equipped with diphenyl carbonate feed inlet and bisphenol A feed inlet on the raw materials proportioning tank, the bisphenol A feed inlet and the first desicator 7 of first raw materials proportioning tank 1 are connected, the bisphenol A feed inlet and the second desicator 8 of second raw materials proportioning tank 2 are connected.
Wherein, a candle filter 9 is arranged between the ester exchange reactor 3 and the pre-polymerization reactor, and the filter element precision of the candle filter 9 is preferably 40 microns.
Wherein, the ester exchange reactor 3, the first pre-polymerization reactor 4, the second pre-polymerization reactor 5 and the polycondensation reactor 6 are all provided with exhaust ports.
Wherein, the polycondensation reactor 6 is connected with a granulator 10.
Wherein, the discharge hole of the granulator 10 is connected with an electrostatic dust collector 11.
Wherein, be equipped with dynamic mixer 12 between polycondensation reactor 6 and pelleter 10, be equipped with the additive entry on the dynamic mixer 12.
The process for producing an aromatic polycarbonate by using the above-mentioned apparatus is specifically described below, and specifically comprises the steps of:
a material mixing procedure: after being unpacked and metered, the bisphenol A solid powder enters a first dryer 7 and a second dryer 8, moisture and air carried by bisphenol A solid are sufficiently removed by using dry nitrogen, and then the bisphenol A solid powder and molten diphenyl carbonate are mixed in a ratio of 1: 1.06 mol ratio is introduced into the first raw material batching tank 1 and the second raw material batching tank 2 to be stirred and mixed evenly.
An ester exchange process: the mixed raw materials are sent into a transesterification reactor 3 through a fluid pump for carrying out the transesterification reaction, and simultaneously, a transesterification catalyst tetramethyl ammonium hydroxide is added, wherein the adding amount of the catalyst is 2 multiplied by 10-6mol/mol BPA. The temperature of the ester exchange reactor 3 is maintained at 130-160 ℃, the reaction pressure is maintained at 60-70KPa (A) by a vacuum system connected with an exhaust port, and the generated phenol is discharged from the exhaust port.
Pre-polycondensation: the melt material in the transesterification reactor 3 is filtered through a candle filter 9 and then enters the first prepolymerization reactor 4. The temperature of the first prepolymerization reactor 4 is maintained at 190 ℃ to 210 ℃, the reaction pressure is maintained at 20-35KPa (A) by a vacuum system connected with an exhaust port, and the generated phenol is discharged from the exhaust port. The melt material in the first pre-polymerization reactor 4 is pumped to the second pre-polymerization reactor 5 by a fluid pump, the temperature of the second pre-polymerization reactor 5 is maintained at 240-270 ℃, the reaction pressure is maintained at 3-8KPa (A) by a vacuum system connected with an exhaust port, and the generated phenol is discharged from the exhaust port.
A polycondensation step: the melt material in the second prepolymerization reactor 5 is pumped to a polycondensation reactor 6 by a fluid pump, and a polycondensation catalyst cerium acetylacetonate is added at the same time, wherein the addition amount of the catalyst is 5 multiplied by 10-6mol/mol BPA. The stirring speed of the feed side of the polycondensation reactor 6 was 10rpm, the stirring speed of the discharge side was 6rpm, the temperature was maintained at 270 ℃ and 295 ℃, the reaction pressure was maintained at 0.1 to 1.5KPa (A) by a vacuum system connected to the vent, and the produced phenol was discharged from the vent.
An additive blending procedure: the polycarbonate obtained in the polycondensation step is introduced into the dynamic mixer 12 and mixed with additives. In this example, the additive was BASF antioxidant rganox1076 added in an amount of 1500 ppm.
A granulation process: the polycarbonate obtained in the additive blending procedure is sent to a granulator 10 through a fluid pump for granulation, and a polycarbonate product with the required particle size is obtained according to the requirement.
A dust removal process: and the polycarbonate product obtained in the granulating procedure enters the electrostatic dust collector 11 for dust removal and then is sent out for packaging.
Example two
As shown in fig. 2, the difference between the second embodiment and the first embodiment is that the batching process is different: the first raw material batch tank 1 and the second raw material batch tank 2 of the third example were provided with exhaust ports, and the transesterification catalyst tetramethylammonium hydroxide was added to the first raw material batch tank 1 and the second raw material batch tank 2 in an amount of 2X 10-6mol/mol BPA. The temperature is maintained at 135-155 ℃, the pressure is maintained at 75-90KPa (A) by a vacuum system connected with an exhaust port, the raw materials undergo transesterification pre-reaction in the batching process, and the generated phenol is discharged from the exhaust port.
EXAMPLE III
As shown in fig. 3, the difference between the third example and the first example is in the additive blending step: in the third embodiment, a first dynamic mixer 12 is arranged between the polycondensation reactor 6 and the granulator 10, a side line return line is arranged on a pipeline connecting the polycondensation reactor 6 with the first dynamic mixer 12, a second dynamic mixer 13 is arranged on the side line return line, and an additive inlet is arranged on the second dynamic mixer 13; one part of the polycarbonate melt obtained in the third polycondensation step of the example directly enters the first dynamic mixer 12, the other part of the polycarbonate melt firstly enters the second dynamic mixer 13 through the side line return line to be mixed with the additives, then enters the first dynamic mixer 12 to be fully mixed, and the melt coming out of the first dynamic mixer 12 is sent to the granulation step.
In this example, the additive was BASF antioxidant rganox1076, and the polycarbonate melt taken for mixing with the additive accounted for 8% of the total polycarbonate melt and was added in an amount of 1500 ppm.
Example four
As shown in fig. 4, the fourth embodiment is different from the first embodiment in that:
(1) ingredientsDifferent in procedure, the first raw material batching tank 1 and the second raw material batching tank 2 of the fourth example are provided with exhaust ports, the ester exchange catalyst tetramethylammonium hydroxide is added into the first raw material batching tank 1 and the second raw material batching tank 2, and the addition amount of the catalyst is 2X 10-6mol/mol BPA. The temperature is maintained at 135-155 ℃, the pressure is maintained at 75-90KPa (A) by a vacuum system connected with an exhaust port, the raw materials undergo transesterification pre-reaction in the batching process, and the generated phenol is discharged from the exhaust port.
(2) Different in additive blending process, in the third embodiment, a first dynamic mixer 12 is arranged between the polycondensation reactor 6 and the granulator 10, a lateral line return line is arranged on a pipeline connecting the polycondensation reactor 6 with the first dynamic mixer 12, a second dynamic mixer 13 is arranged on the lateral line return line, and an additive inlet is arranged on the second dynamic mixer 13; one part of the polycarbonate melt obtained in the third polycondensation step of the example directly enters the first dynamic mixer 12, the other part of the polycarbonate melt firstly enters the second dynamic mixer 13 through the side line return line to be mixed with the additives, then enters the first dynamic mixer 12 to be fully mixed, and the melt coming out of the first dynamic mixer 12 is sent to the granulation step.
In this example, the additive was BASF antioxidant rganox1076, and the polycarbonate melt taken for mixing with the additive accounted for 8% of the total polycarbonate melt and was added in an amount of 1500 ppm.
Comparative example 1
The difference between the first comparative example and the first example is that the polycondensation step is different: comparative example-a polycondensation reactor was a uniaxial polycondensation reactor used in the conventional process.
In the above examples, the physical properties of the obtained polycarbonate were measured by the following methods:
viscosity average molecular weight Mv, weight average molecular weight Mw: polycarbonate samples were analyzed by GPC chromatography using chloroform as the solvent at room temperature, and the calibration parameter K was 14.1000 and α was 0.7000.
Content of branched matter: hydrolyzing a polycarbonate sample under alkaline conditions, and performing high performance chromatography analysis on the hydrolysate (shown as formula 1) by using an HPLC chromatograph to determine the content of the branched substances.
Melt index: the measurement is carried out by a melt flow rate meter, and the required data are measured after the polycarbonate sample is heated to 300 ℃ according to the mass method in GB/T3682 or ISO 3311.
Hue index: the absorbance A of polycarbonate in methylene chloride (1g/10mL) was measured at a wavelength of 380nm and an absorption cell length of 10nm using a Hitachi UV-160A UV spectrophotometer380Deducting its absorbance A at 580nm580The degree of coloration of the polycarbonate was evaluated, namely: hue index ═ A380-A580。
The experiments of examples 1 to 4 and comparative example 1 described above were each carried out 3 times to determine the average value of each index of the product, as specifically shown in table 1.
Table 1 shows the results of measurements of the production cycle of the apparatus, the energy consumption of the product, and various physical indicators (viscosity-average molecular weight, weight-average molecular weight, content of branched substances, melt index, Hue index) of the product in examples 1 to 4 and comparative example 1.
TABLE 1
As is clear from Table 1, in comparison with comparative example 1, the polycondensation reactors of examples 1 to 4 of the present invention were biaxial polycondensation reactors, and when the differential stirring control was performed on the materials having different viscosities on the feed side and the discharge side, the viscosity-average molecular weight and the weight-average molecular weight of the polycarbonate increased, and the content of the branched matter in the product decreased.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (21)
1. A method for producing an aromatic polycarbonate using an apparatus for producing an aromatic polycarbonate, the apparatus comprising:
a raw material batching tank; the ester exchange reactor (3) is connected with the raw material batching tank; a prepolymerization reactor connected with the transesterification reactor (3); the polycondensation reactor (6) is connected with the prepolymerization reactor, and is characterized in that the polycondensation reactor (6) is connected with a granulator (10), at least one independent stirring shaft is respectively arranged on the feeding side and the discharging side of the polycondensation reactor (6), and stirring paddles are arranged on the stirring shaft; a first dynamic mixer (12) is arranged between the polycondensation reactor (6) and the granulator (10), a lateral line return pipeline is arranged on a pipeline of the polycondensation reactor (6) connected with the first dynamic mixer (12), a second dynamic mixer (13) is arranged on the lateral line return pipeline, an additive inlet is arranged on the second dynamic mixer (13), an outlet of the second dynamic mixer (13) is arranged in front of the first dynamic mixer (12), and materials of the second dynamic mixer (13) enter the first dynamic mixer (12);
wherein the method for preparing the aromatic polycarbonate comprises the following steps:
a material preparation process: uniformly mixing bisphenol A and the melted diphenyl carbonate in a raw material batching tank;
an ester exchange process: carrying out transesterification reaction on the mixed raw materials in the transesterification reactor (3);
pre-polycondensation: carrying out pre-polycondensation reaction on the product of the transesterification reaction in the pre-polymerization reactor;
a polycondensation step: carrying out polycondensation reaction on the product of the pre-polycondensation reaction in the polycondensation reactor (6) to obtain a polycarbonate product;
wherein, pelleter (10) is connected in polycondensation reactor (6), electrostatic precipitator (11) is connected to pelleter (10) discharge gate, include after the polycondensation process:
a granulation process: the polycarbonate melt obtained in the polycondensation process enters the granulator (10) for granulation, and a polycarbonate product with the required particle size is obtained according to the requirement;
a dust removal process: the polycarbonate product obtained in the granulating procedure enters the electrostatic dust collector (11) for dust collection;
a first dynamic mixer (12) is arranged between the polycondensation reactor (6) and the granulator (10), a lateral line return pipeline is arranged on a pipeline of the polycondensation reactor (6) connected with the first dynamic mixer (12), and a second dynamic mixer (13) is arranged on the lateral line return pipeline; an additive inlet is arranged on the second dynamic mixer (13), and the polycondensation process and the granulation process comprise the following steps:
an additive blending procedure: one part of the polycarbonate product obtained in the polycondensation process directly enters the first dynamic mixer (12), the other part of the polycarbonate product firstly enters the second dynamic mixer (13) through the side line return line to be mixed with additives and then enters the first dynamic mixer (12), and the polycarbonate melt used for mixing with the additives accounts for 3-10% of the total polycarbonate melt amount.
2. The method according to claim 1, wherein the raw material dosing tank is at least two parallel connected primary (1) and secondary (2) raw material dosing tanks.
3. The method of claim 1, wherein the raw material batching tank is provided with a diphenyl carbonate feed inlet and a bisphenol A feed inlet, and the bisphenol A feed inlet is connected with a dryer.
4. The method of claim 2, wherein the raw material batching tank is provided with a diphenyl carbonate feed inlet and a bisphenol A feed inlet, and the bisphenol A feed inlet is connected with a dryer.
5. The process according to claim 1, wherein a candle filter (9) is provided between the transesterification reactor (3) and the prepolymerization reactor, the candle filter (9) having a cartridge precision of 10-100 microns.
6. The process according to claim 1, wherein the prepolymerization reactor comprises a first prepolymerization reactor (4) and a second prepolymerization reactor (5) connected in series.
7. The process according to claim 4, wherein the prepolymerization reactor comprises a first prepolymerization reactor (4) and a second prepolymerization reactor (5) connected in series.
8. The process according to claim 5, wherein the prepolymerization reactor comprises a first prepolymerization reactor (4) and a second prepolymerization reactor (5) connected in series.
9. The method of claim 4, wherein the raw material batching tank is provided with an air vent.
10. The method of claim 7, wherein the raw material batching tank is provided with an air vent.
11. The process according to claim 1, wherein the transesterification reactor (3), the prepolymerization reactor and the polycondensation reactor (6) are each provided with a vent.
12. The method according to claim 1, wherein the discharge port of the pelletizer (10) is connected with an electrostatic precipitator (11).
13. The method according to claim 11, wherein the discharge port of the pelletizer (10) is connected to an electrostatic precipitator (11).
14. The method of claim 2, wherein the discharge port of the pelletizer (10) is connected to an electrostatic precipitator (11).
15. The method of any one of claims 1-14, wherein the bisphenol a is in powder form and is dried by the dryer before entering the raw material batching tank.
16. The method according to any one of claims 1 to 14, wherein a transesterification catalyst is added in the transesterification process, and the transesterification catalyst is a nitrogen-containing basic compound.
17. The method of claim 16, wherein the nitrogen-containing basic compound is tetramethylammonium hydroxide.
18. The method as claimed in claim 1 or 2, wherein the raw material batching tank is provided with an exhaust port, the temperature of the raw material batching tank is maintained at 135-155 ℃, and an ester exchange catalyst is added in the batching process, wherein the ester exchange catalyst is a nitrogen-containing basic compound.
19. The method of claim 18, wherein the nitrogen-containing basic compound is tetramethylammonium hydroxide.
20. The method according to claim 1 or 2, wherein a polycondensation catalyst is added in the polycondensation process, and the polycondensation catalyst is an acetylacetonato-based metal complex.
21. The method of claim 20, wherein the acetylacetonate-based metal complex is a lanthanide metal acetylacetonate-based compound.
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