CN105291297B - A kind of polycarbonate production system - Google Patents
A kind of polycarbonate production system Download PDFInfo
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- CN105291297B CN105291297B CN201510811619.5A CN201510811619A CN105291297B CN 105291297 B CN105291297 B CN 105291297B CN 201510811619 A CN201510811619 A CN 201510811619A CN 105291297 B CN105291297 B CN 105291297B
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Abstract
A kind of polycarbonate production system; including devolatilization granulating system; the devolatilization granulating system includes twin-screw devolatilization extruder, comminutor and cistern, and the twin-screw devolatilization extruder is connected with comminutor, and the particle delivery outlet of the comminutor is immersed under the liquid level of cistern.During makrolon is granulated, since the particle of defeated makrolon is at this time also in higher temperature, so substantial amounts of hydroxyaryl reaction product still can be volatilized, and the hydroxyaryl reaction product that twin-screw devolatilization extruder can be volatilized while makrolon is extruded sponges.And the particle delivery outlet of comminutor is located at the underwater of cistern, due to the cooling effect of cooling water so after particle exports, so particle can shape quickly; simultaneously; in the case where being quickly cooled down, the ester bond in particle combines more secured, so as to the rigidity reinforced of particle.Furthermore cooling water can also absorb hydroxyaryl reaction product, it is avoided to enter in air.
Description
Technical field
The present invention relates to chemical field more particularly to a kind of polycarbonate production systems.
Background technology
Makrolon (abbreviation PC) is the high molecular polymer containing carbonate group in strand, can according to the structure of ester group
It is divided into the polytypes such as aliphatic, aromatic series, aliphatic-aromatic.Wherein due to aliphatic and the poly- carbonic acid of aliphatic-aromatic
The mechanical performance of ester is relatively low, so as to limit its application in terms of engineering plastics.Only aromatic copolycarbonate obtains at present
Industrialized production.It is most fast as growth rate in five large-engineering plastics due to the particularity on polycarbonate structure
General engineering plastic.
Such as the Chinese patent of Application No. 201280016769.1《The manufacturing method of makrolon and makrolon
Grain》A kind of manufacturing method of makrolon is disclosed, which uses the specific dihydroxy chemical combination with-CH2-O- structures
Object manufactures makrolon as raw material, and thermal stability is low compared with the bisphenols of the raw material in the past as makrolon, can be with
Solve the problems, such as described above multiple, the object of the invention further relates to a kind of manufacturing method, can be with stable quality and high finished product
Manufacture to rate the makrolon with characteristics such as excellent tones and mechanical performance.
But it is mainly what is carried out in normal atmospheric environment in granulation process, so often being distributed into air
Go out substantial amounts of hydroxyaryl reaction product, thus cause serious environmental pollution, serious danger is caused to the body of staff
Evil.
The content of the invention
In view of the deficiencies of the prior art, the present invention intends to provide can produce it is a kind of low in the pollution of the environment
Polycarbonate production system.
A kind of polycarbonate production system, including devolatilization granulating system, the devolatilization granulating system includes twin-screw devolatilization
Extruder, comminutor and cistern, the twin-screw devolatilization extruder are connected with comminutor, the particle output of the comminutor
Mouth is immersed under the liquid level of cistern.
Preferably, the devolatilization extruder is connected with vacuum system, the vacuum system is communicated with multi-stage condensing device, more
Grade condenser is connected with ground flare combustion system.
Preferably, the liquid in the cistern is the ethanol-water solution of 5.3%~5.7% (volume), cistern
Air on the water surface is connected with vacuum system.
Preferably, the twin-screw devolatilization extruder is connected with the horizontal disc polycondensation reactor of hydraulic-driven.
Preferably, the horizontal disc polycondensation reactor of the hydraulic-driven is connected with the Prepolycondensating reactor of autoclave, institute
The Prepolycondensating reactor and the first transesterification reactor, the second transesterification reactor for stating autoclave are respectively communicated with.
Preferably, the horizontal disc polycondensation reactor, Prepolycondensating reactor, the first transesterification reactor and the second ester
Exchange reactor is connected with vacuum system.
Preferably, first raw material blending tank of first transesterification reactor with being connected with bisphenol-A and dimethyl oxalate
Connection, second transesterification reactor are connected with being connected with the second raw material blending tank of isobide and dimethyl oxalate.
Preferably, it is added in through acetated in first transesterification reactor and the second transesterification reactor
18%MoO3/ 6%TiO2-SiO2Catalyst.
Preferably, the temperature of the first raw material blending tank and the second raw material blending tank is controlled at 54 DEG C~59 DEG C,
Pressure is controlled in 100kPa~120kPa.
Preferably, the material for the pipeline being connected with above-mentioned all reactors is at least one in 316Ti or 316L
Kind.
Present invention tool has the advantage that：During makrolon is granulated, due to the particle of defeated makrolon
At this time also in higher temperature, so substantial amounts of hydroxyaryl reaction product still can be volatilized, and twin-screw devolatilization squeezes out
The hydroxyaryl reaction product that machine can be volatilized while makrolon is extruded sponges.And the particle output of comminutor
Mouth is located at the underwater of cistern, so due to the cooling effect of cooling water after particle exports, so particle can be determined quickly
Shape, meanwhile, in the case where being quickly cooled down, the ester bond in particle combines more secured, so as to the rigidity reinforced of particle.Again
Person, cooling water can also absorb hydroxyaryl reaction product, it avoided to enter in air.So further ensure environment not
Contaminated possibility.
Meanwhile twin-screw devolatilization extruder and cistern are all connected with vacuum system, it will by the effect of vacuum system
Hydroxyaryl reaction product sponges rapidly caused by the two, and vacuum system is also associated with multi-stage condensing device and ground fire
Torch combustion system so can be quickly cooled to liquid by the reactant that vacuum system absorbs, and then pass to ground flare burning
It burns in system, so as to avoid the health of the pollution of air, also guarantee staff.
And the horizontal disc polycondensation reactor of hydraulic-driven can make prepolymerization reaction object be polycondensed into polycarbonate melt, this
Sample can improve the reaction rate of polycondensation reaction in the molten state.
Secondly, the Prepolycondensating reactor of autoclave is by the first transesterification reactor and the reaction product of the second transesterification reactor
Mixing carries out prepolymerization reaction, and the molecule of isobide is so just embedded in the strand of bisphenol A polycarbonate, so as to
The copolymer makrolon arrived has stronger degradation capability, avoids it and is retained for a long time caused by environment in natural environment
Pollution.
In addition, the 18%MoO handled through acetic acid is added in during esterification3/ 6%TiO2-SiO2Catalyst can
The rate of esterification is greatly improved, and then improves the production efficiency of whole makrolon.And by the first raw material blending tank and
The temperature of second raw material blending tank is controlled at 54 DEG C~59 DEG C, be since dimethyl oxalate is molten condition at such a temperature, and
The dimethyl oxalate of the molten condition is a kind of good solvent, so as to which effectively bisphenol-A and isobide are dissolved, this
Sample is completed to save the substantial amounts of energy again while dissolution of raw material in the environment of low temperature, improves the entirety of polycarbonate production
Benefit.
Finally, pipeline is manufactured at least one of 316Ti or 316L, the anticorrosive energy of pipeline can be effectively improved
Power extends the service life of entire polycarbonate production system.
Description of the drawings
Fig. 1 is a kind of polycarbonate production system schematic.
In figure：1st, twin-screw devolatilization extruder；2nd, comminutor；2.1st, cistern；3rd, horizontal disc polycondensation reactor；4th, it is pre-
Polycondensation reactor；5th, vacuum system；6th, multi-stage condensing device；7th, ground flare combustion system；8th, first esterification reactor；9th, second
Esterifier；10th, the first raw material blending tank；11st, the second raw material blending tank；12nd, reflux pump.
Specific embodiment
The embodiment of the present invention is described further with reference to Fig. 1.
A kind of polycarbonate production system, including devolatilization granulating system, devolatilization granulating system is squeezed out including twin-screw devolatilization
Machine 1, comminutor 2 and cistern 2.1, the delivery outlet of twin-screw devolatilization extruder 1 are connected with the input port of comminutor 2, are granulated
The delivery outlet of machine 2 is immersed under the liquid level of cistern 2.1.Due to makrolon from twin-screw devolatilization extruder 1 be extruded after by
Appoint in temperature at this time in 265 DEG C~305 DEG C, be carried over so having substantial amounts of hydroxyaryl reaction product at this time, and it is double
Screw rod devolatilization extruder 1 is connected with a vacuum system 5, and vacuum system 5 can extract the air in twin-screw devolatilization extruder 1,
So as to which the hydroxyaryl reaction product that ensure that volatilization can be detached rapidly by vacuum system 5 from twin-screw devolatilization extruder 1
Out, it is avoided to pollute the environment into air.
Meanwhile the liquid in cistern 2.1 is ethanol-water solution, wherein the alcohol volume content in solution for 5.3%~
5.7%, it is preferably the ethanol-water solution that alcohol volume content is 5.4%.It on the one hand can be generated using the solution with absorbing particles
When the volatile hydroxyaryl reactant taken out of, on the other hand, reduce what makrolon dissolved in ethanol-water solution
Amount.As described in table one,
Table one, the ethanol-water solution of 10min different volumes contents are to the hydroxyaryl reactant that is discharged from cistern 2.1
And the influence of the quality of makrolon
By table one as it can be seen that the volume content of ethyl alcohol is when 5.4% in ethanol-water solution, hydroxyaryl reaction production
The amount that object is released from cistern 2.1 has met the environmental protection standard of national regulation, while makrolon is in the solution
The amount of loss is also relatively fewer, thus the solution that 5.4% (volume) ethanol-water solution is selected to make in cistern 2.1 is relatively to be preferred
's.
Meanwhile the ullage of cistern 2.1 is connected in closed state, and with vacuum system 5.Thus from
The hydroxyaryl reaction product released in cistern 2.1 can be detached by vacuum system 5 in time, avoided it and be leaked to ring
It is polluted the environment in border.
Twin-screw devolatilization extruder 1 is connected with the horizontal disc polycondensation reactor 3 of hydraulic-driven, horizontal disc polycondensation reaction
3 pressure of device is 0.03kPa~3kPa, and temperature is 265 DEG C~305 DEG C.From horizontal disc polycondensation reactor 3 precondensation can be made anti-
Object is answered to be polycondensed into polycarbonate melt, can so improve the reaction rate of polycondensation reaction in the molten state.
And horizontal disc polycondensation reactor 3 is connected with the Prepolycondensating reactor 4 of autoclave, 4 pressure of Prepolycondensating reactor is
1kPa~15kPa, temperature are 240 DEG C~280 DEG C.It can be enhanced in advance by carrying out prepolymerization reaction to the product through esterification
The length of strand improves the reaction efficiency of polycondensation reaction, meanwhile, it can be maintained at molecular weight during prepolymerization reaction
Between 500 to 700, can so there be larger gap to avoid the molecular chain length of final product, so as to ensure that the poly- of production
Carbonic ester possesses relatively stable rigidity on the whole.
Prepolycondensating reactor 4 is communicated with 8 and second esterifier 9 of first esterification reactor, the first transesterification reactor
It is connected with the first raw material blending tank 10 for being connected with bisphenol-A and dimethyl oxalate, second transesterification reactor is with being connected with different mountain
Pears alcohol is connected with the second raw material blending tank 11 of dimethyl oxalate, here the quantity and raw material of esterifier and raw material blending tank
Material in blending tank can be determined according to actual conditions.
Here the temperature of the first raw material blending tank 10 and the second raw material blending tank 11 control is at 54 DEG C~59 DEG C, pressure control
System is primarily due to the dimethyl oxalate in the case of 54 DEG C here in 100kPa~120kPa to melt, meanwhile,
Bisphenol-A and isobide at this temperature and pressure the solubility in the dimethyl oxalate of molten condition for 85.1g/DMO and
87.4/DMO.Fusing of the high temperature to bisphenol-A and isobide is thus avoided significantly, reduces the input of the energy.
When the mixture in the first raw material blending tank 10 enters 8 and second raw material blending tank 11 of first esterification reactor
Mixture when enter in the second esterifier 9, put into 18%MoO into two esterifiers3/ 6%TiO2-
SiO2Catalyst.Catalyst used is MoO3/TiO2-SiO2, SiO is shown by XRD, BET, ICP2Surface is uniformly divided
Scattered TiO2It can make MoO3With carrier S iO2Between interaction force enhancing so that MoO3Dispersity be obviously improved,
Improve the catalytic activity of catalyst.
Meanwhile MoO3/TiO2-SiO2The content of each component has bigger influence to the catalytic activity of catalyst in catalyst,
The MoO used herein3/TiO2-SiO2Catalyst is 18%MoO3/ 6%TiO2-SiO2Catalyst.In the process due to SiO2
It is carrier, therefore its content does not have large effect to catalyst activity.
As shown in table two and table three：
In the state of two, 54 DEG C of table, bisphenol-A is in MoO3And TiO2Conversion ratio under different content in 2h
In the state of three, 54 DEG C of table, isobide is in MoO3And TiO2Conversion ratio under different content in 2h
By being understood in table two and table three in MoO3Content be 18%, TiO2Content when be 6%, bisphenol-A and different mountain
Pears alcohol conversion is all peak, therefore, selects 18%MoO3/ 6%TiO2-SiO2Catalyst can greatly improve bisphenol-A and different
The reaction rate of sorbierite in the esterification reaction.
In addition, horizontal disc polycondensation reactor 3, Prepolycondensating reactor 4,8 and second esterification of first esterification reactor
Device 9 is connected with vacuum system 5, and the hydroxyaryl reaction product so generated during this can rapidly be pulled out system,
So as to ensure that environment is not contaminated.
And vacuum system 5 is also communicated with multi-stage condensing device 6, multi-stage condensing device 6 is connected with ground flare combustion system 7, this
Hydroxyaryl reaction product promptly can be condensed into liquid and exported to ground flare combustion system 7 by sample, so as to quickly lead to
It crosses that hydroxyaryl reaction product is lighted production carbon dioxide by ground flare system and water vapour is discharged into air, avoids pair
Environment pollutes.
Further embodiment is that the pipeline material of all reactors connection is all to use in 316Ti or 316L at least
One kind since 316Ti and 316L inherently has higher corrosion resistant ability, can improve the anticorrosive energy of pipeline
Power extends the service life of whole system.
Further scheme is to be equipped with reflux pump 12 on the first raw material blending tank 10 and the second raw material blending tank 11
And reflux pipeline, the material for mixing pot bottom is got to again by reflux pump 12 and the reflux pipeline at the top of blending tank
In blending tank, so that the material mixing of 11 energy of the first raw material blending tank 10 and the second raw material blending tank is more uniform, under
Trip reaction, which plays, improves superior condition.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (2)
1. a kind of polycarbonate production system, including devolatilization granulating system, it is characterised in that：The devolatilization granulating system includes double
Screw rod devolatilization extruder, comminutor and cistern, the twin-screw devolatilization extruder are connected with comminutor, the comminutor
Particle delivery outlet is immersed under the liquid level of cistern, and the second that the liquid in the cistern is 5.3%~5.7% volume
Alcohol-water solution, the water surface air of cistern are connected with vacuum system, the twin-screw devolatilization extruder and hydraulic-driven it is horizontal
Disk polycondensation reactor connects, and the twin-screw devolatilization extruder is connected with vacuum system, and the vacuum system is communicated with multistage
Condenser, multi-stage condensing device are connected with ground flare combustion system, the horizontal disc polycondensation reactor and kettle of the hydraulic-driven
The Prepolycondensating reactor connection of formula, the Prepolycondensating reactor pressure of autoclave is 1kPa~15kPa, and temperature is 240 DEG C~280 DEG C,
The Prepolycondensating reactor of the autoclave is respectively communicated with the first transesterification reactor, the second transesterification reactor, the horizontal circle
Disk polycondensation reactor, Prepolycondensating reactor, the first transesterification reactor and the second transesterification reactor are connected with vacuum system,
First transesterification reactor is connected with being connected with the first raw material blending tank of bisphenol-A and dimethyl oxalate, and second ester is handed over
It changes reactor and is connected with being connected with the second raw material blending tank of isobide and dimethyl oxalate, the first raw material blending tank and
At 54 DEG C~59 DEG C, pressure is controlled in 100kPa~120kPa, first transesterification for the temperature control of two raw material blending tanks
It is added in through acetated 18%MoO in reactor and the second transesterification reactor3/ 6%TiO2-SiO2Catalyst.
2. a kind of polycarbonate production system according to claim 1, it is characterised in that：With above-mentioned all reactor phases
The material of the pipeline of connection is at least one of 316Ti and 316L.
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| CN201510811619.5A CN105291297B (en) | 2015-11-20 | 2015-11-20 | A kind of polycarbonate production system |
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| CN201510811619.5A CN105291297B (en) | 2015-11-20 | 2015-11-20 | A kind of polycarbonate production system |
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| CN108707224B (en) * | 2018-06-26 | 2020-06-16 | 北京濮源新材料技术研究院(普通合伙) | Environment-friendly polycarbonate and preparation method thereof |
| CN114644776B (en) * | 2022-04-29 | 2023-09-01 | 聊城鲁西聚碳酸酯有限公司 | System and method for recycling polycarbonate powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103459464A (en) * | 2011-03-31 | 2013-12-18 | 三菱化学株式会社 | Method for producing polycarbonate, and polycarbonate pellets |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103459464A (en) * | 2011-03-31 | 2013-12-18 | 三菱化学株式会社 | Method for producing polycarbonate, and polycarbonate pellets |
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