CN101235136A - Process for preparing polycarbonate - Google Patents
Process for preparing polycarbonate Download PDFInfo
- Publication number
- CN101235136A CN101235136A CNA2008100064614A CN200810006461A CN101235136A CN 101235136 A CN101235136 A CN 101235136A CN A2008100064614 A CNA2008100064614 A CN A2008100064614A CN 200810006461 A CN200810006461 A CN 200810006461A CN 101235136 A CN101235136 A CN 101235136A
- Authority
- CN
- China
- Prior art keywords
- reaction
- flow reactor
- impact flow
- organic phase
- polycarbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a method for preparing polycarbonate via impinging stream reactor and interface method, comprising: (a) mixing bisphenol compound and alkali metal hydroxide water solution into aqueous phase, dissolving carbonyl chloride in an inertia solvent of polycarbonate to form organic phase, (b) feeding the aqueous phase and organic phase into an impinging stream reactor to process photochemical reaction, (c) after the impinging stream reactor, carrying out sealing reaction and coupling reaction, separating to obtain polycarbonate. The invention can improve the reaction efficiency of carbonyl chloride and phenolate, to react completely, shorten the interface photochemical reaction and the whole condensation, reduce side product and reduce energy consumption.
Description
Technical field
The present invention relates to the method that a kind of interface phosgenation prepares polycarbonate, relate in particular to and adopt impact flow reactor to strengthen the method that the interface photochmeical reaction prepares polycarbonate.
Background technology
Polycarbonate resin excellent combination property, particularly its optical property, mechanical mechanics property, shock resistance, thermotolerance and electrology characteristic etc. are widely used in Application Areass such as electric, electronics, automobile, household electrical appliances, building as engineering plastics.
The polycarbonate suitability for industrialized production mainly contains two kinds of methods, is respectively interface phosgenation and melt transesterification process.The interface phosgenation is produced the method for polycarbonate and can recognize for example " Chemistry and Physics of polycarbonates ", Polymer Reviews, H.Schnell, the 9th volume, John Wiley﹠amp from following document; Sons, Inc. (1964), 50-51 page or leaf; And JP 02133425; JP 03109420; JP 02214722; US 4055544; US 4973664; JP 07165899; Patent documentations such as NL9400785.
Usually the step of interface phosgenation production polycarbonate is: at first the aqueous phase solution with bis-phenol and alkali composition mixes with the organic phase solution that phosgene and organic solvent are formed, finish photochmeical reaction and form performed polymer, add molecular weight terminator or chain branching agent, catalyzer, alkaline solution etc. subsequently and proceed interfacial polymerization, finish molecular chain and increase, generate polycarbonate resin at last.
The production technique that existing interface phosgenation prepares polycarbonate mainly contains two kinds.A kind of is the photochmeical reaction at intermittence that adopts stirred-tank reactor to carry out, concrete scheme is as follows: the bis-phenol and the basic metal aqueous solution are mixed with the phenates aqueous solution in advance, join in the stirring tank with suitable organic solvent, under the violent stirring of stirring rake, continue to feed phosgene, can replenish the adding alkali metal hydroxide aqueous solution, the phenates of aqueous phase contacts at the interface of water and organic phase with phosgene photochmeical reaction takes place.This technology is owing to mix the restriction of intensity, and phosgene is difficult for rapidly, mixes fully with phenates, is easy to generate the dead band in the stirring tank, makes by-products content increase, and separation system is caused big difficulty; In addition because the essence of intermittent process, in this technology actual production the phosgene loss more, huge, the complex process of the required appliance arrangement of scale operation, operational stability is relatively poor, energy consumption is higher.Another kind is the continuous photochmeical reaction that adopts static mixer to carry out as the tubular type actinic reactor, concrete scheme is as follows: phosgene is dissolved in the suitable organic solvent, mix in static mixer with the phenates aqueous solution for preparing in advance, the phenates photoreactive gas contacts concurrent third contact of a total solar or lunar eclipse reaction at water and generates performed polymer with the organic phase interface.This technology is in fact owing to the portion of energy of being imported is dissipated on the internal friction resistance of the static mixer that overcomes the various hybrid elements of inner filling; And during mixed solution process static mixing element, the liquid-liquid phase interface of reacting required increases gradually, and the mixing efficiency when in fact beginning is not high.
Therefore, need to seek a kind of reaction efficiency, transformation efficiency height that can improve phosgene and phenates; And stable operation, the method for preparing polycarbonate that energy consumption is low.
Impact flow reactor has obtained application in some fields, and for example CN200510045867.X has described impact flow reactor is applied in the fraction oil oxidation desulfurizing aspect, and this technology can be handled more high sulfur content and worse raw material, obtains low-sulfur fuel; CN200510047515.8 adopts impact flow reactor, makes vegetable and animals oils or fat and low-carbon alcohol carry out transesterification reaction, the preparation biofuel.But the report that impact flow reactor is applied to prepare polycarbonate is not also arranged at present.
Summary of the invention
The purpose of this invention is to provide a kind of reaction efficiency, transformation efficiency height that can improve phosgene and phenates; And stable operation, the method for preparing polycarbonate that energy consumption is low.
For achieving the above object, the invention provides a kind of method that adopts impact flow reactor to prepare polycarbonate, this method may further comprise the steps:
A) a kind of bisphenol cpd is mixed with alkali metal hydroxide aqueous solution form water, phosgene is dissolved in a kind of inert solvent of polycarbonate and forms organic phase;
B) above-mentioned water and organic phase material are sent in the impact flow reactor, carried out photochmeical reaction;
C) treat that photochmeical reaction is finished after, carry out end capping and linked reaction successively, obtaining polycarbonate final the separation.
The bisphenol cpd that uses in the step a) of the present invention can be dihydroxyphenyl propane (BPA, promptly 2,2-two (4-hydroxy phenyl) propane) or tetrabromo-bisphenol, described alkali metal hydroxide aqueous solution can be the aqueous sodium hydroxide solution of 5-50 quality % or the potassium hydroxide aqueous solution of 5-50 quality %, wherein the mol ratio of alkali metal hydroxide and bisphenol cpd is 2: 1-2.5: 1, and both form phenates at aqueous phase.
The solvent that uses in the step a) of the present invention can be one or more in methylene dichloride, toluene, chlorobenzene or the tetracol phenixin, and the concentration of phosgene in organic phase is 3-20 quality %.
The impact flow reactor that uses in the step b) of the present invention can be to be used for liquid reactive various types of impact flow reactor in the prior art, can determine the concrete size of impact flow reactor according to unit scale and operational condition.The impact flow reactor that the present invention uses can be as described in patent CN02138720.6, CN00230326.4, CN03235518.1 etc. and " percussion flow---principle character is used " (Wu Yuanzhu, the Chemical Industry Press).
In order further to realize purpose of the present invention, preferred impact flow reactor is the impact flow reactor that adopts form of nozzle, and the turbulence impingement region that collision jet produces is on impact flow reactor homeostasis liquid level.The speed that reaction mass enters the import of impact flow reactor impingement region is the 1.7-3.8 meter per second, and preferred speed is about 3 meter per seconds.Preferably, the mean residence time in impact flow reactor is 18.5-26.5 second, is preferably 20-25 second.Material is 0.5-2 second at the mean residence time of impact flow reactor liquid-liquid impingement region, is preferably 1-1.5 second.The mean residence time in material mixing of materials district in impact flow reactor is 18-24.5 second.
In the step b) of the present invention,, the reaction gains can be divided into two portions, send into once more in another or a plurality of impact flow reactor and proceed knock-on reaction, finish until photochmeical reaction if photochmeical reaction is incomplete.
In the end capping and linked reaction in step c) of the present invention, can replenish adding concentration respectively is the alkali hydroxide soln of 5-50 quality %, and the pH that keeps reaction system is greater than 11.
The exemplary of the suitable chain terminator that end capping described in the step c) adopts for example has description in DE-A3833953, can be phenol or p-tert-butylphenol.Chain terminator can be dissolved in earlier in the suitable organic solvent, and then this solution is joined after the photochmeical reaction in the resulting mixed solution, or is dissolved in the alkali hydroxide soln and adds.
The catalyzer that linked reaction described in the step c) adopts can be the ammonium salt compounds, preferred triethylamine (TEA).Catalyst consumption is about 1 quality % of bisphenol cpd.
In the step c) of the present invention, described end capping is divided into two portions with material after can comprising the steps: in the step b) gains to add chain terminator and optional alkali hydroxide soln, sends into respectively in another impact flow reactor and reacts.
In the impact flow reactor that the present invention adopts, two strands of monophasic fluids leave guide shell or nozzle at a high speed, form an impact surface at the container intermediate phase to bump, produce the radial and axial turbulent velocity component of intensive, bump forms the impingement region of height turbulence, very helps mass transfer; And the high shearing force that high velocity impact produced can cause the breakup of drop, produce huge and phase interface fast updating, strengthened dispersion and transmittance process widely, increased rate of mass transfer by increasing the dispersant liquid drop surface-area, thereby impel interface phosgenation reaction; Drop repeatedly vibrating and infiltrate the mean residence time that reverse direction flow etc. can prolong the impingement region drop effectively simultaneously through impingement region.Impact flow reactor generally can significantly improve reaction conversion ratio and selectivity, significantly dwindles reactor volume, simplifies technical process, and implementation procedure energy-efficient reduces disposal of pollutants.Generally than improving 1～3 order of magnitude in traditional reactor, microcosmic mixes interphase mass transfer speed and mass transfer process is greatly strengthened in the impact flow reactor.
The polycarbonate interface polymerization mechanism shows, phosgenation reaction only carries out at the interface, and liquid-liquid poor dispersion and cause interfacial area little between the two-phase among the preparation method of prior art causes photochmeical reaction efficient lower thus.The present invention adopts impact flow reactor, acting on the fluid dynamic energy overwhelming majority greatly, forced fluid-liquid dispersion process, transmittance process and microcosmic mix, increase phase contact area, improve phosgene and phenates reaction efficiency, sufficient reacting, interface photochmeical reaction and whole polycondensation reaction time have been shortened, the final product molecular weight distribution that obtains is narrower, and small molecular weight impurity significantly reduces in the product, has reduced side reaction product, and can reduce process phosgene usage quantity and solvent usage quantity, reduce the production process energy consumption.In addition, present method stable operation, equipment used volume little, be convenient to move, dismantle and install.
Description of drawings
Fig. 1 is an impact flow reactor structural representation of the present invention;
Fig. 2 is the reaction system continuous operation process schematic flow sheet of the present invention's one specific embodiments;
Fig. 3 is the reaction system continuous operation process schematic flow sheet of another specific embodiments of the present invention.
Embodiment
Further specify embodiment of the present invention below in conjunction with drawings and Examples.But the invention is not restricted to listed embodiment, also should be included in other any known change in the interest field of the presently claimed invention.
As shown in Figure 1, impact flow reactor of the present invention comprises: 3, two feed-pipes 4 of main body container and 5, and material outlet 9.Wherein feed- pipe 4 and 5 is coaxial respectively and be installed in symmetrically in the container 3.And container 3 is the useful volume district of reaction for downward projection is circular cylindrical shell.The size that feed- pipe 4 and 5 stretches into container 3 is changeable, feed- pipe 4 and 5 port diameter d can change, feed- pipe 4 and 5 is on the suitable height of container 3, to guarantee that turbulence impingement region 8 that collision jet was produced is at impact flow reactor homeostasis liquid level more than 10.
Material enters impact flow reactor from two feed- pipes 4 and 5 respectively, material is under the high speed of pump 1 and 2 promotes, leave nozzle 6 and 7 and form at a high speed the central position that jet in opposite directions enters container 3, and intensive turbulence bump takes place in opposite directions in the center, around impact surface, form high speed turbulence impingement region 8.From violent move toward one another between the stream group of different directions, make and effectively shear and collision between stream group and between liquid phase, increased alternate area, impel surface reaction.
After this time bump finished, reaction solution can still stay for some time in impact flow reactor, and continued at the interface that had formed already photochmeical reaction to take place, and will flow out from exporting 9 after material stays for some time.
From the material that impact flow reactor comes out, still do not finish as photochmeical reaction, can enter next impact flow reactor and proceed photochmeical reaction, finish as photochmeical reaction, can carry out next step reaction.
The recycle stock handling equipment (as pump) of impact flow reactor can adopt one or more.
Fig. 2 is the reaction system continuous operation process schematic flow sheet of the present invention's one specific embodiments.
As shown in Figure 2, at first in premix tank A, the alkali metal hydroxide aqueous solution of 5-50 quality % is mixed the formation water with bisphenol cpd according to reaction desired raw material amount.Simultaneously in premix tank B, phosgene is mixed the formation organic phase with suitable solvent, then by pump 21 and 22, be input to impact flow reactor 23, material enters the impingement region central zone by nozzle ejection at a high speed under pressure, the V-bar that material enters impingement region is the 1.7-3.8 meter per second, and clashes in opposite directions in the center.Wherein mixture is 0.5-2 second in the residence time of impingement region, preferred 1-1.5 second.If phosgenation reaction is not finished, then above-mentioned reacted reaction solution is input to next or a plurality of impact flow reactors by pump again, clashes into once more, finishes until phosgenation reaction.The flow velocity in each impact flow reactor and the residence time can be basic identical.When phosgenation reaction is finished, flow to tundish C through the reaction solution behind the bump from outlet, add chain terminator therein, and randomly add the alkali metal hydroxide aqueous solution that replenishes, by pump 24, be input to another impact flow reactor 25 and continue end capping then.In impact flow reactor, carry out the flow velocity of end capping and the residence time can with photochmeical reaction in basic identical.Through behind at least one impact flow reactor, reaction solution by among the pump 26 input stirring tank D, adds catalyzer again in reaction solution, and randomly replenishes and add alkali hydroxide soln, mixes reacting, thereby obtains final polycarbonate resin.At last, separate and reclaim above-mentioned polycarbonate resin.
Fig. 3 is the reaction system continuous operation process schema of another specific embodiments of the present invention.
As shown in Figure 3, at first in premix tank A, the alkali metal hydroxide aqueous solution of 5-50 quality % is mixed the formation water with bisphenol cpd according to reaction desired raw material amount.Simultaneously in premix tank B, phosgene is mixed the formation organic phase with suitable solvent, then by pump 31 and 32, be input to impact flow reactor 33, material enters the impingement region central zone by nozzle ejection at a high speed under pressure, the V-bar that material enters impingement region is the 1.7-3.8 meter per second, and clashes in opposite directions in the center.Wherein mixture is 0.5-2 second in the residence time of impingement region, preferred 1-1.5 second.If photochmeical reaction is not finished, then above-mentioned reacted reaction solution is input to another or a plurality of impact flow reactor by pump again, clashes into once more, finishes until phosgenation reaction.The flow velocity in each impact flow reactor and the residence time can be basic identical.Be input among the reactor E by pump 34 again through the reaction solution behind the bump, add chain terminator and optional alkali hydroxide soln therein earlier, to carry out end capping; Subsequently, add catalyzer and optional alkali hydroxide soln therein, carrying out linked reaction, thereby obtain final polycarbonate resin.At last, separate and reclaim above-mentioned polycarbonate resin.
The following examples will give further instruction to method provided by the present invention, but therefore the present invention is not subjected to any restriction.
Used raw material is respectively in following examples: dihydroxyphenyl propane: technical grade, available from Dow Chemical; 50 quality % sodium hydroxide solutions: analytical pure, available from Tianjin Kermel Chemical Reagent Co., Ltd.; Phosgene: technical grade, self-control; Methylene dichloride: analytical pure, available from Tianjin Kermel Chemical Reagent Co., Ltd.; Phenol: analytical pure, available from Chemical Inst., Shandong Prov.; Triethylamine: analytical pure, available from Tianjin Kermel Chemical Reagent Co., Ltd..
In premix tank A, add 206.6g dihydroxyphenyl propane, 2925g water respectively and mix the formation water with 146g50 quality % sodium hydroxide solution, in premix tank B, mix with the 2095g methylene dichloride by the liquid phosgene of 84g respectively and form organic phase, by pump water and organic phase material are input to respectively in the feed-pipe of nozzle-type impact flow reactor, thereby make material enter the impingement region central zone by nozzle ejection at a high speed, the speed that material enters the impingement region import is 1.7 meter per seconds, and the residence time is 24 seconds in impact flow reactor.Reaction solution enters among the reactor E subsequently, adds 2.19g phenol and 1.85g50 quality % aqueous sodium hydroxide solution, and making the pH value of solution value is 11.5, react after 45 minutes, add 1.03g triethylamine and 50 quality % aqueous sodium hydroxide solutions, making the pH value of solution value is 11.5, and mixing time is 2 minutes.Reaction product is through water phase separated and organic phase, with deionized water wash organic phase 3 times, obtains polycarbonate resin 229g after removing organic solvent, and productive rate is 98.7%, and number-average molecular weight is 15300, and weight-average molecular weight is 29700; Analyze to such an extent that the content of aqueous phase dihydroxyphenyl propane is 84ppm in addition.
In premix tank A, add 206.6g dihydroxyphenyl propane, 2925g water respectively and mix the formation water with 146g50 quality % sodium hydroxide solution, the liquid phosgene of 83g mixes the formation organic phase with the 2000g methylene dichloride respectively in premix tank B, by pump water and organic phase material are input to respectively in the feed-pipe of nozzle-type impact flow reactor, material high speed under pressure enters the impingement region center by nozzle ejection, it is 3.8 meter per seconds that material enters the impingement region inlet velocity, and the residence time is 5 seconds in the knock-on reaction device.Reaction afterreaction liquid enters among the tundish C, add 2.19g phenol and 1.85g50 quality % sodium hydroxide solution, making the pH value of solution value is 11.5, be input to respectively by pump in the feed-pipe of another nozzle-type impact flow reactor, the speed that material enters the impingement region import is 2.6 meter per seconds, and the residence time is 15 seconds in impact flow reactor.Reaction solution enters among the stirring tank D then, adds 1.03g triethylamine and 50 quality % sodium hydroxide solutions, and making the pH value of solution value is 11.5, and mixing time is 2 minutes.Reaction product is through water phase separated and organic phase, with deionized water wash organic phase 3 times, obtains polycarbonate resin 232g after removing organic solvent, and productive rate is 99.5%, number-average molecular weight 14900, weight-average molecular weight 31250; Analyze to such an extent that aqueous phase BPA content is 46ppm in addition.
In premix tank A, add 207.4g dihydroxyphenyl propane, 2925g water respectively and mix the formation water with 146g50 quality % sodium hydroxide solution, in premix tank B, mix with the 2095g methylene dichloride by the liquid phosgene of 84g respectively and form organic phase, by pump water and organic phase material are input to respectively in the feed-pipe of nozzle-type impact flow reactor, material high speed under pressure enters the impingement region center by nozzle ejection, it is 2.1 meter per seconds that material enters the impingement region inlet velocity, and the residence time is 20 seconds in the knock-on reaction device.Reaction solution enters among the tundish C then, add 1.46g phenol and 1.85g50 quality % sodium hydroxide solution, making the pH value of solution value is 11.8, be input to respectively by pump in the feed-pipe of another nozzle-type impact flow reactor, it is 3.2 meter per seconds that material enters the impingement region inlet velocity, and the residence time is 12 seconds in impact flow reactor.Reaction solution enters among the stirring tank D subsequently, adds 1.04g triethylamine and 50 quality % sodium hydroxide solutions, and making the pH value of solution value is 11.8, and mixing time is 2 minutes.Reaction product is through water phase separated and organic phase, with deionized water wash organic phase 3 times, obtains polycarbonate resin 232g after removing organic solvent, and productive rate is 99.5%, number-average molecular weight 17700, weight-average molecular weight 33500; Analyze to such an extent that aqueous phase BPA content is 38ppm in addition.
In premix tank A, add 207.8g dihydroxyphenyl propane, 2925g water respectively and mix the formation water with 146g50 quality % sodium hydroxide solution, in premix tank B, mix with the 2095g methylene dichloride by the liquid phosgene of 84g respectively and form organic phase, by pump water and organic phase material are input to respectively in the feed-pipe of nozzle-type impact flow reactor, material high speed under pressure enters the impingement region center by nozzle ejection, it is 1.7 meter per seconds that material enters the impingement region inlet velocity, and the residence time is 25 seconds in the knock-on reaction device.Reaction solution enters among the tundish C then, add 1.10g phenol and 1.85g50 quality % sodium hydroxide solution, making the pH value of solution value is 11.6, be input to respectively by pump in the feed-pipe of another nozzle-type impact flow reactor, it is 1.7 meter per seconds that material enters the impingement region inlet velocity, and the residence time is 30 seconds in impact flow reactor.Reaction solution enters among the stirring tank D subsequently, adds 1.04g triethylamine and 50 quality % sodium hydroxide solutions, and making the pH value of solution value is 11.6, and mixing time is 2 minutes.Reaction product is through water phase separated and organic phase, with deionized water wash organic phase 3 times, obtains polycarbonate resin 232g after removing organic solvent, and productive rate is 99.0%, number-average molecular weight 16900, weight-average molecular weight 36500; Analyze to such an extent that aqueous phase BPA content is 47ppm in addition.
Comparative Examples 1
In premix tank A, add 207.4g dihydroxyphenyl propane, 2925g water respectively and mix the formation water with 146g50 quality % sodium hydroxide solution, in premix tank B, mix with the 2125g methylene dichloride by the 90g phosgene respectively and form organic phase, by pump water and organic phase material are input to tank reactor (stirring tank respectively, robot company limited is found by Yantai section) in, material residence time in tank reactor is 20 minutes.Reaction solution enters among the tundish C then, adds 1.46g phenol and 1.85g50% sodium hydroxide solution, and making the pH value of solution value is 11.8, behind pump, reaction solution is input in another tank reactor, and the residence time is 30 minutes in tank reactor.Reaction solution enters among the stirring tank D then, adds 1.04g triethylamine and 50% sodium hydroxide solution, and making the pH value of solution value is 11.8, and mixing time is 60 minutes.Reaction product is through water phase separated and organic phase, obtains polycarbonate resin 213g, productive rate 92%, number-average molecular weight 14020, weight-average molecular weight 33500 with deionized water wash organic phase 3 times, after removing organic solvent; Analyze to such an extent that aqueous phase BPA content is 178ppm in addition.
Comparative Examples 2
In premix tank A, add 207.4g dihydroxyphenyl propane, 2925g water respectively and mix the formation water with 146g50 quality % sodium hydroxide solution, in premix tank B, mix with the 2095g methylene dichloride by the liquid phosgene of 84g respectively and form organic phase, by pump water and organic phase material are input to static mixer (Smv type respectively, sulzer company) in, material residence time in static mixer is 3 minutes.Reaction solution enters among the tundish C then, adds 1.46g phenol and 1.85g50% sodium hydroxide solution, behind pump, reaction solution is input in the tank reactor, and the residence time is 25 minutes in tank reactor.Reaction solution enters among the stirring tank D then, adds 1.04g triethylamine and 50% sodium hydroxide solution, makes the pH value of solution value between 10.5-11, and mixing time is 60 minutes.Reaction product is through water phase separated and organic phase, obtain polycarbonate resin 226g, productive rate 97.1%, number-average molecular weight 16500 with deionized water wash organic phase 3 times, after removing organic solvent, weight-average molecular weight 42300 is analyzed to such an extent that aqueous phase BPA content is 126ppm in addition.
Claims (10)
1, a kind of method for preparing polycarbonate comprises the steps:
A) a kind of bisphenol cpd is mixed with alkali metal hydroxide aqueous solution form water, phosgene is dissolved in a kind of inert solvent of polycarbonate and forms organic phase;
B) above-mentioned water and organic phase material are sent in the impact flow reactor, carried out photochmeical reaction;
C) treat that photochmeical reaction is finished after, carry out end capping and linked reaction successively, obtaining polycarbonate final the separation.
2, method according to claim 1 is characterized in that, to enter the speed of impact flow reactor impingement region be the 1.7-3.8 meter per second to material in the step b), and the mean residence time of material in impact flow reactor is 18.5-26.5 second.
3, method according to claim 2 is characterized in that, to enter the speed of impact flow reactor impingement region be 3 meter per seconds to material in the step b), and the mean residence time of material in impact flow reactor is 20-25 second.
4, according to each described method among the claim 1-3, it is characterized in that the impact flow reactor that is adopted in the step b) is the impact flow reactor of form of nozzle, the turbulence impingement region that percussion flow produces is on impact flow reactor homeostasis liquid level.
5, method according to claim 4, it is characterized in that, bisphenol cpd described in the step a) is dihydroxyphenyl propane or tetrabromo-bisphenol, described alkali metal hydroxide aqueous solution is the aqueous sodium hydroxide solution of 5-50 quality % or the potassium hydroxide aqueous solution of 5-50 quality %, and wherein the mol ratio of alkali metal hydroxide and bisphenol cpd is 2: 1-2.5: 1.
6, method according to claim 5 is characterized in that, the solvent described in the step a) is one or more in methylene dichloride, toluene, chlorobenzene or the tetracol phenixin, and the concentration of phosgene in organic phase is 3-20 quality %.
7, method according to claim 6 is characterized in that, in described end capping of step c) and the linked reaction, replenishing adding concentration respectively is the alkali hydroxide soln of 5-50 quality %, and the pH that keeps reaction system is greater than 11.
8, method according to claim 7 is characterized in that, the chain terminator that end capping described in the step c) adopts is phenol or p-tert-butylphenol; The catalyzer that described linked reaction adopts is a triethylamine.
9, method according to claim 8 is characterized in that, before carrying out step c), the step b) gains enter one or more impact flow reactors and proceed reaction, so that photochmeical reaction is complete;
10, method according to claim 9, it is characterized in that, after end capping described in the step c) comprises the steps: in the step b) gains to add chain terminator and optional alkali hydroxide soln, material is divided into two portions, sends into respectively in another impact flow reactor and react.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100064614A CN101235136B (en) | 2008-02-28 | 2008-02-28 | Process for preparing polycarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100064614A CN101235136B (en) | 2008-02-28 | 2008-02-28 | Process for preparing polycarbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101235136A true CN101235136A (en) | 2008-08-06 |
| CN101235136B CN101235136B (en) | 2010-11-03 |
Family
ID=39919066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100064614A Active CN101235136B (en) | 2008-02-28 | 2008-02-28 | Process for preparing polycarbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101235136B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702500A (en) * | 2012-06-18 | 2012-10-03 | 陕西延长石油（集团）有限责任公司 | Preparation method of aromatic polycarbonate |
| CN102874877A (en) * | 2012-10-18 | 2013-01-16 | 北京化工大学 | Device and method for preparing manganese dioxide ultrafine powder |
| CN103861544A (en) * | 2012-12-17 | 2014-06-18 | 中国石油化工股份有限公司 | Impinging stream reactor and application thereof |
| CN105771828A (en) * | 2014-12-20 | 2016-07-20 | 中国石油化工股份有限公司 | Impinging stream reactor used for liquid-liquid reaction |
| CN107324304A (en) * | 2017-06-30 | 2017-11-07 | 襄阳泽东化工集团有限公司 | A kind of method that impinging stream reaction method produces high polymerization degree APP |
| CN110882673A (en) * | 2018-09-07 | 2020-03-17 | 上海工程技术大学 | Chemical reaction method and device based on impinging stream |
| CN112876681A (en) * | 2021-02-04 | 2021-06-01 | 武汉柔显科技股份有限公司 | Preparation method for preparing polyimide precursor and film thereof by using impinging stream reactor |
| CN114196002A (en) * | 2022-01-11 | 2022-03-18 | 万华化学（宁波）有限公司 | Preparation method of transparent flame-retardant novel polycarbonate, polycarbonate and application thereof |
-
2008
- 2008-02-28 CN CN2008100064614A patent/CN101235136B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702500A (en) * | 2012-06-18 | 2012-10-03 | 陕西延长石油（集团）有限责任公司 | Preparation method of aromatic polycarbonate |
| CN102874877A (en) * | 2012-10-18 | 2013-01-16 | 北京化工大学 | Device and method for preparing manganese dioxide ultrafine powder |
| CN102874877B (en) * | 2012-10-18 | 2014-11-05 | 北京化工大学 | Device and method for preparing manganese dioxide ultrafine powder |
| CN103861544A (en) * | 2012-12-17 | 2014-06-18 | 中国石油化工股份有限公司 | Impinging stream reactor and application thereof |
| CN103861544B (en) * | 2012-12-17 | 2016-07-27 | 中国石油化工股份有限公司 | A kind of impact flow reactor and application thereof |
| CN105771828A (en) * | 2014-12-20 | 2016-07-20 | 中国石油化工股份有限公司 | Impinging stream reactor used for liquid-liquid reaction |
| CN105771828B (en) * | 2014-12-20 | 2018-11-06 | 中国石油化工股份有限公司 | A kind of impact flow reactor for reactive liquid solution |
| CN107324304A (en) * | 2017-06-30 | 2017-11-07 | 襄阳泽东化工集团有限公司 | A kind of method that impinging stream reaction method produces high polymerization degree APP |
| CN110882673A (en) * | 2018-09-07 | 2020-03-17 | 上海工程技术大学 | Chemical reaction method and device based on impinging stream |
| CN112876681A (en) * | 2021-02-04 | 2021-06-01 | 武汉柔显科技股份有限公司 | Preparation method for preparing polyimide precursor and film thereof by using impinging stream reactor |
| CN114196002A (en) * | 2022-01-11 | 2022-03-18 | 万华化学（宁波）有限公司 | Preparation method of transparent flame-retardant novel polycarbonate, polycarbonate and application thereof |
| CN114196002B (en) * | 2022-01-11 | 2023-08-11 | 万华化学（宁波）有限公司 | Preparation method of transparent flame-retardant novel polycarbonate, polycarbonate and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101235136B (en) | 2010-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101235136B (en) | Process for preparing polycarbonate | |
| CN205042452U (en) | Percussion flow heterogeneous reaction ware | |
| CN101274249B (en) | Novel liquid-liquid heterophase reactor | |
| KR102159044B1 (en) | Reactor and alkylation process using the reactor | |
| CN101279923B (en) | Preparation of polymethylene polyphenyl polyamine | |
| CN102030895B (en) | Method for preparing polycarbonate with continuous two-phase interface phosgene method | |
| CN102516519B (en) | Method for preparing polycarbonate | |
| Lin et al. | Highly Efficient Self‐Assembly of Metallacages and Their Supramolecular Catalysis Behaviors in Microdroplets | |
| CN107130953A (en) | A kind of chemical enhanced gas producing technology | |
| CN110683953B (en) | Method for continuously synthesizing isooctyl nitrate and extracting residual acid in isooctyl nitrate in microreactor | |
| CN117327265B (en) | Preparation method of polycarbonate | |
| CN104673359B (en) | A kind of preparation method of phenolic aldehyde amine resinae demulsifier | |
| CN107056670B (en) | A kind of preparation method of two tertiary base peroxide | |
| CN102127017B (en) | Method for fast producing caprolactam by means of strengthening and mixing | |
| US9745259B2 (en) | Process for preparing alcohol ether sulfates | |
| CN210385821U (en) | Ultrasonic intensified jet reactor | |
| CN110036055A (en) | The continuous current method of polymerization for alkylene oxide | |
| CN112827215B (en) | Cyclone extraction method and device for C5 petroleum resin polymerization liquid | |
| Takei et al. | Anionic surfactants: lauric products | |
| CN1951915A (en) | Sulfur trioxide gas jet sulfonation process and device for bisalkyl benzene | |
| Wang et al. | Reaction Principle of Alcohol Ether Sulfonates by Sulfonated Alkylation Method–A Review | |
| CN205856428U (en) | A kind of combination type impinging stream reaction device | |
| CN1757630A (en) | Equipment and method for washing prodn. of nitrobenzene | |
| CN106496544A (en) | A kind of preparation method of methyl blocking allyl alcohol polyether | |
| CN105018062A (en) | Thick oil viscosity reducer, preparing method thereof and thick oil viscosity reducing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 315812 Zhejiang province Ningbo city circle road Wanhua Industrial Park Daxie Economic Development Zone, Ningbo Wanhua Polyurethane Co., Ltd. Patentee after: Ningbo Wanhua Polyurethane Co., Ltd. Patentee after: Wanhua Chemical Group Co., Ltd. Address before: 315812 Zhejiang province Ningbo city circle road Wanhua Industrial Park Daxie Economic Development Zone, Ningbo Wanhua Polyurethane Co., Ltd. Patentee before: Ningbo Wanhua Polyurethane Co., Ltd. Patentee before: Yantai Wanhua Polyurethane Co., Ltd. |
|
| C56 | Change in the name or address of the patentee |
Owner name: WANHUA CHEMICAL (NINGBO) CO., LTD. Free format text: FORMER NAME: NINGBO WANHUA POLYURETHANE CO., LTD. |
|
| CP03 | Change of name, title or address |
Address after: 315812 Zhejiang province Ningbo Daxie Economic Development Zone North Island Wanhua Industrial Park Patentee after: Wanhua Chemical (Ningbo) Co., Ltd. Patentee after: Wanhua Chemical Group Co., Ltd. Address before: 315812 Zhejiang province Ningbo city circle road Wanhua Industrial Park Daxie Economic Development Zone, Ningbo Wanhua Polyurethane Co., Ltd. Patentee before: Ningbo Wanhua Polyurethane Co., Ltd. Patentee before: Wanhua Chemical Group Co., Ltd. |