CN101775128B - Method for preparing polycarbonate by continuous two-phase interface method - Google Patents
Method for preparing polycarbonate by continuous two-phase interface method Download PDFInfo
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Abstract
The invention discloses a method for preparing polycarbonate by a continuous two-phase interface method, which comprises the following steps of: firstly, premixing an alkali metal hydroxide aqueous solution containing polyphenol with phosgene which accounts for 5-20 parts by weight of the formula amount and an organic solvent and reacting for 1-60s to form an initial emulsion; then mixing the emulsion with the residual phosgene and a given amount of organic solvent and reacting to prepare a polycarbonate prepolymer emulsion; and finally, obtaining a polycarbonate resin after end capping and coupling reaction. The method can effectively reduce the phosgene consumption and improve the monomer percent conversion.
Description
Technical field
The present invention relates to the continuous production method of polycarbonate, more specifically to the method for the standby polycarbonate of two-phase interface legal system.
Background technology
Polycarbonate (PC) has outstanding shock resistance, creep resistance, higher tensile strength, bending strength, elongation and rigidity, be able to take the blast of television screen, and have higher thermotolerance and winter hardiness, and can in-100 ℃～140 ℃ scopes, use, electrical property is good, water-intake rate is low, light transmission is good, and the transmitance of visible light can reach about 90%, and can impose any painted.Large-scale industrial production mainly is aromatic copolycarbonate at present, the second largest engineering plastics that the present whole world is only second to nylon, in national economy, have been widely used, entered into the numerous areas such as automobile, electric, building, office equipment, packing, sports equipment, health care, household supplies.
Suitability for industrialized production mainly adopts interface phosgenation and melt transesterification process to prepare polycarbonate at present, and what wherein occupy industrial main flow is the interface phosgenation.The interface phosgenation refers in the situation of the aqueous solution that acid acceptor such as alkali metal hydroxide are arranged and catalyzer existence, be dissolved in the basic metal aqueous solution phenates be dissolved in phosgene in inert organic solvents such as the methylene dichloride the reacting at the interface of profit two-phase, prepare again the method for polycarbonate resin through separation and purification.Catalyzer is generally tertiary amine such as triethylamine or phase-transfer catalyst such as tetrabromo butyl ammonium.
The traditional interface phosgenation divides single stage method and two-step approach, present industrial main employing two-step approach, the first step mainly prepares polycarbonate prepolymer, second step carries out end-blocking and chain extending reaction again, wherein photochmeical reaction is carried out in the first step, be mainly phosgene and phenol negative oxygen ion and generate the chloro-formic ester end group in the oil-water two-phase interfaces reaction, and phosgene is a kind of active carbonyl chloride, very easily with the basic metal aqueous solution hydrolysis and alkaline hydrolysis reaction occurs in photochmeical reaction.Direct and phenates water hybrid reaction after phosgene is dissolved in organic solvent in traditional two-step approach, because the effect that the initial stage two-phase is mixed is relatively poor, two-phase interface tension force is larger, the emulsion that forms is unstable, and phenol negative oxygen ion and hydroxide ion have all increased hydrolysis and the alkaline hydrolysis side reaction of phosgene greatly in the factors such as discrete distribution of aqueous phase, cause the phosgene utilising efficiency not high, phosgene feeds intake overrate more than 12% molar fraction usually.In addition, in this type of photochmeical reaction process, be difficult to for above-mentioned reasons effectively control prepolymer middle-end chloroformate group and the equivalence ratio of end phenol negative oxygen ion group and the polymerization degree of prepolymer, thereby affect molecular weight and distribution thereof in the finished product.
US Patent No. 5210172 and US6613868 have provided respectively a kind of synthetic technology of circulation reaction preparation polycarbonate prepolymer, by the continuous circulation of polycarbonate prepolymer emulsion, the stability of photochmeical reaction stage emulsion and the form of polycarbonate prepolymer have effectively been controlled.Phosgene organic phase and phenates water all directly add in a large amount of circulation emulsions in this technique, although guaranteed the stability of emulsion, be beneficial to the morphology Control to prepolymer, but because reaction active groups is diluted in emulsion greatly, hydrolysis and the alkaline hydrolysis side reaction of phosgene have been increased, the circulation of simultaneously a large amount of emulsions needs large power conveying machinery, has increased energy consumption.
US Patent No. 4338429 has provided a kind of method of adding cationic emulsifier in the photochmeical reaction process, and emulsifying agent can adopt tetraalkylammonium salt etc.Adopt emulsifying agent can effectively reduce interfacial tension between organic phase and water, be conducive to the formation of emulsion, improve the stability of emulsion, but the interpolation of emulsifying agent is so that the separation and purification difficult in later stage and complexity.
US Patent No. 3530094 has provided a kind of technology of the standby polycarbonate of two-phase interface legal system of many still series connection, this technology adopts many stills tandem reactor, carry out photochmeical reaction in the first still, the residence time is about 5min, carries out end-blocking and linked reaction in the second still.This patent is also pointed out when interfacial polycondensation prepares PC simultaneously, and the chloro-formic ester end group can be excessive usually, makes it be converted into the phenolic hydroxyl group end-blocking after crossing alkaline hydrolysis.
US Patent No. 5258484 has provided a kind of plug flow and the complete mixing flow device makes up the polycarbonate technology of preparing of carrying out interfacial polycondensation, at first will be dissolved with the organic phase solution of phosgene and bisphenol sodium salt solution after the tubular reactor hybrid reaction, enter again and carry out linked reaction in the continuous stir reactor, end-capping reagent then can add at the stages of reaction all can, wherein the residence time of two-phase in tubular reactor is 10～30s.
In the US Patent No. 6780961 by control in the polycarbonate prepolymer hydroxyl and relative concentration and the amount of chloroformate group, thereby make the phosgene usage quantity reduce to minimum, the whole end-blockings of final product.This patent points out that chloroformate group net concentration in polycarbonate prepolymer (chloroformate group concentration-phenolic hydroxyl group concentration) is the solution greater than 0.04mol chloroformate group/every liter polycarbonate prepolymer and methylene dichloride.
US Patent No. 5182361 is introduced continuous interfacial polycondensation two step process, and the first step prepolymer reaction is to carry out in stirring tank, subsequently prepolymer and chain terminator is carried out polycondensation in the continuous tubular reactor that is comprised of static mixer and obtains product.
Chinese patent CN1017115 has provided a kind of preparation technology who polycarbonate prepolymer is converted into high-molecular-weight polycarbonate, relative concentration and amount by hydroxyl and chloro manthanoate group in the control polycarbonate prepolymer effectively prepare polycarbonate resin, can effectively reduce the phosgene usage quantity.The polycarbonate prepolymer that has in the method the specified end group structure is to realize by the method that passes into dihydroxyphenyl propane melt, methylene dichloride, phosgene and alkali lye in continuous stirred tank.
Chinese patent CN1258550 provides a kind of recycle pump reactor continuous polymerization technique, can produce high-quality product in the low organic content in keeping waste water.The method is to introduce organic phase and water in comprising the recirculation reactor loop of remaining tank, mixing tank, pump and heat exchanger, generates thus and obtains the polycarbonate of excellent property and comparatively pure waste water.The method intermixing process is that the organic phase that is dissolved with phosgene, the formed water of bis-phenol, the circulating reaction emulsion three who is dissolved in the alkali metal soln mix by mixing tank simultaneously, and mentioning mixing tank among the embodiment is T-shaped mixing tank.
Chinese patent CN1339517 provides a kind of semicontinuous autoclave polymerization technique, wherein phosgene adopts the Multistep feeding mode, the phosgene that the first step adds is liquid phosgene or is dissolved in phosgene solution in the organic solvent, second step is to blast gaseous phosgene, the former accounts for 60～96% massfractions of phosgene total amount, and the latter is 4～40% massfractions.
The early stage Smirnova of narration mixes with the basic metal aqueous solution interface that is dissolved with bis-phenol for strengthening the organic phase that is dissolved with phosgene in " Interfacial Synthesis " book of publishing in 1977 that Frank Millich edits, once adding tensio-active agent increases total interfacial area and reduces surface tension, include sodium oleate, sodium laurylsulfonate etc., but concrete molecular weight and polymer yield there is very big-difference with employed catalyzer.
Summary of the invention
The purpose of this invention is to provide a kind of novel method for preparing polycarbonate, a kind of method of preparing polycarbonate by continuous two-phase interface method namely is provided, described method comprises the steps:
A) bis-phenol or polyphenolic substance are dissolved in form water in the alkali metal hydroxide aqueous solution; The phosgene and the inert organic solvents that account for total phosgene amount 5～20% massfractions are formed the first organic phase; Phosgene and the inert organic solvents of residual content are formed Second Organic Phase, and wherein the phosgene concentration in the first organic phase or the Second Organic Phase is 5～20% massfractions;
B) water and the first organic phase are carried out premixing reaction, the premixing reaction residence time is 1～60s, namely gets the premixing reaction product;
C) then premixing reaction product and Second Organic Phase are carried out dispersing and mixing and carry out photochmeical reaction, the photochmeical reaction residence time is 5s to 20min;
D) after photochmeical reaction is finished, add first end-capping reagent and carry out end capping, then add catalyzer and carry out linked reaction, add alkali hydroxide soln control pH value greater than 12 when adding end-capping reagent and catalyzer, last separation and purification obtains polycarbonate resin.
The described step of the inventive method a) in, as one of preferred embodiment, the phosgene in the first organic phase accounts for 6～15% massfractions of total phosgene amount.
The described step of the inventive method a) in, the bis-phenol that uses or polyphenolic substance can ability in the bis-phenol of routine or the compound of polyphenol, the present invention includes but be not limited to dihydroxyphenyl propane (2,2-two (4-hydroxy phenyl), tetrabromo-bisphenol, three p-hydroxybenzene ethane or other polyhydroxy aromatic compounds or its mixture, preferred dihydroxyphenyl propane; Wherein, contain bis-phenol or polyphenol aqueous phase, the concentration that should control bis-phenol or polyphenol is 5～20% massfractions, preferred 6～15% massfractions, more preferably 10～15% massfractions.
Described alkali metal hydroxide aqueous solution can be sodium hydroxide, potassium hydroxide, preferred sodium hydroxide;
The inventive method step a) in, described inertia organic phase solvent is that make up arbitrarily methylene dichloride, ethylene dichloride, trichloroethane, tetrachloroethane, toluene, chlorobenzene, tetracol phenixin or they; Preferred methylene dichloride.Wherein, the preferred concentration of phosgene in the-organic phase or Second Organic Phase is the 5-10% massfraction.
Step b of the present invention) to carry out the residence time of premixing reaction be 1～60s for water and the first organic phase in, and preferably the residence time is 2～30s, makes the premixing reaction product.Should control the concentration of chloro-formic ester end group greater than 0.1 mole of chloroformate group/every liter of inertia organic phase solution that is dissolved with phosgene in the premixing reaction product, preferred concentration range is 0.3～0.7 mole of chloroformate group/every liter of inertia organic phase solution that is dissolved with phosgene.
Step b of the present invention) in, the mixing reactor that adopts in the premixing reaction should comprise tubular reactor, T-shaped mixing reactor or its combination; Should comprise at least a tubular reactor, or comprise at least a T-shaped mixing reactor, or the combination of these reactors, wherein, water and the first organic phase are carried out premixing reaction and are preferably carried out in the continuous pipe type mixing tank, more preferably carry out in being filled with the tubular reactor of static mixing element.
Step c of the present invention) in, the reactor of the second step photochmeical reaction that premixing reaction product and Second Organic Phase react comprises tubular reactor, continuous stirred tank reactor (CSTR) or loop reactor, or they make up arbitrarily; Wherein should comprise at least a tubular reactor, or comprise at least a continuous stirred tank reactor (CSTR), or comprise at least a loop reactor, or the combination of these reactors; The second step phosgenation reaction preferably carries out in continuous tubular reactor.
The present invention adds the organic phase phosgene solution, i.e. step b when preparation polycarbonate prepolymer emulsion in two steps) and step c); Step b) adds the first organic phase to the aqueous phase that contains bis-phenol or polyphenol in and react formation premixing reaction product, step c) add the Second Organic Phase that is formed by residual content phosgene and organic solvent again in the premixing reaction product in, reaction forms the polycarbonate prepolymer emulsion.The concentration range of phosgene is 5～20% massfractions in the organic phase, preferred 5-10% massfraction, and wherein phosgene concentration can be the same or different in the first organic phase and the Second Organic Phase.
Steps d of the present invention) for finishing rear in reaction solution until two step photochmeical reactions, add respectively end-capping reagent and catalyzer and carry out end-blocking and linked reaction, and when adding end-capping reagent and catalyzer, add alkali hydroxide soln to control pH value in reaction greater than 12, separation and purification obtained polycarbonate resin after question response finished.
The inventive method steps d) in, described end-capping reagent can be single phenolic compounds such as phenol, p-tert-butylphenol, cumyl phenol or isooctyl phenol, preferred phenol or p-tert-butylphenol add in the random time section before wherein end-capping reagent can be chosen in after initial bisphenol sodium salt aqueous phase or the photochmeical reaction and to add to catalyzer.
Steps d in the inventive method) in, described catalyzer can prepare catalyzer known in the polycarbonate technique for interface phosgenations such as triethylamine, N-ethylpiperidine, trialkylamine, N-sec.-propyl piperidines or N-ethylmorpholines, preferred triethylamine or N-ethylpiperidine.。
In the inventive method, when carrying out the end-blocking linked reaction, also need add an amount of alkali metal hydroxide with the pH value that guarantees reaction process greater than 12.Finally by removing water impurity and inert organic solvents, namely make the polycarbonate resin of high molecular.
The inventive method steps d) in, described alkali metal hydroxide is sodium hydroxide or potassium hydroxide, preferred sodium hydroxide.Described alkali metal hydroxide aqueous solution can be sodium hydroxide, potassium hydroxide etc., preferred sodium hydroxide.
The present invention also provides a kind of reactive system for aforesaid method, and described system comprises: three mixing tanks 1,2,3, three pumps 4,5,6, two tubular reactors 7,8, with two reactors 9,10, wherein, mixing tank 1,2 is connected with the entrance of tubular reactor 7 by pump 4,5 respectively; The outlet of tubular reactor 7 is connected with the entrance of tubular reactor 8; Mixing tank 3 is connected with tubular reactor 8 entrances by pump 6; The outlet of tubular reactor links to each other with reactor 9, and reactor 9 is provided with end-capping reagent and alkali metal soln adds pipeline; Reactor 9 is connected with reactor 10, and reactor 10 is provided with the adding pipeline of catalyzer and alkali metal soln.
The present invention considers that the phosgene that is dissolved in the organic solvent and the bis-phenol reaction meeting that is dissolved in the alkali metal hydroxide aqueous solution are chloro manthanoate group with the phenol negative oxygen ion groups converted of a part, and phenol negative oxygen ion group and chloro manthanoate group have the different hydrophilic lipophilicity, when only using a small amount of phosgene, can obtain a certain amount of prepolymer that contains simultaneously two kinds of end groups, the similar a kind of surfactant of this prepolymer, directional profile is in the oil-water two-phase interfaces place, can effectively reduce interfacial tension, keep the stability of emulsion.Take dihydroxyphenyl propane as example, its structural formula is as follows:
The organic phase solution that the present invention at first will be dissolved with total phosgene formula ratio 5～20% massfraction phosgene is pre-mixed with the basic metal aqueous solution that is dissolved with bis-phenol and reacts, form initial latex, subsequently this initial latex is mixed with remaining phosgene organic phase solution again and react.Because in the first step, a small amount of phosgene and aqueous phase phenol negative oxygen ion radical reaction generate a certain amount of surfactant that reduces interfacial tension, can effectively increase the stability of water-oil interface, improve the mixed effect of organic phase and water, impel more phenol negative oxygen ion to be distributed in phase interface, thereby effectively reduce hydrolysis and alkaline hydrolysis side reaction that phosgene occurs at water oil phase interface, the end group concentration of control polycarbonate prepolymer, reduce the phosgene consumption, improve the quality of products.
From the disclosed polycarbonate interface phosgenation preparation technologies such as present existing document and patent, do not utilize like this mode of phosgene Multistep feeding, the class tensio-active agent that generates by reaction process reduces interfacial tension, strengthen the intermixing of water and organic phase, the specific examples of control reaction oil water termination.The present invention adopts above-mentioned measure to improve dexterously intermixing efficient, more effectively utilizes phosgene, has reduced the phosgene loss, the wastage rate of phosgene can be reduced in 10%, guarantees simultaneously to produce high-quality polycarbonate products.
The present invention can effectively reduce hydrolysis and the alkaline hydrolysis side reaction that phosgene occurs at water oil phase interface, and the end group concentration of control polycarbonate prepolymer reduces the phosgene consumption, improves the quality of products.
Description of drawings
Fig. 1 is reaction system continuous operation process schematic flow sheet 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, at first in mixing tank 1, a certain amount of alkali metal hydroxide aqueous solution and bis-phenol or polyphenolic substance are formed water according to reaction desired raw material amount mixed dissolution; In mixing tank 2 and 3, the phosgene of formula ratio mixed respectively by a certain percentage forming organic phase one and organic phase two with inert organic solvents.Then the water in mixing tank 1 and 2 and organic phase one are delivered in the premixing reaction device 6 simultaneously, wherein the phosgene amount of mixing tank 2 interior conveyings accounts for 5～20% massfractions of total formula ratio, the profit two-phase is interior after the required residence time at premixing reaction device 6, enter actinic reactor 7, simultaneously the organic phase that is dissolved with phosgene two in the mixing tank 3 is delivered to actinic reactor 7 and reacts, wherein the phosgene amount of mixing tank 3 interior conveyings accounts for 80～95% massfractions of total formula ratio.Reaction entered after the required residence time carries out end-blocking and linked reaction successively in polycondensation reactor 8 and 9, add simultaneously a certain amount of alkali hydroxide soln with the pH value of control reaction, finally be prepared into polycarbonate resin through the two-phase separation and purification with after removing organic solvent.
Used raw material is respectively in following examples:
Dihydroxyphenyl propane: technical grade, available from Lanxing Chemical New Material Co., Ltd. (Wuxi resin processing plant);
Sodium hydroxide: 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.;
Hydrochloric acid: analytical pure, available from Laiyang Shandong Province city economic and technological development zone Fine Chemical Works.
The content analysis of chloroformate group adopts ultraviolet spectroscopy in the reaction solution organic phase.Utilize the reaction product of chloroformate group and 4-(4-nitrobenzyl) pyridine (NBP) that the principle of absorption is arranged under visible light, choose 420nm as detecting wavelength, extrapolate the content of chloroformate group by the concentration of measuring the two reaction product.
Embodiment 1
Add respectively 600.5g dihydroxyphenyl propane, 3186.5g water and 214.3g sodium hydroxide in mixing tank 1, mixed dissolution forms water; In mixing tank 2, add respectively the liquid phosgene of 28.1g and 440.2g methylene dichloride, mix forming organic phase one; In mixing tank 3, add respectively the liquid phosgene of 252.9g and 3961.4g methylene dichloride, mix forming organic phase two.Water and organic phase one are squeezed in the premixing reaction device that is made of static mixer with the flow of 133.4g/min and 15.6g/min respectively, stop and to enter behind the 10s equally in the actinic reactor that is consisted of by static mixer, simultaneously in reactor, squeeze into organic phase two, both hybrid reactions with the flow of 140.5g/min.Material enters in the stirred-tank reactor of two stills series connection stop 30s in actinic reactor after, and add the end-capping reagent phenol/dichloromethane solution of 5% massfraction in the first still with the flow of 4.3g/min, catalyst of triethylamine/the dichloromethane solution that adds 1.5% massfraction with the flow of 2.9g/min in the second still, in reactor, add a certain amount of 30% aqueous sodium hydroxide solution respectively simultaneously, control pH value is reacted 30min more than 12.Reaction product obtains polycarbonate resin 670.1g through separation and purification and after removing organic solvent.The phosgene charging accounts for 10% of total formula ratio in the organic phase one, and the phosgene overrate is 8% molar fraction.Final dihydroxyphenyl propane transformation efficiency is 99.1%, adopting the number-average molecular weight of the final polycarbonate resin of gpc analysis is 19938, molecular weight distribution is 1.9, and the concentration of chloroformate group is 0.54 mole of chloroformate group/every liter of dichloromethane solution that is dissolved with phosgene in the initial latex of employing ultra-violet analysis premixing reaction device outlet.
Add respectively 600.8g dihydroxyphenyl propane, 3186.9g water and 214.5g sodium hydroxide in mixing tank 1, mixed dissolution forms water; In mixing tank 2, add respectively the liquid phosgene of 56.2g and 880.3g methylene dichloride, mix forming organic phase one; In mixing tank 3, add respectively the liquid phosgene of 224.8g and 3521.2g methylene dichloride, mix forming organic phase two.Water and organic phase one are squeezed in the premixing reaction device that is made of static mixer with the flow of 133.4g/min and 31.2g/min respectively, stop and to enter behind the 10s equally in the actinic reactor that is consisted of by static mixer, simultaneously in reactor, squeeze into organic phase two, both hybrid reactions with the flow of 124.9g/min.Material enters in the stirred-tank reactor of two stills series connection stop 30s in actinic reactor after, and add the end-capping reagent phenol/dichloromethane solution of 5% massfraction in the first still with the flow of 4.3g/min, catalyst of triethylamine/the dichloromethane solution that adds 1.5% massfraction with the flow of 2.9g/min in the second still, in reactor, add a certain amount of 30% aqueous sodium hydroxide solution respectively simultaneously, control pH value is reacted 30min more than 12.Reaction product obtains polycarbonate resin 666.6g through separation and purification and after removing organic solvent.The phosgene charging accounts for 20% of total formula ratio in the organic phase one, and the phosgene overrate is 8% molar fraction.Final dihydroxyphenyl propane transformation efficiency is 98.6%, adopting the number-average molecular weight of the final polycarbonate resin of gpc analysis is 20140, molecular weight distribution is 2.1, and the concentration of chloroformate group is 0.52 mole of chloroformate group/every liter of dichloromethane solution that is dissolved with phosgene in the initial latex of employing ultra-violet analysis premixing reaction device outlet.
Embodiment 3
Add respectively 600.6g dihydroxyphenyl propane, 3186.6g water and 214.3g sodium hydroxide in mixing tank 1, mixed dissolution forms water; In mixing tank 2, add respectively the liquid phosgene of 14.1g and 220.1g methylene dichloride, mix forming organic phase one; In mixing tank 3, add respectively the liquid phosgene of 266.9g and 4181.5g methylene dichloride, mix forming organic phase two.Water and organic phase one are squeezed in the premixing reaction device that is made of static mixer with the flow of 133.4g/min and 7.8g/min respectively, stop and to enter behind the 10s equally in the actinic reactor that is consisted of by static mixer, simultaneously in reactor, squeeze into organic phase two, both hybrid reactions with the flow of 148.3g/min.Material enters in the stirred-tank reactor of two stills series connection stop 30s in actinic reactor after, and add the end-capping reagent phenol/dichloromethane solution of 5% massfraction in the first still with the flow of 4.3g/min, catalyst of triethylamine/the dichloromethane solution that adds 1.5% massfraction with the flow of 2.9g/min in the second still, in reactor, add a certain amount of 30% aqueous sodium hydroxide solution respectively simultaneously, control pH value is reacted 30min more than 12.Reaction product obtains polycarbonate resin 652g through separation and purification and after removing organic solvent.The phosgene charging accounts for 5% of total formula ratio in the organic phase one, and the phosgene overrate is 8% molar fraction.Final dihydroxyphenyl propane transformation efficiency is 96.4%, adopting the number-average molecular weight of the final polycarbonate resin of gpc analysis is 19141, molecular weight distribution is 2.3, and the concentration of chloroformate group is 0.57 mole of chloroformate group/every liter of dichloromethane solution that is dissolved with phosgene in the initial latex of employing ultra-violet analysis premixing reaction device outlet.
Add respectively 600.5g dihydroxyphenyl propane, 3186.3g water and 214.4g sodium hydroxide in mixing tank 1, mixed dissolution forms water; In mixing tank 2, add respectively the liquid phosgene of 28g and 440.1g methylene dichloride, mix forming organic phase one; In mixing tank 3, add respectively the liquid phosgene of 253g and 3961.5g methylene dichloride, mix forming organic phase two.Water and organic phase one are squeezed in the premixing reaction device that is made of static mixer with the flow of 133.4g/min and 15.6g/min respectively, stop and to enter behind the 20s equally in the actinic reactor that is consisted of by static mixer, simultaneously in reactor, squeeze into organic phase two, both hybrid reactions with the flow of 140.5g/min.Material enters in the stirred-tank reactor of two stills series connection stop 30s in actinic reactor after, and add the end-capping reagent phenol/dichloromethane solution of 5% massfraction in the first still with the flow of 4.3g/min, catalyst of triethylamine/the dichloromethane solution that adds 1.5% massfraction with the flow of 2.9g/min in the second still, in reactor, add a certain amount of 30% aqueous sodium hydroxide solution respectively simultaneously, control pH value is reacted 30min more than 12.Reaction product obtains polycarbonate resin 647.3g through separation and purification and after removing organic solvent.The phosgene charging accounts for 10% of total formula ratio in the organic phase one, and the phosgene overrate is 8% molar fraction.Final dihydroxyphenyl propane transformation efficiency is 95.7%, adopting the number-average molecular weight of the final polycarbonate resin of gpc analysis is 19380, molecular weight distribution is 2.4, and the concentration of chloroformate group is 0.28 mole of chloroformate group/every liter of dichloromethane solution that is dissolved with phosgene in the initial latex of employing ultra-violet analysis premixing reaction device outlet.
Embodiment 5
Add respectively 600.4g dihydroxyphenyl propane, 3186.4g water and 214.5g sodium hydroxide in mixing tank 1, mixed dissolution forms water; In mixing tank 2, add respectively the liquid phosgene of 28g and 440.2g methylene dichloride, mix forming organic phase one; In mixing tank 3, add respectively the liquid phosgene of 253g and 3961.4g methylene dichloride, mix forming organic phase two.Water and organic phase one are squeezed in the premixing reaction device that is made of static mixer with the flow of 133.4g/min and 15.6g/min respectively, stop and to enter behind the 30s equally in the actinic reactor that is consisted of by static mixer, simultaneously in reactor, squeeze into organic phase two, both hybrid reactions with the flow of 140.5g/min.Material enters in the stirred-tank reactor of two stills series connection stop 30s in actinic reactor after, and add the end-capping reagent phenol/dichloromethane solution of 5% massfraction in the first still with the flow of 4.3g/min, catalyst of triethylamine/the dichloromethane solution that adds 1.5% massfraction with the flow of 2.9g/min in the second still, in reactor, add a certain amount of 30% aqueous sodium hydroxide solution respectively simultaneously, control pH value is reacted 30min more than 12.Reaction product obtains polycarbonate resin 630.6g through separation and purification and after removing organic solvent.The phosgene charging accounts for 10% of total formula ratio in the organic phase one, and the phosgene overrate is 8% molar fraction.Final dihydroxyphenyl propane transformation efficiency is 93.2%, adopting the number-average molecular weight of the final polycarbonate resin of gpc analysis is 18156, molecular weight distribution is 2.5, and the concentration of chloroformate group is 0.17 mole of chloroformate group/every liter of dichloromethane solution that is dissolved with phosgene in the initial latex of employing ultra-violet analysis premixing reaction device outlet.
Add respectively 600.4g dihydroxyphenyl propane, 3186.3g water and 214.3g sodium hydroxide in mixing tank 1, mixed dissolution forms water; In mixing tank 2, add respectively the liquid phosgene of 28.1g and 440.1g methylene dichloride, mix forming organic phase one; In mixing tank 3, add respectively the liquid phosgene of 252.9g and 3961.5g methylene dichloride, mix forming organic phase two.Water and organic phase one are squeezed in the premixing reaction device that is made of static mixer with the flow of 133.4g/min and 15.6g/min respectively, stop and to enter behind the 5s equally in the actinic reactor that is consisted of by static mixer, simultaneously in reactor, squeeze into organic phase two, both hybrid reactions with the flow of 140.5g/min.Material enters in the stirred-tank reactor of two stills series connection stop 30s in actinic reactor after, and add the end-capping reagent phenol/dichloromethane solution of 5% massfraction in the first still with the flow of 4.3g/min, catalyst of triethylamine/the dichloromethane solution that adds 1.5% massfraction with the flow of 2.9g/min in the second still, in reactor, add a certain amount of 30% aqueous sodium hydroxide solution respectively simultaneously, control pH value is reacted 30min more than 12.Reaction product obtains polycarbonate resin 640g through separation and purification and after removing organic solvent.The phosgene charging accounts for 10% of total formula ratio in the organic phase one, and the phosgene overrate is 8% molar fraction.Final dihydroxyphenyl propane transformation efficiency is 94.6%, adopting the number-average molecular weight of the final polycarbonate resin of gpc analysis is 18757, molecular weight distribution is 2.4, and the concentration of chloroformate group is 0.33 mole of chloroformate group/every liter of dichloromethane solution that is dissolved with phosgene in the initial latex of employing ultra-violet analysis premixing reaction device outlet.
Embodiment 7
Add respectively 600.3g dihydroxyphenyl propane, 3186.4g water and 214.2g sodium hydroxide in mixing tank 1, mixed dissolution forms water; In mixing tank 2, add respectively the liquid phosgene of 28.1g and 1760.6g methylene dichloride, mix forming organic phase one; In mixing tank 3, add respectively the liquid phosgene of 252.9g and 2640.9g methylene dichloride, mix forming organic phase two.Water and organic phase one are squeezed in the premixing reaction device that is made of static mixer with the flow of 133.4g/min and 59.6g/min respectively, stop and to enter behind the 10s equally in the actinic reactor that is consisted of by static mixer, simultaneously in reactor, squeeze into organic phase two, both hybrid reactions with the flow of 96.5g/min.Material enters in the stirred-tank reactor of two stills series connection stop 30s in actinic reactor after, and add the end-capping reagent phenol/dichloromethane solution of 5% massfraction in the first still with the flow of 4.3g/min, catalyst of triethylamine/the dichloromethane solution that adds 1.5% massfraction with the flow of 2.9g/min in the second still, in reactor, add a certain amount of 30% aqueous sodium hydroxide solution respectively simultaneously, control pH value is reacted 30min more than 12.Reaction product obtains polycarbonate resin 626.6g through separation and purification and after removing organic solvent.The phosgene charging accounts for 10% of total formula ratio in the organic phase one, and the phosgene overrate is 8% molar fraction.Final dihydroxyphenyl propane transformation efficiency is 92.6%, adopting the number-average molecular weight of the final polycarbonate resin of gpc analysis is 18465, molecular weight distribution is 2.4, and the concentration of chloroformate group is 0.106 mole of chloroformate group/every liter of dichloromethane solution that is dissolved with phosgene in the initial latex of employing ultra-violet analysis premixing reaction device outlet.
Add respectively 600.3g dihydroxyphenyl propane, 3186.4g water and 214.4g sodium hydroxide in mixing tank 1, mixed dissolution forms water; In mixing tank 2, add respectively the liquid phosgene of 28.1g and 264.1g methylene dichloride, mix forming organic phase one; In mixing tank 3, add respectively the liquid phosgene of 252.9g and 4137.4g methylene dichloride, mix forming organic phase two.Water and organic phase one are squeezed in the premixing reaction device that is made of static mixer with the flow of 133.4g/min and 9.7g/min respectively, stop and to enter behind the 10s equally in the actinic reactor that is consisted of by static mixer, simultaneously in reactor, squeeze into organic phase two, both hybrid reactions with the flow of 146.4g/min.Material enters in the stirred-tank reactor of two stills series connection stop 30s in actinic reactor after, and add the end-capping reagent phenol/dichloromethane solution of 5% massfraction in the first still with the flow of 4.3g/min, catalyst of triethylamine/the dichloromethane solution that adds 1.5% massfraction with the flow of 2.9g/min in the second still, in reactor, add a certain amount of 30% aqueous sodium hydroxide solution respectively simultaneously, control pH value is reacted 30min more than 12.Reaction product obtains polycarbonate resin 631.3g through separation and purification and after removing organic solvent.The phosgene charging accounts for 10% of total formula ratio in the organic phase one, and the phosgene overrate is 8% molar fraction.Final dihydroxyphenyl propane transformation efficiency is 93.3%, adopting the number-average molecular weight of the final polycarbonate resin of gpc analysis is 18735, molecular weight distribution is 2.3, and the concentration of chloroformate group is 0.702 mole of chloroformate group/every liter of dichloromethane solution that is dissolved with phosgene in the initial latex of employing ultra-violet analysis premixing reaction device outlet.
Embodiment 9
Add respectively 600.5g dihydroxyphenyl propane, 3186.4g water and 214.2g sodium hydroxide in mixing tank 1, mixed dissolution forms water; In mixing tank 2, add respectively the liquid phosgene of 28g and 440.1g methylene dichloride, mix forming organic phase one; In mixing tank 3, add respectively the liquid phosgene of 253g and 3961.5g methylene dichloride, mix forming organic phase two.Water and organic phase one squeezed into the flow of 133.4g/min and 15.6g/min respectively carry out hybrid reaction in the T-shaped premixer, enter in the actinic reactor that is consisted of by static mixer after stopping 10s, simultaneously in reactor, squeeze into organic phase two, both hybrid reactions with the flow of 140.5g/min.Material enters in the stirred-tank reactor of two stills series connection stop 30s in actinic reactor after, and add the end-capping reagent phenol/dichloromethane solution of 5% massfraction in the first still with the flow of 4.3g/min, catalyst of triethylamine/the dichloromethane solution that adds 1.5% massfraction with the flow of 2.9g/min in the second still, in reactor, add a certain amount of 30% aqueous sodium hydroxide solution respectively simultaneously, control pH value is reacted 30min more than 12.Reaction product obtains polycarbonate resin 658.9g through separation and purification and after removing organic solvent.The phosgene charging accounts for 10% of total formula ratio in the organic phase one, and the phosgene overrate is 8% molar fraction.Final dihydroxyphenyl propane transformation efficiency is 97.6%, adopting the number-average molecular weight of the final polycarbonate resin of gpc analysis is 19031, molecular weight distribution is 2.1, and the concentration of chloroformate group is 0.47 mole of chloroformate group/every liter of dichloromethane solution that is dissolved with phosgene in the initial latex of employing ultra-violet analysis premixing reaction device outlet.
Comparative Examples 1
Add respectively 600.4g dihydroxyphenyl propane, 3186.5g water and 214.2g sodium hydroxide in mixing tank 1, mixed dissolution forms water; In mixing tank 2, add respectively the liquid phosgene of 28g and 440.1g methylene dichloride, mix forming organic phase one; In mixing tank 3, add respectively the liquid phosgene of 253g and 3961.5g methylene dichloride, mix forming organic phase two.Water and organic phase squeezed into the flow of 133.4g/min and 156.1g/min respectively carry out photochmeical reaction in the actinic reactor that is consisted of by static mixer, material enters in the stirred-tank reactor of two stills series connection stop 30s in actinic reactor after, and add the end-capping reagent phenol/dichloromethane solution of 5% massfraction in the first still with the flow of 4.3g/min, catalyst of triethylamine/the dichloromethane solution that adds 1.5% massfraction with the flow of 2.9g/min in the second still, in reactor, add a certain amount of 30% aqueous sodium hydroxide solution respectively simultaneously, control pH value is reacted 30min more than 12.Reaction product obtains polycarbonate resin 591g through separation and purification and after removing organic solvent.The phosgene overrate is 8% molar fraction, and the dihydroxyphenyl propane transformation efficiency is 87.3%, and the number-average molecular weight that adopts gpc analysis to get final polycarbonate resin is 17769, and molecular weight distribution is 2.7.
Claims (18)
1. the method for a preparing polycarbonate by continuous two-phase interface method is characterized in that, described method comprises the steps:
A) bis-phenol or polyphenolic substance are dissolved in form water in the alkali metal hydroxide aqueous solution; The phosgene and the inert organic solvents that account for total phosgene amount 5～20% massfractions are formed the first organic phase; The phosgene of residual content and inert organic solvents are formed Second Organic Phase, wherein in the first organic phase or the phosgene concentration in the Second Organic Phase be 5～20% massfractions;
B) water and the first organic phase are carried out premixing reaction, the premixing reaction residence time is 1～60s, namely gets the premixing reaction product;
C) premixing reaction product and Second Organic Phase are carried out dispersing and mixing and carry out photochmeical reaction, the photochmeical reaction residence time is 5s to 20min;
D) after photochmeical reaction is finished, add first end-capping reagent and carry out end capping, then add catalyzer and carry out linked reaction, and when adding end-capping reagent and catalyzer, add alkali hydroxide soln to control pH value in reaction greater than 12, separation and purification obtained polycarbonate resin after question response finished.
2. method according to claim 1 is characterized in that, bis-phenol or the polyphenol of described step in a) is dihydroxyphenyl propane, tetrabromo-bisphenol or three p-hydroxybenzene ethane.
3. method according to claim 2 is characterized in that, the inert organic solvents of described step in a) is that make up arbitrarily methylene dichloride, ethylene dichloride, trichloroethane, tetrachloroethane, toluene, chlorobenzene, tetracol phenixin or they.
4. method according to claim 3 is characterized in that, described step a) the middle concentration of phosgene in the first organic phase or Second Organic Phase is the 5-10% massfraction.
5. method according to claim 4 is characterized in that, the alkali metal hydroxide aqueous solution of described step described in a) is sodium hydroxide or potassium hydroxide.
6. method according to claim 5 is characterized in that, described step a) in the concentration of aqueous phase bis-phenol or polyphenol be 5～20% massfractions.
7. method according to claim 6 is characterized in that, described step a) in the concentration of aqueous phase bis-phenol or polyphenol be 6～15% massfractions.
8. method according to claim 7 is characterized in that, described step a) in the concentration of aqueous phase bis-phenol or polyphenol be 10～15% massfractions.
9. method according to claim 6 is characterized in that, described step a) in phosgene in the first organic phase account for 6～15% massfractions of total phosgene amount.
10. method according to claim 9 is characterized in that, described step b) in water and the residence time of phosgene organic phase in the premixing reaction device be 2～30s.
11. method according to claim 10 is characterized in that, step b) concentration of chloroformate group should be greater than 0.1 mole of chloroformate group/every liter of inertia organic phase solution that is dissolved with phosgene in the gained premixing reaction product.
12. method according to claim 11 is characterized in that, step b) concentration of chloroformate group is 0.3～0.7 mole of chloroformate group/every liter of inertia organic phase solution that is dissolved with phosgene in the gained premixing reaction product.
13. method according to claim 11 is characterized in that, described step b) in premixing reaction in the mixing reactor of tubular reactor, T-shaped mixing reactor or its combination, carry out.
14. method according to claim 13 is characterized in that, described step b) in premixing reaction in the continuous pipe type mixing tank, carry out.
15. method according to claim 14 is characterized in that, described step b) in premixing reaction in being filled with the tubular reactor of static mixing element, carry out.
16. method according to claim 14 is characterized in that, described step c) middle photochmeical reaction is at tubular reactor, continuous stirred tank reactor (CSTR) or loop reactor, or they carry out in the combined hybrid reactor arbitrarily.
17. method according to claim 16 is characterized in that, described step c) in photochmeical reaction in continuous tubular reactor, carry out.
18. method according to claim 16 is characterized in that, described steps d) in end-capping reagent be phenol, p-tert-butylphenol, cumyl phenol or isooctyl phenol; Catalyzer is triethylamine, N-ethylpiperidine, trialkylamine, N-sec.-propyl piperidines or N-ethylmorpholine.
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| WO2010110984A1 (en) * | 2009-03-24 | 2010-09-30 | Dow Global Technologies Inc. | Method for monitoring monomer concentration in interfacial polycarbonate manufacturing process |
| CN102030895B (en) * | 2010-11-05 | 2012-04-25 | 烟台万华聚氨酯股份有限公司 | Method for preparing polycarbonate with continuous two-phase interface phosgene method |
| CN102516519B (en) | 2011-11-18 | 2014-05-21 | 万华化学（宁波）有限公司 | Method for preparing polycarbonate |
| CN102675619B (en) * | 2011-12-05 | 2013-06-12 | 陕西延长石油（集团）有限责任公司 | Polymerization reaction device for producing aromatic polycarbonate by melting transesterification method |
| CN102558532B (en) * | 2011-12-14 | 2013-12-18 | 湖南海利化工股份有限公司 | Preparation method of polycarbonate |
| CN104419000B (en) * | 2013-08-30 | 2016-01-20 | 万华化学集团股份有限公司 | A kind of continuous two-phase interface phosgenation prepares the method for branching polycarbonate |
| CN111408319B (en) * | 2020-03-26 | 2022-01-28 | 北京理工大学 | Method for preparing p-tert-butyl toluene |
| CN114230779A (en) * | 2022-01-10 | 2022-03-25 | 万华化学集团股份有限公司 | Polycarbonate and preparation method and application thereof |
| CN114653330B (en) * | 2022-03-30 | 2023-08-11 | 西安近代化学研究所 | Device and process for dynamically and continuously preparing polycarbonate |
| CN115785426B (en) * | 2022-11-21 | 2024-04-16 | 万华化学集团股份有限公司 | Polycarbonate and preparation method thereof |
| CN117327265B (en) * | 2023-11-09 | 2024-04-16 | 上海芮澜工程科技有限公司 | Preparation method of polycarbonate |
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| EP0520272B1 (en) * | 1991-06-27 | 1995-08-09 | Bayer Ag | Continuous preparation of polycarbonates |
| CN1385453A (en) * | 2001-04-12 | 2002-12-18 | 拜尔公司 | Method for preapring polycarbonic ester |
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| EP0520272B1 (en) * | 1991-06-27 | 1995-08-09 | Bayer Ag | Continuous preparation of polycarbonates |
| CN1385453A (en) * | 2001-04-12 | 2002-12-18 | 拜尔公司 | Method for preapring polycarbonic ester |
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