CN1194656A - Process for producing aromatic polycarbonate resin - Google Patents
Process for producing aromatic polycarbonate resin Download PDFInfo
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- CN1194656A CN1194656A CN 97190631 CN97190631A CN1194656A CN 1194656 A CN1194656 A CN 1194656A CN 97190631 CN97190631 CN 97190631 CN 97190631 A CN97190631 A CN 97190631A CN 1194656 A CN1194656 A CN 1194656A
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- monohydroxy compound
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- freezing point
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Abstract
A process for producing an aromatic polycarbonate resin by melt polycondensing an aromatic dihydroxy compound and an aromatic carbonic acid diester, wherein a mixture solution comprising the same aromatic monohydroxy compound as an aromatic monohydroxy compound by-produced from a reaction system as a main component and a freezing-point depressant for the aromatic monohydroxy compound, such as a glycol, is used as a scrubbing solution for the recovery of the by-produced aromatic monohydroxy compound by a scrubber type condenser.
Description
Invention field
The present invention relates to produce the method for aromatic polycarbonate resin, more particularly, relate to the method for the production aromatic polycarbonate resin with following characteristics: it comprises the step of aromatic dihydroxy compound with aromatic carbonate diester melt phase polycondensation; And it can be with technical scale operation continuously for a long time.
Prior art
Aromatic polycarbonate resin has good mechanical property, and for example the shock resistance and the good thermotolerance and the transparency are widely used as moulding material.This class aromatic polycarbonate resin is produced with currently known methods, and these methods comprise: for example diphenol is directly and the interfacial process of phosgene reaction to allow aromatic dihydroxy compound; With allow aromatic dihydroxy compound for example diphenol and aromatic carbonate diester for example diphenyl carbonate under molten state, carry out the melt polycondensation method of transesterification reaction.
In these methods, allowing aromatic dihydroxy compound and aromatic carbonate diester carry out transesterify produces the method for polycarbonate and is: aromatic dihydroxy compound and aromatic carbonate diester are heated to highly make its fusing to 250～330 ℃, and for example make it carry out transesterification reaction in the presence of organic acid salt, inorganic acid salt, oxyhydroxide, hydride or the alkoxide of metal at molten state, reduced pressure and catalyzer.
In this transesterification reaction, need reclaim aromatic monohydroxy compound steam with condenser as byproduct, use cold aromatic monohydroxy compound to be suitable for use as this condenser as the washing type condenser of washing soln.But because the zero pour of aromatic monohydroxy compound is very high, the temperature of washing soln can not be fallen very lowly, so organic efficiency is very low and be difficult to keep the decompression pressure (degree of reduced pressure) of reaction needed.
For addressing the above problem, JP-A6-065367 (used here term " JP-A " is meant " uncensored and announce Japanese patent application ") suggestion use high boiling point and low melting component and without the by-product aromatic monohydroxy compound as washing soln.As the object lesson of the compound that is used as washing soln, the disclosure text has been enumerated the diphenyl ether of Tetraglycol 99, dibenzyl toluene and list or dialkyl group replacement, and wherein alkyl contains 8～18 carbon atoms.
But in the method, the by-product aromatic monohydroxy compound must be separated with a large amount of washing solns and allow washing soln circulate then.And general, the internal circulating load of washing soln must be that hundreds of times of by-product aromatic composition just can reach thorough washing.Therefore, this method causes cost of equipment and energy charge to increase, this industrial be disadvantageous.
In addition, if with the technical scale operation, aforesaid method can't be said and can be fit to long-term operate continuously.In other words, aforesaid method can not steady in a long-termly move, this is can solidify because of contained unreacted product and oligopolymer in the aromatic monohydroxy compound steam of discharging in reaction system, accumulates and be deposited on the washer bottom in washer, thereby outlet line is stopped up.Unreacted product and oligopolymer solidifies composition and the solubleness that is considered to depend on washing soln in the washer.Above-mentioned open text is mentioned, and this solidifying (page 3, the 3rd hurdle, the 36th～40 row) taken place in the washer of aforesaid method, and in an embodiment, after moving 7 days continuously, the washer bottom line begins to stop up (page 4, the 6th hurdle, the 30th～40 row).
Summary of the invention
Therefore first purpose of the present invention provides a kind of method, this method is being solidified and is being reclaimed and use washing type condenser and washing soln in the step of aromatic monohydroxy compound steam, this condenser has excellent organic efficiency, this washing soln mainly is made up of aromatic monohydroxy compound, and said steam is to be discharged by the reactive system in the melt polycondensation method.
Second purpose of the present invention provides process for producing aromatic polycarbonate resin, this method can be carried out the long-term stability operation, this is because in the aromatic monohydroxy compound steam process in reclaiming melt polycondensation method, contained unreacted product and oligopolymer can not solidify in the steam.
The 3rd purpose of the present invention provides process for producing aromatic polycarbonate resin, this method can reduce equipment cost and operation energy expenditure, these costs and consume to be for reclaim aromatic monohydroxy compound steam in the melt polycondensation method carry out washing soln circulation spent.
By discovering that the present inventor carried out, above-mentioned purpose of the present invention can reach with the method for producing aromatic polycarbonate resin by allowing aromatic dihydroxy compound and aromatic carbonate diester carry out melt phase polycondensation, wherein use mixing solutions to make washing soln, reclaim the aromatic monohydroxy compound of reaction system by-product by washing type condenser, said mixing solutions contains the aromatic monohydroxy compound identical with the aromatic monohydroxy compound of reactive system by-product, and with this freezing point lowering agent as main component and aromatic monohydroxy compound.Detailed Description Of The Invention
The detailed description of the invention is as follows.
Aromatic polycarbonate resin of the present invention is produced with melt polycondensation method.One of used parent material of the present invention is an aromatic dihydroxy compound.The illustrative examples of this aromatic dihydroxy compound comprises: two (4-hydroxyphenyl) methane, 2,2-two (4-hydroxyphenyl) propane [dihydroxyphenyl propane], 2,2-two (4-hydroxy-3-methyl phenyl) propane, 4,4-two (4-hydroxyphenyl) pentane, 2,2-two (4-hydroxyl-3, the 5-dichlorophenyl) propane, 2,2-two (4-hydroxyl-3, the 5-dibromo phenyl) propane, two (4-hydroxyphenyl) ether, two (3,5-two chloro-4-hydroxyphenyl) ether, P, P '-dihydroxybiphenyl, 3,3 '-two chloro-4,4 '-dihydroxybiphenyl, two (4-hydroxyphenyl) sulfone, two (3,5-dimethyl-4-hydroxyphenyl) sulfone, dihydroxy-benzene, Resorcinol, Resorcinol, 1,4-dihydroxyl-2, the 5-dichlorobenzene, 1,4-dihydroxyl-3-methylbenzene, two (4-hydroxyphenyl) thioether, two (4-hydroxyphenyl) sulfoxide etc.Wherein two (hydroxyaryl) alkane for example 2, and 2-two (4-hydroxyphenyl) propane is preferred especially.
The illustrative examples that is used as the aromatic carbonate diester of another kind of parent material comprises: diphenyl carbonate, carbonic acid dinaphthyl ester and carbonic acid bigeminy phenyl ester, wherein diphenyl carbonate is preferred especially.
Usually, the method for carrying out melt polycondensation reaction is: (in nitrogen atmosphere) limit heating under reduced pressure, limit are stirred aromatic dihydroxy compound and aromatic carbonate diester and are boiled off the aromatic monohydroxy compound of by-product.
For improving polymerization velocity, can use catalyzer.The illustrative examples of catalyzer comprises: the oxyhydroxide of basic metal and alkaline-earth metal is sodium hydroxide and potassium hydroxide for example; An alkali metal salt, the oxyhydroxide quaternary ammonium salt of alkaline earth salt and boron and aluminium; Basic metal and alkaline-earth alkoxides; Basic metal and alkaline-earth metal organic acid salt; Zn cpds; Boron compound; Silicon compound; Germanium compound; Organo-tin compound; Lead compound; Compounds; Antimony compounds; Manganic compound; Titanium compound; Zirconium compounds; Or the like, all these compounds are generally used for esterification and transesterification reaction.But catalyzer is not limited to these.Above-mentioned substance can use separately, or two or multiplely unite use.Per 1 mole of aromatic dihydroxy compound as parent material, catalyst levels is 10
-8～10
-3Mole, preferred 10
-7～5 * 10
-4Mole, more preferably 5 * 10
-7～2 * 10
-4Mole.
, in above-mentioned method of producing aromatic polycarbonate resin with melt-polycondensation, when carrying out polycondensation, the aromatic monohydroxy compound of by-product is drained into beyond the reactive system with the form of steam according to the present invention.Being drained into reactive system aromatic monohydroxy compound steam in addition is recovered in the condenser of washing type.
When the aromatic monohydroxy compound steam of discharging is not higher than 1 in decompression (reduced pressure), 000Pa preferably is not higher than when being inhaled into and reclaiming under the 500Pa condition, adopts the present invention that superiority is arranged.When this washing type condenser moved under high like this decompression, the temperature that requires washing soln was 10～50 ℃, preferred 20～30 ℃.Under low like this temperature, the aromatic monohydroxy compound of recovery solidifies, and operation is difficult to continuously.
But, in the present invention, use contains the aromatic monohydroxy compound that the aromatic monohydroxy compound of freezing point lowering agent can avoid reclaiming as washing soln and solidifies, the operation continous-stable is carried out, and may command unreacted product and oligopolymer molten state and with cure form not beyond the aromatic monohydroxy compound steam drains into reactive system.Therefore, according to the present invention, washing type condenser can for a long time, continuously and stably move.
Washing the washing soln that uses in the type condenser in the present invention is a kind of mixture solution, wherein contain with by the aromatic monohydroxy compound of reactive system by-product identical aromatic monohydroxy compound and freezing point lowering agent as main component.The content of freezing point lowering agent is counted 0.5～50 weight % with washing soln, preferred 1～30 weight %.
When the ratio of freezing point lowering agent was lower than 0.5 weight % of washing soln weight, the freezing point of washing soln can not be fallen enough lowly, the result, and washing soln solidifies easily.Also unfavorable when the ratio of freezing point lowering agent is higher than 50 weight %, because the cost of recovery and circulation freezing point lowering agent increases, and, stop up easily because oligopolymer solubleness descends.
Contained aromatic monohydroxy compound ratio as main component is 50～99.5 weight % in the washing soln, preferred 70～99 weight %.
To be not less than 190 ℃ under normal pressure be favourable to the boiling point of contained freezing point lowering agent in the washing soln, more preferably 210～350 ℃, preferred especially 220～300 ℃, this is to consider the working pressure of washing type condenser and adopt distillation procedure to carry out the circulation of washing soln.
Freezing point lowering agent can be the dibasic alcohol with following general formula (1) representative:
HO-(R-O) n-H (1) wherein R is-C
2H
4-or-C
3H
6-(it can be-CHCH
3-CH
2-or-CH
2CH
2GH
2-), n is 1～5 integer.
The illustrative examples of this di-alcohols comprises glycol ether, triglycol, Tetraglycol 99, hexaethylene glycol, propylene glycol, 1, ammediol and-dipropylene glycol that contracts (dipropylene glycol).Wherein, glycol ether, triglycol and composition thereof are preferred.
In the present invention, above-mentioned freezing point lowering agent can use separately, or can or multiplely unite use by two kinds.When only with a kind of freezing point lowering agent, triglycol most preferably.When multiple freezing point lowering agent was united use, the gross weight of freezing point lowering agent should be in above-mentioned scope.
The aromatic monohydroxy compound of washing soln use in the present invention is identical with the aromatic monohydroxy compound of by-product.According to the difference of used aromatic carbonate diester, the aromatic monohydroxy compound of by-product is also different, when using diphenyl carbonate, and by-product phenol, when using carbonic acid dinaphthyl ester, the by-product naphthols, when using carbonic acid bigeminy phenyl ester, the by-product phenylphenol.
Various types of condensers are spray tower, wet-wall tower, eddy flow washer, Venturi scrubber etc. for example, all can be used as the washing type condenser among the present invention, wherein is preferred with the spray tower.As long as use above-mentioned washing soln, the present invention just can implement in various types of condensers.
The method of contained aromatic monohydroxy compound and freezing point lowering agent concentration comprises in control and the adjusting washing soln of the present invention: freezing point lowering agent is added in the washing soln continuously to keep its constant concentration; Freezing point lowering agent added off and on make its concentration remain on stated limit in the washing soln; Or the like.Method therefor of the present invention do not had particular restriction.But no matter use which kind of method, the concentration of aromatic monohydroxy compound and freezing point lowering agent must be remained in the above-mentioned scope.
Washing soln is 10～50 ℃ of operations down, preferred 20～30 ℃.When the washing soln temperature was lower than 10 ℃, if do not increase the freezing point lowering agent consumption, then aromatic series list alkyl compound can be separated, thereby positions such as nozzle are stopped up easily.When the temperature of washing soln surpasses 50 ℃, decompression pressure and the organic efficiency that is difficult to keep in the system descended.
Pressure generally is not higher than 1 after decompression in the condenser, 000Pa, and when preferably not being higher than 500Pa, it is very approaching each other that the fusing point of aromatic monohydroxy compound and boiling point become, and the freezing point of washing soln can advantageously reduce.It is preferred especially that decompression pressure is not higher than 300Pa.
When the washing soln that is taken out by condenser bottom is carried out aftertreatment, can adopt this solution is all carried out purifying-separate and the abandon method of (scrapping).Can use any method that the present invention is not caused restriction.Purifying-separation method comprises distillation, crystallization etc., and discarding method comprises burning etc.No matter carry out which kind of aftertreatment, importantly reduce cost and energy charge.Since among the present invention the consumption of freezing point lowering agent seldom, cost can reduce.
Referring now to Fig. 1 the preferred post-treating method of washing soln is described.
The phenol steam that is produced by polymerization reactor is introduced into washing type condenser 9 through pipeline 1.In this washing type condenser 9, the washing soln that is cooled at condenser 11 contacts so that make the phenol condensation and be washed solution by the nozzle ejection and with the phenol steam and is absorbed.Washing soln is recovered in washing soln storage tank 10 by the condenser 9 bottoms pipeline 3 of flowing through.
With pump washing soln is circulated through pipeline 4 and water cooler 11.For avoiding the washing soln composition to change, the part washing soln is continuously supplied in the fractional column 12 through pipeline 5 because of the accumulation of phenol.Condenser of reference number 6 expressions.
In fractional column 12, phenol is recovered by the column top and washing soln is recovered by the column bottom.In case of necessity, with the washing soln cooling, send it back to washing soln storage tank 10 through pipeline 7 then.When the concentration of high boiling substance surpasses preset value, it is discharged through pipeline 8 by the column bottom.Well heater of reference number 13 expressions.When reclaimer operation intermittently carries out, surge tank is installed in pipeline 5 and 7 can be made reclaimer operation easier.The invention effect
According to the present invention, adopting with the aromatic monohydroxy compound that contains freezing point lowering agent is the washing type condenser of washing soln, and a kind of industrial favourable polycarbonate resin production method is provided.Promptly, the present invention can be recovered in the aromatic monohydroxy compound of by-product in the aforementioned production method with high efficient, can make the high decompression pressure of condenser maintenance and carry out the long-term stability operation, and can reduce the energy consumption that reclaims aromatic monohydroxy compound greatly with low heat loads.
[embodiment]
Provide following examples and comparative example so that further explain the present invention.As not pointing out in addition that " % " in embodiment and the comparative example is meant " being the % of benchmark with weight ".By use limiting viscosity that the Ubbelohde viscometer measures the 0.7g/dl dichloromethane solution by under establish an equation and try to achieve viscosity-average molecular weight.
[η]=1.23 * 10
-4M
0.83[embodiment 1]
Temperature of reaction and decompression back pressure are remained on 200 ℃ and 100mmHg (13 respectively, 300Pa), in the vertical stirred pot that fractional column is housed, supply with 2 continuously, 2-two (4-hydroxyphenyl) propane (dihydroxyphenyl propane), with 1 mole of dihydroxyphenyl propane is 1.05 diphenyl carbonates of benchmark, 2 * 10
-6Equivalent dihydroxyphenyl propane disodium salt and 1 * 10
-4The molten mixture of equivalent tetramethylammonium hydroxide and by the phenol of removing by-product in the rectifying column, thus react.
Temperature of reaction and decompression back pressure are remained on 270 ℃ and 10mmHg (1 less respectively, 330Pa) molten polymer of discharging in the vertical retort is supplied with in second vertical stirred pot that fractional column is housed continuously, and by the phenol of removing by-product in the rectifying column, thereby react.
To supply with the horizontal retort that washing type condenser and agitator are housed again continuously by the molten polymer that the second vertical retort is discharged, temperature of reaction and decompression pressure will be remained on 290 ℃ and 1mmHg (133Pa) respectively, and allow retort move for 2 weeks.
The phenol vapor of by-product is washed the type condenser and reclaims in horizontal retort, and washing soln is formed and operational condition is shown in table 1.
In operation, periodically take out part washing soln and supply and be used as the ethylene glycol of freezing point lowering agent so that contained glycol concentration in the washing soln is adjusted to 20～25%.
In service in 2 weeks does not observe the variation of decompression pressure, and stably to have obtained viscosity-average molecular weight by horizontal retort outlet be 22,500 polycarbonate resin.
After the operation, when horizontal retort and decompression/recovery system thereof are carried out dissembling inspection, do not find block part.
Operation result is shown in table 1.[embodiment 2]
React in mode similarly to Example 1, the freezing point lowering agent that difference is to be added in the used washing soln of washing type condenser of horizontal retort is a triglycol.
In service in 2 weeks, do not observe the variation of decompression pressure, and stably to have obtained viscosity-average molecular weight by the outlet of horizontal retort be 22,500 polycarbonate resin.
After the operation, when the recovery system of horizontal retort and retort is carried out dissembling inspection, do not find block part.
Operation result is listed in table 1 together with the result of embodiment 1.[comparative example 1]
To react with embodiment 1 and 2 same modes, difference is not add the freezing point depressant in the washing soln of washing type condenser of horizontal retort, make cleaning solvent but be used in 45 ℃ of purified petroleum benzin phenol that heat down, the decompression pressure of horizontal retort can not remain on 1.7mmHg (226Pa) or lower, and can not reclaim the phenol of by-product.Thereby after 20 hours, operate continuously is ended.
After the operation, when horizontal retort and recovery system were carried out dissembling inspection, the pipeline that is extended to vacuum pump by washing type condenser was stopped up by the phenol crystallization of by-product.
Operation result is shown in table 1 together with the result of embodiment 1 and 2.[comparative example 2]
Reacting with embodiment 1 and 2 same modes, difference is that spent glycol makes the washing soln in the washing type condenser of horizontal retort.
In service in 2 weeks, do not observe the variation of decompression pressure, and stably to obtain molecular-weight average by reaction unit outlet be 22,500 polycarbonate resin.
Operation result with embodiment 1 and 2 and the result of comparative example 1 be shown in table 1.
Table 1
| Washing soln is formed | Operational condition | Operation result | |||||
| Phenol (weight %) | Freezing point lowering agent (weight %) | The washing soln temperature (℃) | Decompression pressure (mmHg) [Pa] | Freezing point lowering agent consumption (kg/hr) | Phenol recovery rate (%) | Vapor line stops up | |
| ????Ex.1 | ????75～80 | Ethylene glycol 20～25 | ????20 | 1.0[133] no change | ????0.1 | ????98.4 | Do not have |
| ????Ex.2 | ????75～80 | Triglycol 20～25 | ????20 | 1.0[133] no change | ????0.1 | ????99.8 | Do not have |
| ??Comp.Ex.1 | ????100 | Do not use | ????45 | 1.7[226] change in time | ????0.0 | 0.00 can not reclaim | Vacuum pipeline is blocked |
| ??Comp.Ex.2 | ????0～5 | Ethylene glycol 95～100 | ????20 | 1.0[133] no change | 7.6 it is big | ????99.4 | Do not have |
Ex.: embodiment
Comp.Ex.: comparative example embodiment 3 and comparative example 3
Preparation as parent material contain dihydroxyphenyl propane and with 1 mole of dihydroxyphenyl propane be benchmark 1.02 mole of diphenyl carbonate molten mixture and be dissolved in solution in the phenol that contains 10 weight % water as 0.01 weight % dihydroxyphenyl propane disodium salt of catalyzer and 0.35 weight % tetramethylammonium hydroxide, be that the amount of the dihydroxyphenyl propane disodium salt of benchmark be 2 * 10 with volume pump first polymerization reactor of giving without interruption to guarantee with them with the 1mole dihydroxyphenyl propane
-6Equivalent.First polymerization reactor is vertical stirred pot, and the phenol that fractional column produces with the separation of polymeric process is housed, and with the multi-tubular condenser that is connected with 50 ℃ of hot water the phenol liquefaction that produces is also reclaimed.Part phenol is got back to the fractional column top as reflux solution, beyond other phenol is exhausted from system.First polymerization reactor remain on 200 ℃ and 100mmHg (13,330Pa), the polymkeric substance with utmost point low polymerization degree that wherein generates is taken out and second polymerization reactor of giving without interruption.Second polymerization reactor have answer the same function of device with first polymerization and remain on 250 ℃ and 10mmHg (1,330Pa) further carry out polymerization.Then, resulting polymers is taken out and is supplied to the trimerization reactor continuously.The trimerization reactor is the single screw rod stirred pot of a level, remains on 270 ℃ and 1mmHg (133Pa).The phenol that produces is directly guided in the washing type condenser, contacts so that reclaim and remove from system with washing soln.Again the polymkeric substance that forms in the trimerization reactor is supplied to the 4th polymerization reactor continuously, carries out polymerization until the polymerization degree that obtains being scheduled at this.
The 4th polymerization reactor is horizontal twin screw stirred pot, remains on 280 ℃ and 1mmHg (133Pa) to stir high-viscosity polymer.The phenol that produces directly be introduced in the washing type condenser and with the trimerization reactor in same mode reclaim.
The viscosity-average molecular weight that comes from the polymkeric substance of the 4th polymerization reactor is set in 22,500, contains the triglycol (TEG) of 20 weight % or the phenol (PhOH) of Tetraglycol 99 and washs as washing soln.After washing soln is cooled to 20 ℃, circulate by washing type condenser, polyreaction was carried out for 2 weeks continuously, reclaimed the phenol that polymerization process generates simultaneously.The phenol vapor that is produced by trimerization reactor and the 4th polymerization reactor is introduced into washing type condenser.The results are shown in following table 2.
Table 2
| Washing soln is formed | Operating period | Vapor line stops up | Liquid line stops up | |
| ????Ex.3 | ?PhOH/TEG＝ ????8/2 | 2 weeks | Not stifled | Not stifled |
| ??Comp.Ex.3 | Tetraglycol 99 | 1 week | Not stifled | Slightly stop up after 1 week |
Ex: embodiment
Comp.Ex: comparative example has carried out the solubility test of oligopolymer in washing soln for inquiring into the different reason of blockage.Obtain result shown in the following table 3.
Table 3
When employing contains 20% when making washing soln as the phenol of the triglycol of freezing point lowering agent, find that it can dissolve many oligopolymer.So think that this is the reason that is difficult for blocking pipeline.
| Washing soln is formed | The solubility test result |
| ????PhOH/TEG＝8/2 | Dissolved and be no less than 1.0 weight % oligopolymer |
| Tetraglycol 99 | Only dissolved 0.2 weight % oligopolymer |
Brief Description Of Drawings
Fig. 1 is suitable for schema that used washing soln in the inventive method is carried out aftertreatment.
Claims (7)
1. method of producing aromatic polycarbonate resin, this method comprises carries out melt phase polycondensation with aromatic dihydroxy compound and aromatic carbonate diester, wherein adopt a kind of mixture solution to make washing soln, reclaim the aromatic monohydroxy compound of by-product by washing type condenser, said mixture solution contains the aromatic monohydroxy compound identical with the aromatic monohydroxy compound of reactive system by-product, and with this as main component, also contain the freezing point lowering agent of this aromatic monohydroxy compound.
2. the process of claim 1 wherein that being recovered in of aromatic monohydroxy compound of reactive system by-product is not higher than 1, carries out under the decompression pressure of 000Pa.
3. the process of claim 1 wherein that the boiling point of freezing point lowering agent is not less than 190 ℃ under normal pressure.
4. the process of claim 1 wherein that the ratio that this washing soln contains aromatic monohydroxy compound is 50～99.5 weight %, the ratio of freezing point lowering agent is 0.5～50 weight %.
5. the process of claim 1 wherein that the ratio that this washing soln contains aromatic monohydroxy compound is 70～99 weight %, the ratio of freezing point lowering agent is 1～30 weight %.
6. the process of claim 1 wherein that freezing point lowering agent is the compound by following general formula (1) representative:
HO-(R-O)n-H????????????????(1)
Wherein R is-C
2H
4-or-C
3H
6-, n is 1～5 integer.
7. the process of claim 1 wherein that this freezing point lowering agent is glycol ether, triglycol or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97190631 CN1194656A (en) | 1996-04-11 | 1997-04-04 | Process for producing aromatic polycarbonate resin |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP89365/96 | 1996-04-11 | ||
| CN 97190631 CN1194656A (en) | 1996-04-11 | 1997-04-04 | Process for producing aromatic polycarbonate resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1194656A true CN1194656A (en) | 1998-09-30 |
Family
ID=5178811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97190631 Pending CN1194656A (en) | 1996-04-11 | 1997-04-04 | Process for producing aromatic polycarbonate resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1194656A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293118C (en) * | 2001-03-26 | 2007-01-03 | 拜尔公司 | Method for producing oligocarbonates |
| US7985823B2 (en) | 2006-12-18 | 2011-07-26 | Mitsubishi Chemical Corporation | Production method of polycarbonate resin |
| CN101087830B (en) * | 2004-11-01 | 2011-07-27 | 沙伯基础创新塑料知识产权有限公司 | Method for making polycarbonate |
| CN101087829B (en) * | 2004-11-01 | 2012-05-09 | 沙伯基础创新塑料知识产权有限公司 | Method for making polycarbonate |
| CN111065670A (en) * | 2017-09-06 | 2020-04-24 | 沙特基础工业全球技术有限公司 | Method for recovering phenol in melt polycarbonate polymerization |
-
1997
- 1997-04-04 CN CN 97190631 patent/CN1194656A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293118C (en) * | 2001-03-26 | 2007-01-03 | 拜尔公司 | Method for producing oligocarbonates |
| CN101087830B (en) * | 2004-11-01 | 2011-07-27 | 沙伯基础创新塑料知识产权有限公司 | Method for making polycarbonate |
| CN101087829B (en) * | 2004-11-01 | 2012-05-09 | 沙伯基础创新塑料知识产权有限公司 | Method for making polycarbonate |
| US7985823B2 (en) | 2006-12-18 | 2011-07-26 | Mitsubishi Chemical Corporation | Production method of polycarbonate resin |
| CN111065670A (en) * | 2017-09-06 | 2020-04-24 | 沙特基础工业全球技术有限公司 | Method for recovering phenol in melt polycarbonate polymerization |
| CN111065670B (en) * | 2017-09-06 | 2022-05-27 | 沙特基础工业全球技术有限公司 | Method for recovering phenol in melt polycarbonate polymerization |
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