CN101434695A - Method for preparing polycarbonate resin solution - Google Patents
Method for preparing polycarbonate resin solution Download PDFInfo
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- CN101434695A CN101434695A CNA2008101734596A CN200810173459A CN101434695A CN 101434695 A CN101434695 A CN 101434695A CN A2008101734596 A CNA2008101734596 A CN A2008101734596A CN 200810173459 A CN200810173459 A CN 200810173459A CN 101434695 A CN101434695 A CN 101434695A
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Abstract
The invention provides a method for steadily and efficiently manufacturing polycarbonate resin solution. The manufacturing polycarbonate resin solution manufacturing method comprises a filtering procedure for filtering water-in-oil decentralized emulsion containing panlite by means of a metal filter to enable the emulsion to be separated into aqueous phase and oleic phase containing panlite; the panlite is obtained by means of at least a polymerization reaction of binary phenol compound, wherein, content of binary phenol compound without response dissolved in the emulsion before being filtered is controlled within the scope of 0-0.3 weight percent.
Description
Technical field
The present invention relates to make the method for polycarbonate resin solution, wherein, use metallic filter will contain polycarbonate resin emulsion highly effective be separated into oil phase and the water that contains polycarbonate resin.
Background technology
As the manufacture method of polycarbonate resin, known have interfacial polymerization, a solution polymerization process that uses halogen organic solvents such as vinylchlorid, perhaps utilizes the manufacture method of transesterify.This wherein when adopting interfacial polymerization manufactured polycarbonate resin, obtains containing the organic solvent solution (being designated hereinafter simply as oil phase or O) of polycarbonate resin and the mixture of the aqueous solution (being designated hereinafter simply as water or W) after polyreaction stops.The oil phase that contains polycarbonate resin is emulsion state usually, therefore, is necessary to remove water-soluble impurity from emulsion, and the organic solvent solution of polycarbonate is carried out purifying.
In addition; residual unreacted organic compound and the impurity that trace is arranged in the organic solvent solution of reacted polycarbonate resin; therefore; usually can adopt and in the organic solvent solution of polycarbonate resin, add the method that alkaline aqueous solution, acidic aqueous solution, pure water etc. carry out stirring and washing; in order to improve cleaning efficiency; usually as follows the organic solvent solution of polycarbonate is carried out purifying: the mixture to the organic solvent solution of polycarbonate resin and scavenging solution carries out the brute force stirring; make its emulsionization once more; then, remove water-soluble impurity once more.
Traditionally, when from the resin emulsion that so obtains, removing the impure aqueous solution, use liquid centrifuge of fluid or standing separation groove.Yet when removing the impure aqueous solution by separating centrifuge, not only employed separating centrifuge is very expensive, and also must the very big cost of expenditure aspect the maintenance of separating centrifuge, operation power consumption.In addition, also have following shortcoming: the resin accumulation that the fault of drive part, rotating part, wearing and tearing or vinylchlorid volatilization cause and causing abends, and therefore is necessary to prepare reserve machine.
On the other hand, when removing,,, still exist separator tank to become problem big, that stay liquid measure also to increase in order to ensure the settling time even at inner spacer plate or the baffle plate of inserting of separator tank by leaving standstill.In addition, when commutation is carried out in the separator tank miniaturization, can produce problems, for example, handle because of the reagent that adds or water need carry out draining again.
As the method that addresses these problems, at present known have make polycarbonate resin liquid carry out isolating method (for example with reference to patent documentation 1) at the filtering layer below 40 ° by contact angle with water.Yet, there is following shortcoming in the method: remove relatively difficulty of fine liquid particles, must make it to pass through repeatedly filtering layer, in addition, after separation, more obvious from the pollution of filter material layer, and in order after by filtering material, to separate, need the cost regular hour, therefore, need bigger standing separation groove.
In addition, known following method: make polycarbonate resin liquid by hydrophobic or wetting ability first filtering layer, utilize hydrophobicity second filtering layer to remove the drop of water layer (for example with reference to patent documentation 2) then.Yet there is following shortcoming in this method: use the fine filter material of 0.1～20 μ m in first filtering layer, and thickness is preferably also more than the 0.5mm, therefore, filter pressure drop (
Ya Damage) big; In addition, use in second filtering layer with the hydrophobicity filtering material of tetrafluoroethylene as representative, therefore, isolated water can cause pressure drop further to increase.
In addition, known following method: use the wetting ability scavenging solution of pH2～14 scopes that polycarbonate resin liquid is carried out emulsification, and make it to be separated into 2 phases (for example with reference to patent documentation 3) with the space velocity of the 0.01～2cm/ second layer of fibers by thickness 10～500mm, apparent density 0.2～0.7g/ml.Yet there is following shortcoming in this method: the thickness of filtering material layer is big, and therefore, charges can cause big pressure drop, and then the filtering material outflow not only can occur, also must leave standstill groove.
Also known have a following method: under agitation with rinse water rough polycarbonate solution is cleaned, then, the rough polycarbonate solution that will contain rinse water is separated into water and the organic phase that contains polycarbonate by standing separation or centrifugation, and the filtration strainer that re-uses aperture 20～180 μ m filters (for example with reference to patent documentation 4) to the organic phase that contains polycarbonate under the condition of filtration flow-rate 60～1000mm/min.Yet there is following shortcoming in this method: only can not remove the impure aqueous solution fully by the filtration that utilizes filtering material, must make up and carry out standing separation or centrifugation, need to be provided with and leave standstill groove or separating centrifuge, the isolating benefit of filtering material is few.
In addition, in order to address these problems, known have a following method: after the metallic filter to filtering accuracy 10～200 μ m feeds liquid (logical liquid), carry out 1～30 minute standing separation (for example with reference to patent documentation 5).Yet, in for the above-mentioned research formerly of carrying out the isolating purification process of aggegation, based on the research of following aspect: to the research of the contact angle (for example with reference to patent documentation 1) of filtering layer and water; Research to the combination of filtering layer for example is passed into (for example with reference to patent documentations 2) such as hydrophobic second filtering layers again after by first filtering material; To the research (for example with reference to patent documentation 3) of the density or the space velocity of filtering material, to the research (for example with reference to patent documentation 4) of filtering material aperture and filtration flow-rate, to the research to filtering material such as research (for example with reference to patent documentation 5) of filtering material filtering accuracy.Yet,, do not carry out any research as yet for composition that is suitable for the water in the isolating polycarbonate resin solution etc.
As realistic problem, confirm time and again: because of creating conditions or the influence of running condition of polycarbonate, become the efficient of the organic solvent solution and the aqueous solution significantly to reduce the drop separation of polycarbonate resin fat liquor, therefore, be necessary the composition of the water in the polycarbonate resin solution is studied, with the performance of the filtering material that improves agglomeration separation.
Patent documentation 1: special public clear 46-41622 communique
Patent documentation 2: special public clear 59-22733 communique
Patent documentation 3: the spy opens clear 55-104316 communique
Patent documentation 4: the spy opens flat 9-104747 communique
Patent documentation 5: the spy opens the 2000-204151 communique
Summary of the invention
The problem that invention will solve
The objective of the invention is: solve the aforementioned problems in the prior, a kind of method of making polycarbonate resin solution is provided, wherein, before the drop separation with the polycarbonate resin fat liquor becomes oil phase and water, restriction separates the concentration of influential unreacted organic compound to this, and by using metallic filter to make polycarbonate resin solution efficiently.
The method of dealing with problems
The inventor etc. further investigate for addressing the above problem, found that: before will feeding metallic filter by the water-in-oil decentralized emulsion that water and the oil phase that contains polycarbonate resin constitute, with in the emulsion be contained in the polyreaction of aqueous phase the time unreacted dihydric phenols compound be controlled at below the 0.3 weight %, even under low pressure and pressure drop, also can remove water-soluble impurity stability and high efficiency, thereby finish the present invention.
That is it is as follows, to solve the method for described problem.
[1] a kind of manufacture method of polycarbonate resin solution, this manufacture method comprises filtration step, described filtration step utilizes metallic filter that the water-in-oil decentralized emulsion that contains polycarbonate resin is filtered, with its oil phase that is separated into water and contains polycarbonate resin, described polycarbonate resin is to obtain by the polyreaction of having utilized the dihydric phenols compound at least, wherein, the content of the unreacted dihydric phenols compound that is dissolved in aqueous phase in this emulsion before filtering is controlled at the scope of 0～0.3 weight %.
[2] manufacture method of the polycarbonate resin solution of above-mentioned [1], this manufacture method comprised the steps: before described filtration step, the described separation of emulsions of part is become water and oil phase, and this water carried out solvent extraction, measure the content of described unreacted dihydric phenols compound then by automatic analyser.
[3] manufacture method of the polycarbonate resin solution of above-mentioned [1], the dihydric phenols compound during wherein, by telo merization or the feed rate of phosgene and/or by before filtration step, diluting the content of controlling described unreacted dihydric phenols compound with alkaline aqueous solution, acidic aqueous solution or water.
[4] manufacture method of the polycarbonate resin solution of above-mentioned [1], wherein, before described filtration step, the median of the drip gauge area of the aqueous phase of described emulsion is 0.02～5m
2/ g.
[5] manufacture method of the polycarbonate resin solution of above-mentioned [1], wherein, the filtering accuracy of described metallic filter is 10～200 μ m.
[6] manufacture method of the polycarbonate resin solution of above-mentioned [1], wherein, the thickness of described metallic filter is 0.1～5mm.
[7] manufacture method of the polycarbonate resin solution of above-mentioned [1], wherein, the surface free energy of the material of described metallic filter is 200cal/cm
2More than.
[8] manufacture method of the polycarbonate resin solution of above-mentioned [1], wherein, the material of described metallic filter comprises the Cr of 11～30 weight %.
[9] manufacture method of the polycarbonate resin solution of above-mentioned [1], wherein, the material of described metallic filter is SUS304, SUS304L, SUS316, SUS316L, SUS317, SUS317L or SUS347.
The effect of invention
According to the present invention, the drop of polycarbonate resin fat liquor can be separated into oil phase and water efficiently, stably make the polycarbonate resin solution of having removed impurity, and then stably make the polycarbonate resin of having removed impurity.
Embodiment
In the method for the invention, utilize following polycarbonate resin, described polycarbonate resin is to make by the polyreaction of having utilized the dihydric phenols compound at least.The manufacture method of polycarbonate resin is identical with in the past polycarbonate resin making method with an organic solvent, that is, interfacial polymerization, pyridine method etc. adopt the manufacture method of solution method.In these methods, be principal constituent with dihydric phenols compounds such as bisphenol cpds, and use a spot of molecular weight regulator and branching agent as required, this principal constituent and phosgene are reacted.Method of the present invention can be used for the manufacturing that following viscosity-average molecular weight is 1000～100000 polycarbonate resin: use aromatic series homopolymerization that common bisphenol cpd forms or copolymerized panlite, further imported the polycarbonate resin etc. of chain alkyl by the polycarbonate resin of branching, end.And, can be used for the manufacturing of following solvents soluble poly carbonate resin: but the solvent soluble polycarbonate resin that graft phenylethene etc. forms as terminal terminator or comonomer on the polycarbonate resin with grafting sites such as carbon-to-carbon double bonds; Perhaps, the graft polymerization that copolymerization has phenolic hydroxyl group or other a polycarbonate resin on polystyrene etc. causes the solvent soluble polycarbonate resin that the compound of point forms; The solvent soluble polycarbonate resin that forms of graft polymerization polycarbonate resin thereon; Or the like.As normally used aromatic polycarbonate resin, particularly can list with 2, two (4-hydroxy phenyl) propane [dihydroxyphenyl propane] of 2-are the polycarbonate of main raw material, can be used for above-mentioned aromatic polycarbonate resin and for example 1,1-(4-hydroxy phenyl) hexanaphthene [bisphenol Z] or 2, two (4-hydroxyl-3, the 5-dibromo phenyl) propane [tetrabromo-bisphenol] etc. of 2-are used in combination and the Copolycarbonate that obtains, their branching thing or the manufacturing of polycarbonate resin such as terminal long chain alkyl modified thing.
As the dihydric phenols compound that uses among the present invention, can list particularly: two (4-hydroxy phenyl) methane, two (3-methyl-4-hydroxy phenyl) methane, two (3-chloro-4-hydroxy phenyl) methane, two (3,5-two bromo-4-hydroxy phenyls) methane, 1, two (4-hydroxy phenyl) ethane, 1 of 1-, two (2-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) ethane, 1 of 1-, two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) ethane of 1-, 1-phenyl-1, two (the 3-fluoro-4-hydroxy-3-methyl phenyl) ethane, 2 of 1-, two (4-hydroxy phenyl) propane (dihydroxyphenyl propanes of 2-; BPA), 2,2-two (3,5-two bromo-4-hydroxy phenyls) propane (TBA), 2, two (4-hydroxy phenyl) butane of 2-, 2, two (2-methyl-4-hydroxy phenyl) propane of 2-, 2, two (the 4-hydroxyls-3 of 2-, the 5-dichlorophenyl) propane, 2, two (the 4-hydroxyls-3 of 2-, the 5-difluorophenyl) propane, 2, two (the 4-hydroxyls-3 of 2-, the 5-3,5-dimethylphenyl) propane, 2, two (4-hydroxyl-3-bromophenyl) propane of 2-, 2, two (4-hydroxyl-3-chloro-phenyl-) propane of 2-, 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 2, two (4-hydroxyl-3-fluorophenyl) propane of 2-, 2, two (4-hydroxyl-1-aminomethyl phenyl) propane of 2-, 2, two (the 3-bromo-4-hydroxyl-5-chloro-phenyl-) propane of 2-, 2, two (3-phenyl-4-hydroxy phenyl) propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 1, two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) butane of 1-, 1, two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) Trimethylmethanes of 1-, 1, two (2-tert-pentyl-4-hydroxy-5-methyl base phenyl) butane of 1-, 1,1-two (3,5-two chloro-4-hydroxy phenyls) butane, 1, two (3, the 5-two bromo-4-hydroxy phenyls) butane of 1-, 4, two (4-hydroxy phenyl) heptane of 4-, 1, two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) heptane of 1-, 2, two (hydroxyaryl) paraffinics such as two (4-hydroxy phenyl) octanes of 2-; 1, two (4-hydroxy phenyl) pentamethylene, 1 of 1-, 1-bis(4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 1, two (3-methyl-4-hydroxy phenyl) hexanaphthenes, 1 of 1-, two (3-cyclohexyl-4-hydroxy phenyl) hexanaphthenes, 1 of 1-, two (3-phenyl-4-hydroxy phenyl) hexanaphthenes, 1 of 1-, two (the 4-hydroxy phenyls)-3,5 of 1-, two (4-hydroxy phenyl) cycloalkanes such as 5-trimethyl-cyclohexane; 4,4 '-dihydroxybiphenyl, 4,4 '-dihydroxyl-2,2 '-dimethyl diphenyl, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl, 4,4 '-dihydroxyl-3, dihydroxybiphenyl classes such as 3 '-dicyclohexyl biphenyl; Two (hydroxyaryl) ethers such as two (4-hydroxy phenyl) ether, two (4-hydroxy-3-methyl phenyl) ether; Two (hydroxyaryl) sulfone classes such as two (4-hydroxy phenyl) sulfone, two (3-methyl-4-hydroxy phenyl) sulfone; Two (hydroxyaryl) sulfoxide classes such as two (4-hydroxy phenyl) sulfoxide, two (3-methyl-4-hydroxy phenyl) sulfoxide, two (3-phenyl-4-hydroxy phenyl) sulfoxide; Two (hydroxyaryl) thioether classes such as two (4-hydroxy phenyl) thioether, two (3-methyl-4-hydroxy phenyl) thioether; Two (4-hydroxy phenyl) ketone, two terminal phenol modified siloxane classes and two terminal phenol modified silane classes etc.They also can be used in combination.Wherein, be preferably selected from dihydroxyphenyl propane, 1,1-bis(4-hydroxyphenyl) cyclohexane and 2, the material in two (3, the 5-two bromo-4-hydroxy phenyls) propane of 2-.
As terminal terminator or molecular weight regulator, can list compound with monohydric phenol hydroxyl, except that common phenol, p-tert-butylphenol, tribromophenol, chain alkyl phenol, hydroxy-benzoic acid alkyl ester, alkyl oxide phenol etc. have the compound of monohydric phenol hydroxyl, can also list carboxylic-acid or carboxylic acid halides classes such as aliphatics acyl chlorides, aliphatic carboxylic acid, aromatic carboxylic acid, aromatic series acyl chlorides.In addition, the phenols with reactive double bond can be used as terminal terminator, as example in this case, can list: unsaturated carboxylic acids such as vinylformic acid, vinylacetic acid, 2-pentenoic acid, 3-pentenoic acid, 5-hexenoic acid, 9-undecylenic acid; Acrylate chloride, 2, acyl chlorides or chloro-formic esters such as 4-hexadiene acyl chlorides, vinyl carbinol chloro-formic ester, isopropenyl phenol chloro-formic ester or hydroxy styrenes chloro-formic ester; Isopropenyl phenol, hydroxy styrenes, hydroxyphenyl maleimide, hydroxy-benzoic acid allyl ester or hydroxy-benzoic acid methyl allyl ester etc. have the phenols of unsaturated group, one-sided terminal phenol modified siloxane class and one-sided terminal phenol modified silane class etc.
These terminal terminators can be used in combination, with respect to 1 mole of above-mentioned dihydric phenols compound, usually at 1～25 mole of %, preferably use these terminal terminators in the scope of 1.5～10 moles of %.
As the employed organic solvent of reaction, can list: methylene dichloride, 1, chlorinated hydrocarbons such as 2-ethylene dichloride, chloroform, toluene, chlorobenzene, 1, tetracol phenixin; Aromatic hydrocarbon such as benzene; Ether compounds such as ether, these organic solvents also can mix use more than two kinds.
In addition, can be used in combination 0.01～5 mole of % with respect to above-mentioned dihydric phenols compound, the branching agent of 0.1～3.0 mole of % scope and make branching polycarbonate particularly, as branching agent, can list: Phloroglucinol, 2,6-dimethyl-2,4,6-three (4-hydroxy phenyl) teracrylic acid, 4,6-dimethyl-2,4,6-three (4-hydroxy phenyl) heptene-2,1,3,5-three (2-hydroxy phenyl) benzene, 1,1,1-three (4-hydroxy phenyl) ethane, 2, two (2-hydroxy-5-methyl base the benzyl)-4-methylphenols of 6-, α, α ', α " three (4-hydroxy phenyls)-1,3,5-triisopropylbenzene; 3; two (4-hydroxy phenyl) Oxoindoles (=isatin bis-phenol) of 3-; 5-chlorisatide bis-phenol; 5,7-two chlorisatide bis-phenols; 5-bromoisatin bis-phenol etc.
Molecular weight as the polycarbonate resin of manufacturing, when representing with viscosity-average molecular weight, can in 1000～100000 scope, select, but consider rerum natura that the shock-resistance, wearability etc. of moulding product require or formability etc., be preferably 5000～50000 scope.
Usually, in interface polymerization reaction, the following polyreaction of carrying out: the dihydric phenols compound dissolution in caustic-alkali aqueous solution, is carried out phosgenation reaction in the presence of organic solvent, add polymerizing catalyst and stirring as required.If the concentration of the polycarbonate resin during about polyreaction is the form of solution with an organic solvent, then preferred 5～30 weight % usually.During the polycarbonate resin excessive concentration, viscosity uprises, and is not preferred.
Polyreaction can obtain following mixture after stopping, described mixture comprises the organic solvent solution (oil phase) and the aqueous solution (water) of polycarbonate, impurity such as the unreacted dihydric phenols compound of the described aqueous solution (water) when comprising polyreaction, by product muriate, carbonate, caustic alkali.This mixture is separated into oil phase and water sometimes, but still can contain some moisture in the oil phase, and the mixture after the polymerization is emulsion form.Essential oil phase mostly is W/O (water-in-oil decentralized).
In the present invention, the content of the unreacted dihydric phenols compound when being dissolved in the polyreaction of aqueous phase of polycarbonate resin fat liquor is preferably 0～0.3 weight %, be preferably 0～0.15 weight % especially, wherein, described polycarbonate resin fat liquor comprises the organic solvent solution (oil phase) and the aqueous solution (water) of this polycarbonate, impurity such as the unreacted dihydric phenols compound of the described aqueous solution (water) when comprising polyreaction, by product muriate, carbonate, caustic alkali.
If the content of unreacted dihydric phenols compound surpasses 0.3 weight %, then the efficient of isolating the aqueous solution (water) of impurity such as unreacted dihydric phenols compound when comprising polyreaction, by product muriate, carbonate, caustic alkali from the organic solvent solution (oil phase) of polycarbonate by metallic filter significantly descends, therefore, not preferred.
And, passing through batch-type or tubular reactor (パ イ プ リ ア Network -), during the successive type polymerization procedure continuous production polycarbonate resin of groove overflow mode, can be with the unreacted dihydric phenols compound that water contained in the emulsion after the organic solvent extraction polyreaction, measure this unreacted dihydric phenols compound concentrations with automatic analyser, adjust the feed rate of starting material (for example dihydric phenols compound and/or phosgene) according to its result, the perhaps water-in-oil decentralized emulsion alkaline aqueous solution that contains polycarbonate resin that will obtain by polyreaction, the dilution of acidic aqueous solution or water is controlled at described scope with the content of the unreacted dihydric phenols compound of the aqueous phase of polycarbonate resin fat liquor.For example, collect the emulsion that contains polycarbonate resin after a part of polyreaction, with centrifugal separating device etc. with water and separation of oil, add extraction solvents such as methylene dichloride to aqueous phase, add hydrochloric acid etc. again and be adjusted into acidity, extract the dihydric phenols compound of aqueous phase, then, utilize automatic analysers such as spectrophotometer can obtain the content of unreacted dihydric phenols compound.As described automatic analyser, get final product so long as possess the analysis meter of the test section of the light source in 200～400nm zone and photoabsorption that can test samples, preferred light source is in 250～300nm zone especially.
In addition, the liquid that contains polycarbonate resin as gained after polyreaction (can be W/O decentralized emulsion, also can be the organic solvent solution of homogeneous) in remove impurity and obtain the method for high-purity polycarbonate resin solution, can carry out like this: after polyreaction, add rinse water such as alkaline aqueous solution, acidic aqueous solution, water in the liquid that contains polycarbonate resin of gained, stir extraction.This cleaning can adopt any one to carry out separately, also can be used in combination the purging method more than 2 kinds or 3 kinds sometimes, and the liquid liquid that goes among the present invention after any cleaning separates.
As the liquid that contains polycarbonate resin of gained after the polyreaction and the blending means of rinse water, can use the commercially available any instrument that is mixed into purpose with liquid/liquid, but for the stirring efficiency of realizing wishing, except that unidirectional revolving stirrer, can also use round gyro-mixer, the on-line mixing device, leave standstill mixing tank (static mixer), the orifice flow mixing machine, FULLZONE (refreshing steel Pantech (strain)), MAXBLEND (Sumitomo heavy-duty machine tool industry (strain)), intimate mixing device (special machine chemical industry (strain)), SULZER mixing tank (Sumitomo heavy-duty machine tool industry (strain)) or leave standstill mixing tank etc.
The oil phase and the relation between the water that constitute emulsion comprise O/W (oil-in-water-type) or W/O (water-in-oil-type), in the present invention, in order to improve extraction efficiency, to reduce waste water, utilize the emulsion of W/O (water-in-oil-type).For example, when the liquid that contains polycarbonate resin of gained after the polyreaction is the organic solvent solution of homogeneous, add alkaline aqueous solution, acidic aqueous solution or water, mix as stated above, preparation W/O emulsion.In addition, the drip gauge area that constitutes in the oil phase of emulsion is different because of the volumetric ratio of the kind of the pH of the concentration of polycarbonate resin, the aqueous solution, rinse water, oil phase and water etc., for extraction water solubility impurity effectively, the median of the drip gauge area of water is 0.02～5m in the preferred described emulsion
2The emulsion of/g.If the not enough 0.02m of the median of drip gauge area
2/ g, then cleaning performance reduces, and is not preferred.In addition, if the median of drip gauge area surpasses 5m
2/ g, then the volatilization of solvent increases, and is not preferred.
Use among the present invention with clean the water blended and contain the W/O emulsion of polycarbonate, if it has above-mentioned drip gauge area, even then stop to stir, sedimentation gravity also can resist mutually with surface tension, molecular motion, can not be separated into oil phase and water, be emulsion state usually.
In the method for the invention, implement following filtration step: the water-in-oil decentralized emulsion that contains polycarbonate resin of polyreaction gained is filtered with metallic filter, it is separated into oil phase and water.As the material of used metallic filter, preferably good with contacting of the oil of emulsion and water and surface free energy is 200cal/cm
2Above high energy material, metallic substance is suitable.This wherein preferably contains the metallic substance of the Cr of 11～30 weight %.Particularly, material as metallic filter, the stainless steel that preferably contains the Cr of 11～30 weight %, wherein, consider that from viewpoints such as solvent resistance, erosion resistances preference is as being the austenitic stainless steel of representative with SUS304, SUS304L, SUS316, SUS316L, SUS317, SUS317L and SUS347.In addition, using with the anti-corrosion Langaloy of haas troy (HASTELLOY), Yin Keluoyi heat-resistant corrosion-resistant alloy of chrome-iron-nickel (INCOLOY), Si Telaisi heat-resistant antifriction Wimet (STELLITE) also is effective as the Ni that contains Cr, the Co class alloy type of representative.
The filtering accuracy of metallic filter is preferably 10～200 μ m.10～100 μ m more preferably.In addition, the thickness of metallic filter is in the scope of 0.1～5mm, if thinner than 0.1mm, then undercapacity is damaged easily, can cause separation not good.As strainer, except that the wire netting of various weaving methods, can also use metal system non-woven fabrics or felt, demister weighting material, from the angle of filtering accuracy and thickness, non-woven fabrics is fit to.And these metallic filters preferably clean the back with strongly acidic aqueous solutions such as hydrochloric acid, sulfuric acid, phosphoric acid and use.
Embodiment
Below, the present invention is described in detail by embodiment, but scope of the present invention is not limited thereto.
(viscosity measurement of resin emulsion)
Use Tokyo gauge system E type rotational viscosimeter, model: Digital Viscometer DV L-B measures.
(measuring method of emulsion droplet surface-area)
Use the hole field to make the median of the super centrifugal automatic particle size distribution device of institute's (strain) system, model C APA-700 mensuration drip gauge area.
(the measuring method of viscosity-average molecular weight: Mv)
Use Ubbelodhe type tubule viscometer determining limiting viscosity, convert with the Schnell formula.
(measuring method of water ratio)
With Ka Er-Fei Xier moisture meter (capital of a country electronics: model MKA-210) measure.
(measuring method of the unreacted dihydric phenols compounds content in the impure water liquid of polycarbonate resin)
Use super centrifugal separator that a part of emulsion solution is separated into water and oil phase, add methylene dichloride, add hydrochloric acid again and be adjusted to acidity, the unreacted dihydric phenols compound of aqueous phase is extracted in the methylene dichloride to this aqueous phase.This methylene dichloride is transferred in the 10mm quartz cell, uses spectrophotometer (Shimadzu Seisakusho Ltd.'s (strain) system: model UV-1700) under wavelength 280nm, measure.
According to the reference liquid production standard curve of dihydric phenols compound and methylene dichloride, use this typical curve to calculate the content of the unreacted dihydric phenols compound of aqueous phase in advance.
Embodiment 1
(synthesizing of polycarbonate resin solution)
Dispersing and dissolving 25 premium on currency and 120kg are as the dihydroxyphenyl propane and the 0.6kg hydrosulphite of dihydric phenol in the aqueous sodium hydroxide solution of 600kg9%.To wherein adding 600 liters of methylene dichloride (MC) and stirring, add the 2.1kg p-tert-butylphenol simultaneously, then with slowly liquid phosgene of adding 60kg and stirring in 60 minutes.After adding phosgene, add the 140g triethylamine under the vigorous stirring, stir about 1 hour carries out polymerization.
(viscosity of W/O (water-in-oil decentralized) is 220cp to this emulsion form resin solution, and the median of drip gauge area is 0.3m
2/ g.And, do not detect the unreacted dihydric phenols compound of impure aqueous phase.
Use toothed gear pump with this emulsion form resin solution (W/O (water-in-oil decentralized)) with the flow force feed of 250kg/h to having metallic filter (filtering accuracy 50 μ m: thickness 0.37mm: big or small 52mm φ * 254mm:SUS304: in strainer cavity non-woven fabrics).And the flow direction of this resin solution is the central side flow direction outside from strainer.This moment, the pressure drop of strainer was 0.3kg/cm
2At cavity outlet resin solution is taken a sample, measure moisture, it is 0.6 weight %.
Take out about 10 ml samples from MC mutually, add hydrochloric acid and be adjusted into acidity, then, clean with pure water.Then, make solvent evaporates, obtain solid-state polycarbonate, measure its viscosity-average molecular weight, this viscosity-average molecular weight Mv is 28000.
Embodiment 2
By carrying out with embodiment 1 similar methods, different is: in the polycarbonate resin solution of embodiment 1 synthetic, slowly add 59.8kg liquid state phosgene with 60 minutes times.The viscosity of this emulsion form resin solution (W/O (water-in-oil decentralized)) is 220cp, and the median of drip gauge area is 0.3m
2/ g.And in this resin solution, the content of the unreacted dihydric phenols compound of impure aqueous phase is 0.06 weight %.
With metallic filter (filtering accuracy 50 μ m: thickness 0.37mm: big or small 52mm φ * 254mm:SUS304: non-woven fabrics) be installed on the strainer cavity, extract part emulsion resin solution by steel basin out with the flow of 250kg/h, use toothed gear pump its outside force feed from strainer.At this moment, the pressure drop of strainer is 0.3kg/cm
2At cavity outlet resin solution is taken a sample, measure moisture, it is 0.6 weight %.
Embodiment 3
By carrying out with embodiment 1 similar methods, different is: in the polycarbonate resin solution of embodiment 1 is synthetic, with slowly adding 59.6kg liquid state phosgene in 60 minutes.The viscosity of this emulsion form resin solution (W/O (water-in-oil decentralized)) is 220cp, and the median of drip gauge area is 0.3m
2/ g.And in this resin solution, the content of the unreacted dihydric phenols compound of impure aqueous phase is 0.13 weight %.
With metallic filter (filtering accuracy 50 μ m: thickness 0.37mm: big or small 52mm φ * 254mm:SUS304: non-woven fabrics) be installed on the strainer cavity, extract part emulsion resin solution by steel basin out with the flow of 250kg/h, use toothed gear pump its outside force feed from strainer.At this moment, the pressure drop of strainer is 0.3kg/cm
2At cavity outlet resin solution is taken a sample, measure moisture, it is 0.8 weight %.
Embodiment 4
By carrying out with embodiment 1 similar methods, different is: in polycarbonate resin solution synthetic, with slowly adding 59.1kg liquid state phosgene in 60 minutes.The viscosity of this emulsion form resin solution (W/O (water-in-oil decentralized)) is 220cp, and the median of drip gauge area is 0.3m
2/ g.And in this resin solution, the content of the unreacted dihydric phenols compound of impure aqueous phase is 0.34 weight %.Extract the polycarbonate resin solution (oil phase) that obtains out with 250kg/h, the pure water 7.3L/h that interpolation goes out according to the cubage of aforementioned unreacted dihydric phenols compound, use intimate mixing device (special machine chemical industry) to mix, preparation W/O (water-in-oil decentralized) emulsion solution.The viscosity of this emulsion form resin solution (W/O (water-in-oil decentralized)) is 220cp, and the median of drip gauge area is 0.3m
2/ g.And in this resin solution, the unreacted dihydric phenols compounds content of impure aqueous phase is 0.29 weight %.
With metallic filter (filtering accuracy 50 μ m: thickness 0.37mm: big or small 52mm φ * 254mm:SUS304: non-woven fabrics) be installed on the strainer cavity, extract part emulsion resin solution by steel basin out with the flow of 250kg/h, use toothed gear pump its outside force feed from strainer.At this moment, the pressure drop of strainer is 0.3kg/cm
2At cavity outlet resin solution is taken a sample, measure moisture, it is 1.1 weight %.
Comparative example 1
Undertaken by the operation similar to embodiment 4, different is: synthesize the polycarbonate resin solution (oil phase) that obtains by polycarbonate with 250kg/h output in embodiment 4, do not add pure water, directly mix, prepared W/O (water-in-oil decentralized) emulsion solution with intimate mixing device (special machine chemical industry).The viscosity of emulsion is 220cp, and the median of the drip gauge area of the emulsion of sampling is 0.3m
2/ g.The content of the unreacted dihydric phenols compound of the impure aqueous phase of polycarbonate resin is 0.34 weight %, and the filter pressure drop when handling with the metal filter material is 0.3kg/cm
2At cavity outlet resin solution is taken a sample, measure moisture, it is 3.1 weight %.
Comparative example 2
By carrying out with embodiment 1 similar methods, different is: in the polycarbonate resin solution of embodiment 1 is synthetic, with slowly adding 58.9kg liquid state phosgene in 60 minutes.The viscosity of this emulsion form resin solution (W/O (water-in-oil decentralized)) is 220cp, and the median of drip gauge area is 0.3m
2/ g.And in this resin solution, the content of the unreacted dihydric phenols compound of impure water liquid is 0.41 weight %.
With metallic filter (filtering accuracy 50 μ m: thickness 0.37mm: big or small 52mm φ * 254mm:SUS304: non-woven fabrics) be installed on the strainer cavity, extract part emulsion resin solution by steel basin out with the flow of 250kg/h, use toothed gear pump its outside force feed from strainer.At this moment, the pressure drop of strainer is 0.3kg/cm
2At cavity outlet resin solution is taken a sample, measure moisture, it is 5.9 weight %.
Claims (9)
1. the manufacture method of polycarbonate resin solution, this manufacture method comprises filtration step, described filtration step utilizes metallic filter that the water-in-oil decentralized emulsion that contains polycarbonate resin is filtered, with its oil phase that is separated into water and contains polycarbonate resin, described polycarbonate resin is to obtain by the polyreaction of having utilized the dihydric phenols compound at least, wherein
The content of the unreacted dihydric phenols compound that is dissolved in aqueous phase in this emulsion before filtering is controlled at the scope of 0～0.3 weight %.
2. the manufacture method of the polycarbonate resin solution of claim 1, this manufacture method comprised the steps: before described filtration step, the described separation of emulsions of part is become water and oil phase, and this water carried out solvent extraction, measure the content of described unreacted dihydric phenols compound then by automatic analyser.
3. the manufacture method of the polycarbonate resin solution of claim 1, the dihydric phenols compound during wherein, by telo merization or the feed rate of phosgene and/or by before filtration step, diluting the content of controlling described unreacted dihydric phenols compound with alkaline aqueous solution, acidic aqueous solution or water.
4. the manufacture method of the polycarbonate resin solution of claim 1, wherein, before described filtration step, the median of the drip gauge area of the aqueous phase of described emulsion is 0.02～5m
2/ g.
5. the manufacture method of the polycarbonate resin solution of claim 1, wherein, the filtering accuracy of described metallic filter is 10～200 μ m.
6. the manufacture method of the polycarbonate resin solution of claim 1, wherein, the thickness of described metallic filter is 0.1～5mm.
7. the manufacture method of the polycarbonate resin solution of claim 1, wherein, the surface free energy of the material of described metallic filter is 200cal/cm
2More than.
8. the manufacture method of the polycarbonate resin solution of claim 1, wherein, the material of described metallic filter
The Cr that comprises 11～30 weight %.
9. the manufacture method of the polycarbonate resin solution of claim 1, wherein, the material of described metallic filter is SUS304, SUS304L, SUS316, SUS316L, SUS317, SUS317L or SUS347.
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| JP296738/07 | 2007-11-15 |
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| CN102964583A (en) * | 2012-11-14 | 2013-03-13 | 烟台万华聚氨酯股份有限公司 | Preparation method of bisphenol (polyphenol) solution in preparation of polycarbonate |
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| JP3182327B2 (en) * | 1995-10-11 | 2001-07-03 | 出光石油化学株式会社 | Method for producing purified polycarbonate solution |
| JP4280881B2 (en) * | 1999-07-23 | 2009-06-17 | 三菱瓦斯化学株式会社 | Purification method of polycarbonate resin solution |
| JP4085215B2 (en) * | 1999-01-11 | 2008-05-14 | 三菱瓦斯化学株式会社 | Separation method of polycarbonate resin emulsion |
| JP4093703B2 (en) * | 2000-04-27 | 2008-06-04 | 出光興産株式会社 | Polycarbonate resin for optical disk substrate and optical disk substrate |
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| CN102964583A (en) * | 2012-11-14 | 2013-03-13 | 烟台万华聚氨酯股份有限公司 | Preparation method of bisphenol (polyphenol) solution in preparation of polycarbonate |
| CN102964583B (en) * | 2012-11-14 | 2014-09-17 | 万华化学集团股份有限公司 | Preparation method of bisphenol (polyphenol) solution in preparation of polycarbonate |
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