WO2015146575A1 - Procédé de production d'un copolymère polycarbonate-polyorganosiloxane - Google Patents

Procédé de production d'un copolymère polycarbonate-polyorganosiloxane Download PDF

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WO2015146575A1
WO2015146575A1 PCT/JP2015/057008 JP2015057008W WO2015146575A1 WO 2015146575 A1 WO2015146575 A1 WO 2015146575A1 JP 2015057008 W JP2015057008 W JP 2015057008W WO 2015146575 A1 WO2015146575 A1 WO 2015146575A1
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polyorganosiloxane
polycarbonate
group
polyorganosiloxane copolymer
copolymer
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PCT/JP2015/057008
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English (en)
Japanese (ja)
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智子 阿部
石川　康弘
彰一 古川
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出光興産株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/186—Block or graft polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/26—General preparatory processes using halocarbonates
    • C08G64/28—General preparatory processes using halocarbonates and phenols

Definitions

  • the present invention relates to a method for producing a polycarbonate-polyorganosiloxane copolymer.
  • Polycarbonate-polyorganosiloxane copolymers are attracting attention because of their high impact resistance, chemical resistance, and flame retardancy, and are widely used in various fields such as the electrical / electronic equipment field and the automobile field. Use is expected. In particular, the use of portable telephones, mobile personal computers, digital cameras, video cameras, power tools and other housings, and other daily necessities is expanding.
  • a typical polycarbonate a homopolycarbonate in which the starting dihydric phenol is 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] is generally used.
  • polycarbonate-polyorganosiloxane copolymers obtained by copolymerizing polyorganosiloxane with homopolycarbonate (Patent Documents 1 and 2). reference).
  • the polycarbonate-polyorganosiloxane copolymer can be continuously produced by an interfacial polymerization method, a transesterification method or the like. At this time, it is required to produce a polycarbonate-polyorganosiloxane copolymer containing the raw material polyorganosiloxane in a predetermined content ratio.
  • a step of preparing a polycarbonate oligomer from a dihydric phenol and a carbonate precursor, a copolymerization step of copolymerizing the polycarbonate oligomer and a polyorganosiloxane, and a reaction solution obtained after the copolymerization step are prepared as a polycarbonate-polyorganosiloxane copolymer.
  • a polycarbonate-polyorganosiloxane copolymer is obtained as a solid by the production method having these steps.
  • the raw materials used are used at a constant ratio so as to obtain a preset polyorganosiloxane content.
  • the polyorganosiloxane content in the polycarbonate-polyorganosiloxane copolymer can vary with variations in various production conditions.
  • the present invention provides a method for producing a polycarbonate-polyorganosiloxane copolymer in which the fluctuation range of the polyorganosiloxane content in the copolymer under production conditions is small in the production of a polycarbonate-polyorganosiloxane copolymer. With the goal.
  • the present inventors can quickly adjust the amount of polyorganosiloxane used as a raw material by monitoring the polyorganosiloxane content in the copolymer using fluorescent X-ray analysis instead of the conventional NMR method. I found out that I can. That is, the present invention includes the following. 1.
  • a method for producing a polycarbonate-polyorganosiloxane copolymer which is obtained by adding polyorganosiloxane to a reaction system for polymerizing a dihydric phenol and a carbonate precursor and copolymerizing the polycarbonate-polyorganosiloxane copolymer obtained after the copolymerization, A portion of the sample is collected, the polyorganosiloxane content in the copolymer is measured by fluorescent X-ray analysis, and the amount of polyorganosiloxane added to the reaction system is controlled based on the measured value.
  • a method for producing an organosiloxane copolymer is controlled based on the measured value.
  • R 1 and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms.
  • X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO- , -SO 2- , -O-, or -CO-.
  • a and b are each independently an integer of 0 to 4.
  • Y is -R 7 O -, - R 7 COO -, - R 7 NH -, - R 7 NR 8 -, - COO -, - S -, - R 7 COO-R 9 -O-, or -R 7 O—R 10 —O— is shown.
  • R 7 represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group.
  • R 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group.
  • R 9 represents a diarylene group.
  • R 10 represents a linear, branched or cyclic alkylene group, or a diarylene group.
  • Z represents a hydrogen atom or a halogen atom.
  • ⁇ represents a divalent group derived from a diisocyanate compound or a divalent group derived from dicarboxylic acid or a halide of dicarboxylic acid.
  • the sum of p and q is n, and n represents an average number of repetitions of 30 to 500. ] 10.
  • the polyorganosiloxane content in the polycarbonate-polyorganosiloxane copolymer is measured by fluorescent X-ray analysis, and the amount of polyorganosiloxane added to the reaction system based on the measured value
  • fluorescent X-ray analysis method a trace amount analysis in a short time is possible, and the amount of polyorganosiloxane added to the reaction system can be quickly controlled.
  • 1 is a schematic view showing an embodiment of a production line for performing a production method of a polycarbonate-polyorganosiloxane copolymer of the present invention by an interfacial polymerization method.
  • 1 is a schematic view showing an embodiment of a production line for performing the method for producing a polycarbonate-polydimethylsiloxane copolymer of the present invention.
  • the present invention relates to a method for producing a polycarbonate-polyorganosiloxane copolymer in which a polyorganosiloxane is added to a reaction system for polymerizing a dihydric phenol and a carbonate precursor and copolymerized. Taking a part of the polymer, measuring the polyorganosiloxane content in the copolymer by fluorescent X-ray analysis, and controlling the amount of polyorganosiloxane added to the reaction system based on the measured value Features.
  • PC-POS copolymer A polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes abbreviated as “PC-POS copolymer”) is obtained by adding polyorganosiloxane to a reaction system for polymerizing a dihydric phenol and a carbonate precursor. After the copolymerization by the interfacial polymerization method (phosgene method), the transesterification method (melting method), etc., it can be continuously produced through various treatment steps.
  • an organic phase containing a polycarbonate-polyorganosiloxane copolymer which will be described later, is separated from an aqueous phase containing unreacted substances and catalyst residues, and alkali washing, acid washing, pure water
  • a polycarbonate-polyorganosiloxane copolymer with few impurities such as chlorine ions can be produced efficiently. it can.
  • a polycarbonate oligomer is first prepared, and an alkali aqueous solution of polyorganosiloxane and dihydric phenol is added to the polycarbonate oligomer.
  • a terminal terminator molecular weight regulator
  • the polymer solution containing the copolymer is separated / washed and then concentrated, and the concentrate is pulverized / granulated.
  • a polycarbonate-polyorganosiloxane copolymer can be produced.
  • a polycarbonate-polyorganosiloxane copolymer can be produced by dephenolization and granulation.
  • the content of polyorganosiloxane in the polycarbonate-polyorganosiloxane copolymer obtained after copolymerization is measured by fluorescent X-ray analysis.
  • the polycarbonate-polyorganosiloxane copolymer obtained after copolymerization used for the fluorescent X-ray analysis may be a polycarbonate-polyorganosiloxane copolymer obtained after pulverization / granulation.
  • a solution containing a polycarbonate-polyorganosiloxane copolymer obtained by separating an organic phase from a polymerization solution or a melt obtained after polymerization, particularly a polymerization solution obtained by an interfacial polymerization method may be used.
  • the amount of polyorganosiloxane in the reaction system is set to a constant ratio so that the copolymer has a preset polyorganosiloxane content ratio.
  • the polyorganosiloxane content in the polycarbonate-polyorganosiloxane copolymer can vary with variations in various production conditions.
  • the fluorescent X-ray analysis method a part of the powder or granulated product obtained after pulverization / granulation is collected, and the powder or granulated product itself, or a sheet or film processed from the powder or granulated product Furthermore, the organic phase containing the polycarbonate-polyorganosiloxane copolymer obtained by separating the polymerization solution in an optional step after the copolymerization is collected in a petri dish and the solvent is evaporated from the organic phase. Sheet or film can be used as a sample for measurement.
  • the form of the polycarbonate-polyorganosiloxane copolymer at the time of measurement by X-ray fluorescence analysis may be any of powder, pellet (granulated product), sheet, or film.
  • a sheet or film is obtained by, for example, hot press molding powder or pellets.
  • the sheet or film is processed so as to have a thickness of about 0.2 to 5 mm.
  • a sheet is a soft sheet with a thickness of 0.2 mm or more
  • a film is a soft sheet with a thickness of less than 0.2 mm and a hard sheet with a thickness of less than 0.5 mm. It is stipulated that the thing.
  • the measurement sample for fluorescent X-ray analysis may be a film even if it has a thickness of about 0.2 to 5 mm. There may be. From the viewpoint of measurement accuracy, the thickness of the sheet or film is preferably 0.5 mm or more, more preferably 1.0 mm or more.
  • the polycarbonate-polyorganosiloxane copolymer is preferably in the form of a sheet or film. Processing into a sheet or film makes the sample density uniform. Since the uniformity of the sample density makes the incident depth of the excitation X-ray dose and the generation amount of the fluorescent X-ray dose constant, the measurement accuracy can be guaranteed. Further, by processing into a sheet or film, the surface flatness (no irregularities) becomes good, and the X-ray optical path length is stabilized.
  • Fluorescence X-ray analysis generally has the following advantages. That is, no complicated pretreatment as in the NMR method is required, and as described above, sample preparation is unnecessary, or it can be carried out easily and quickly by pressure treatment or the like. The resulting spectrum is relatively simple and easy to interpret. It is also suitable for trace analysis and has high quantitative accuracy.
  • One of the features of the fluorescent X-ray analysis method is that the analysis can be performed in a very short time.
  • the above-mentioned polysiloxane is obtained from sampling in an arbitrary step after copolymerization. Only about one hour is required until the measurement result of the organosiloxane content ratio is obtained. Therefore, the measurement results are fed back quickly to a control device that controls the amount of polyorganosiloxane added, the amount of polyorganosiloxane added to the reaction system is adjusted, and the deviation of the polyorganosiloxane content from the set value is quickly achieved. Can be adjusted. As a result, a polycarbonate-polyorganosiloxane copolymer having a small variation width of the polyorganosiloxane content can be obtained, and the quality can be improved.
  • the steps from the addition of the polyorganosiloxane to the control of the addition amount of the polyorganosiloxane based on the measurement value by the fluorescent X-ray analysis method are continuously performed.
  • the measurement result of the polyorganosiloxane content in the copolymer obtained by X-ray fluorescence analysis is quickly fed back to the controller to adjust the amount of polyorganosiloxane added to the reaction system.
  • the deviation of the polyorganosiloxane content from the set value can be adjusted quickly.
  • Measurement of the polycarbonate-polyorganosiloxane copolymer by X-ray fluorescence analysis is performed, for example, as follows. A part of the polymerization solution obtained in an arbitrary step after copolymerization is collected, and a solution containing a polycarbonate-polyorganosiloxane copolymer obtained by separating the organic phase from the polymerization solution is collected in a petri dish or the like, and the organic A sheet or film obtained by evaporating the phase can be subjected to measurement by an X-ray fluorescence analyzer.
  • a part of the powder or granulated material is collected continuously or intermittently after pulverization / granulation, and the collected powder or granulated material or a sheet or film thereof is subjected to measurement by a fluorescent X-ray analyzer. Can be done.
  • the polycarbonate-polyorganosiloxane obtained after the copolymerization continuously or intermittently the polyorganosiloxane content in the copolymer at any intervals in the polycarbonate-polyorganosiloxane copolymer production line Can be monitored.
  • X-ray fluorescence analyzers are roughly classified into energy dispersion type and wavelength dispersion type, and any of them may be used in the fluorescence X-ray analysis in the present invention.
  • concentration (content ratio) of the target element in the sample is measured by measuring the intensity of the line spectrum (characteristic X-ray) of the wavelength unique to each element obtained by irradiating the sample with X-rays. ).
  • line spectrum characteristic X-ray
  • a wide range of elements can be targeted, but in practice, an element having an atomic number of sodium or higher is often measured.
  • the concentration of silicon in the polycarbonate-polyorganosiloxane copolymer can be determined using a calibration curve.
  • the calibration curve is prepared from the X-ray intensity of the quantitative element (silicon) obtained by performing fluorescent X-ray analysis using a sample whose polyorganosiloxane concentration has been previously determined by NMR.
  • the silicon concentration in the copolymer can be measured in a short time by comparing with the X-ray intensity of the silicon atom obtained from the actual measurement sample.
  • the lower limit of determination of the polyorganosiloxane content by the fluorescent X-ray method is about 0.1% by mass. When the polyorganosiloxane content is 0.1% by mass or more, it can be preferably used as the measurement value of the production method of the present invention, assuming that the quantitative value obtained by fluorescent X-ray analysis is significant.
  • FIG. 1 A schematic diagram of a production line for carrying out the production method of the polycarbonate-polyorganosiloxane copolymer of the present invention when the interfacial polymerization method is used is shown in FIG.
  • the production line is generally a dihydric phenol, here bisphenol A from a bisphenol A dissolution tank 111 in which bisphenol A is dissolved in an alkaline aqueous solution, a carbonate precursor (indicated by phosgene in the figure), and a molecular weight regulator as required.
  • oligomer preparation step 1 polycarbonate oligomer, polyorganosiloxane and dihydric phenol are reacted in the presence of an aqueous alkaline solution 2, polycarbonate-poly Separation step 3 for separating an organic phase containing an organosiloxane copolymer and an aqueous phase containing excess dihydric phenol, a washing step 4 for washing the resulting organic phase, and a concentration step for concentrating the washed organic phase 5. It has a pulverization / granulation step 6 for pulverizing or granulating the concentrate.
  • the polyorganosiloxane content ratio in the polycarbonate-polyorganosiloxane using the fluorescent X-ray analysis method according to the present invention is measured with the powder or pellets after the powdering / granulating step 6 or with a hot press molding machine shown in FIG.
  • a sheet or film obtained by (evaporation to dryness) is used as a measurement sample.
  • control valve 13 for adjusting the amount of the polyorganosiloxane introduced into the copolymerization step 2
  • the control valve 13 is connected to the control device 12, and the control device 12 is connected to the fluorescent X-ray analyzer 11.
  • a sample sampled at an arbitrary interval after the copolymerization step 2 is measured by the fluorescent X-ray analyzer 11, and the measurement data is manually input to the control device 12 or automatically sent, and based on the measurement result.
  • the control valve 13 can be automatically controlled by the control device 12 to adjust the amount of polyorganosiloxane.
  • any device can be used as long as it can control a control valve for adjusting the amount of polyorganosiloxane to be added.
  • the reaction between the dihydric phenol and the carbonate precursor is not particularly limited, and a known method can be adopted, and the reaction is preferably carried out by an interfacial polymerization method in the presence of a water-insoluble organic solvent. If necessary, the reaction can be carried out in the presence of a molecular weight regulator and a polymerization catalyst.
  • the dihydric phenol is used as an aqueous alkali solution of dihydric phenol in which dihydric phenol is dissolved in an aqueous solution of an alkali compound.
  • dihydric phenol As the dihydric phenol, it is preferable to use a dihydric phenol represented by the following general formula (1). In addition, it is preferable to similarly use the dihydric phenol represented by the following general formula (1) for the dihydric phenol used in the present invention regardless of whether or not it has (1) a PC oligomer preparation step.
  • R 1 and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms.
  • X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO- , -SO 2- , -O-, or -CO-.
  • a and b are each independently an integer of 0 to 4.
  • Examples of the dihydric phenol represented by the general formula (1) include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis ( Bis (hydroxyphenyl) alkanes such as 4-hydroxyphenyl) ethane and 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) And cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, and bis (4-hydroxyphenyl) ketone. It is done.
  • dihydric phenols may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • bis (hydroxyphenyl) alkane is preferable as the dihydric phenol
  • bisphenol A is more preferable.
  • dihydric phenols other than bisphenol A include bis (hydroxyaryl) alkanes, bis (hydroxyaryl) cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, and dihydroxy. Examples include diphenyls, dihydroxydiarylfluorenes, dihydroxydiaryladamantanes and the like. These dihydric phenols may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • bis (hydroxyaryl) alkanes examples include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- Bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxy Phenyl) naphthylmethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy) -3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorofe) Le) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane.
  • Examples of bis (hydroxyaryl) cycloalkanes include 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) norbornane, 1,1-bis (4-hydroxyphenyl) cyclododecane and the like.
  • Examples of dihydroxyaryl ethers include 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether.
  • dihydroxydiaryl sulfides include 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, and the like.
  • dihydroxydiaryl sulfoxides include 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, and the like.
  • dihydroxydiaryl sulfones include 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.
  • dihydroxydiphenyls examples include 4,4'-dihydroxydiphenyl.
  • dihydroxydiarylfluorenes include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.
  • dihydroxydiaryladamantanes examples include 1,3-bis (4-hydroxyphenyl) adamantane, 2,2-bis (4-hydroxyphenyl) adamantane, 1,3-bis (4-hydroxyphenyl) -5,7- Examples thereof include dimethyladamantane.
  • dihydric phenols for example, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxyphenyl) -9-anthrone, 1,5 -Bis (4-hydroxyphenylthio) -2,3-dioxapentane and the like.
  • the carbonate precursor used in the present invention is not limited to the interfacial polymerization method, and examples thereof include carbonyl halide, carbonic acid diester, haloformate and the like. Specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like. Among these, phosgene used in the interfacial polymerization method is preferable.
  • aqueous alkali solution for dissolving the dihydric phenol those having an alkali concentration of 1 to 15% by mass are preferably used.
  • the amount of dihydric phenol in the alkaline aqueous solution is usually selected in the range of 0.5 to 20% by mass.
  • the alkaline aqueous solution include aqueous solutions of alkaline inorganic compounds such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide.
  • an aqueous solution of an alkali metal hydroxide is preferable, and an aqueous solution of sodium hydroxide is more preferable.
  • the water-insoluble organic solvent for example, halogenated hydrocarbons such as methylene chloride, chlorobenzene and chloroform are preferable, and methylene chloride is more preferable.
  • the amount of the water-insoluble organic solvent used is usually selected so that the volume ratio of the organic phase to the aqueous phase is preferably 5/1 to 1/7, more preferably 2/1 to 1/4. .
  • the reaction temperature in the oligomer preparation step (1) is usually selected in the range of 0 to 50 ° C., preferably 5 to 40 ° C.
  • Polymerization catalysts include tertiary amines and quaternary ammonium salts.
  • tertiary amine include trimethylamine, triethylamine, and tripropylamine.
  • quaternary ammonium salt include trimethylbenzylammonium chloride and triethylbenzylammonium chloride.
  • a tertiary amine is preferable, and triethylamine is more preferable.
  • a molecular weight regulator may be added as necessary.
  • the molecular weight regulator is not particularly limited as long as it is a monohydric phenol.
  • the obtained reaction mixture is a mixture containing an organic phase containing a polycarbonate oligomer and an aqueous phase containing impurities such as sodium chloride. Therefore, the organic phase containing the polycarbonate oligomer obtained by performing stationary separation etc. is used in a copolymerization process.
  • an example of the copolymerization step (2) includes a polycarbonate oligomer solution obtained by the polycarbonate oligomer preparation step (1), a polyorganosiloxane solution diluted with a water-insoluble organic solvent, and a water-insoluble organic solvent.
  • an aqueous alkaline compound solution are optionally mixed in the presence of a polymerization catalyst and subjected to interfacial polymerization usually at a temperature in the range of 0 to 80 ° C., preferably 5 to 40 ° C.
  • a molecular weight modifier, an alkaline aqueous solution, and an alkaline aqueous solution of dihydric phenol are mixed, and the interfacial polymerization is completed at a temperature usually in the range of 0 to 50 ° C., preferably 5 to 40 ° C.
  • the alkaline aqueous solution, the water-insoluble organic solvent, the polymerization catalyst, the aromatic dihydric phenol and the molecular weight regulator in the copolymerization step include those described in the polycarbonate oligomer preparation step (1). Is the same.
  • the volume ratio of the organic phase to the aqueous phase in the interfacial polymerization is also the same as in the polycarbonate oligomer preparation step (1).
  • polyorganosiloxane those represented by the following general formulas (2) and (3) can be used.
  • R 3 to R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • Y is -R 7 O -, - R 7 COO -, - R 7 NH -, - R 7 NR 8 -, - COO -, - S -, - R 7 COO-R 9 -O-, or -R 7 R 7 represents O—R 10 —O—, and R 7 represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group.
  • R 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group.
  • R 9 represents a diarylene group.
  • R 10 represents a linear, branched or cyclic alkylene group, or a diarylene group.
  • Z represents a hydrogen atom or a halogen atom.
  • ⁇ represents a divalent group derived from a diisocyanate compound or a divalent group derived from dicarboxylic acid or a halide of dicarboxylic acid.
  • the sum of p and q is n, and n represents an average number of repetitions of 30 to 500. ]
  • Examples of the halogen atom independently represented by R 3 to R 6 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkyl group independently represented by R 3 to R 6 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups (“various” means linear and all branched ones) And the same applies hereinafter), various pentyl groups, and various hexyl groups.
  • Examples of the alkoxy group independently represented by R 3 to R 6 include a case where the alkyl group moiety is the alkyl group.
  • Examples of the aryl group independently represented by R 3 to R 6 include a phenyl group and a naphthyl group.
  • R 3 to R 6 are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • the polyorganosiloxanes represented by the general formulas (2) and (3) are preferably those in which R 3 to R 6 are all methyl groups.
  • R 7 O—R 10 —O— examples include an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and examples of the cyclic alkylene group include Examples thereof include a cycloalkylene group having 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms.
  • the aryl-substituted alkylene group represented by R 7 may have a substituent such as an alkoxy group or an alkyl group on the aromatic ring.
  • a substituent such as an alkoxy group or an alkyl group on the aromatic ring.
  • Specific examples of the structure include, for example, the following general formula (4) or ( The structure of 5) can be shown.
  • the alkylene group is couple
  • the diarylene group represented by R 7 , R 9 and R 10 is a group in which two arylene groups are linked directly or via a divalent organic group.
  • —Ar 1 —W— A group having a structure represented by Ar 2 —.
  • Ar 1 and Ar 2 represent an arylene group
  • W represents a single bond or a divalent organic group.
  • the divalent organic group represented by W is, for example, an isopropylidene group, a methylene group, a dimethylene group, or a trimethylene group.
  • Examples of the arylene group represented by R 7 , Ar 1, and Ar 2 include arylene groups having 6 to 14 ring carbon atoms such as a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group. These arylene groups may have an arbitrary substituent such as an alkoxy group or an alkyl group.
  • the alkyl group represented by R 8 is linear or branched having 1 to 8, preferably 1 to 5 carbon atoms.
  • Examples of the alkenyl group include straight or branched chain groups having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms.
  • Examples of the aryl group include a phenyl group and a naphthyl group.
  • Examples of the aralkyl group include a phenylmethyl group and a phenylethyl group.
  • the linear, branched or cyclic alkylene group represented by R 10 is the same as R 7 .
  • Y is preferably —R 7 O—, wherein R 7 is an aryl-substituted alkylene group, particularly a residue of a phenolic compound having an alkyl group, and is an organic residue derived from allylphenol or eugenol. The organic residue derived from is more preferable.
  • ⁇ represents a divalent group derived from a diisocyanate compound or a divalent group derived from dicarboxylic acid or a halide of dicarboxylic acid.
  • ⁇ is represented by the following general formulas (3-1) to (3-5): And a divalent group represented.
  • Examples of the polyorganosiloxane represented by the general formula (2) include compounds represented by the following general formulas (2-1) to (2-11).
  • R 3 to R 6 , n and R 8 are as defined above, and preferred ones are also the same.
  • c represents a positive integer and is usually an integer of 1 to 6.
  • the phenol-modified polyorganosiloxane represented by the general formula (2-1) is preferable from the viewpoint of ease of polymerization.
  • ⁇ , ⁇ -bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane which is one of the compounds represented by the general formula (2-2), ⁇ , ⁇ -bis [3- (4-hydroxy-3-methoxyphenyl) propyl] polydimethylsiloxane which is one of the compounds represented by the general formula (2-3) is preferable.
  • the method for producing the crude polyorganosiloxane used in the present invention is not particularly limited.
  • cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize ⁇ , ⁇ -dihydrogenorganopentasiloxane, Phenol compounds having an unsaturated group in the ⁇ , ⁇ -dihydrogenorganopentasiloxane in the presence of a hydrosilylation catalyst (eg 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.), etc.
  • a crude polyorganosiloxane can be obtained by addition reaction.
  • octamethylcyclotetrasiloxane and tetramethyldisiloxane are reacted in the presence of sulfuric acid (acidic catalyst), and the resulting ⁇ , ⁇ -dihydrogenorgano is obtained.
  • a crude polyorganosiloxane can be obtained by subjecting polysiloxane to an addition reaction with a phenol compound having an unsaturated group in the presence of a hydrosilylation reaction catalyst.
  • the ⁇ , ⁇ -dihydrogenorganopolysiloxane can be used by appropriately adjusting the chain length n depending on the polymerization conditions, or a commercially available ⁇ , ⁇ -dihydrogenorganopolysiloxane may be used. .
  • a transition metal catalyst may be mentioned, and among them, a platinum catalyst is preferably used from the viewpoint of reaction rate and selectivity.
  • a platinum catalyst is preferably used from the viewpoint of reaction rate and selectivity.
  • Specific examples of the platinum-based catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, a complex of platinum and a vinyl group-containing siloxane, platinum-supported silica, platinum-supported activated carbon, and the like.
  • the transition metal derived from the transition metal catalyst used as the hydrosilylation reaction catalyst contained in the crude polyorganosiloxane is adsorbed on the adsorbent and removed. It is preferable to do.
  • the adsorbent for example, one having an average pore diameter of 1000 mm or less can be used. If the average pore diameter is 1000 mm or less, the transition metal in the crude polyorganosiloxane can be efficiently removed. From such a viewpoint, the average pore diameter of the adsorbent is preferably 500 mm or less, more preferably 200 mm or less, still more preferably 150 mm or less, and still more preferably 100 mm or less. From the same viewpoint, the adsorbent is preferably a porous adsorbent.
  • the adsorbent is not particularly limited as long as it has the above average pore diameter.
  • Cellulose and the like can be used, and at least one selected from the group consisting of activated clay, acidic clay, activated carbon, synthetic zeolite, natural zeolite, activated alumina, silica and silica-magnesia-based adsorbent is preferable.
  • the adsorbent can be separated from the polyorganosiloxane by any separation means.
  • means for separating the adsorbent from the polyorganosiloxane include a filter and centrifugal separation.
  • a filter such as a membrane filter, a sintered metal filter, or a glass fiber filter can be used, but it is particularly preferable to use a membrane filter.
  • the average particle diameter of the adsorbent is usually 1 ⁇ m to 4 mm, preferably 1 to 100 ⁇ m.
  • the amount used is not particularly limited.
  • An amount of the porous adsorbent in the range of preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the crude polyorganosiloxane can be used.
  • the crude polyorganosiloxane to be treated is not in a liquid state due to its high molecular weight, it may be heated to a temperature at which the polyorganosiloxane is in a liquid state when adsorbing with the adsorbent and separating the adsorbent. Good. Alternatively, it may be carried out by dissolving in a solvent such as methylene chloride or hexane.
  • a line mixer, a static mixer, an orifice mixer, a stirring tank, a multi-stage tower type stirring tank, a non-stirring tank, piping, and the like can be used as a reactor.
  • the number of reactors used in the copolymerization step (2) may be one or plural. That is, the copolymerization step (2) may be composed of a plurality of reactors.
  • it is preferable to use a reactor having a stirring function in the reactor it is preferable to use a line mixer, a static mixer, an orifice mixer, a stirring tank, or the like.
  • a line mixer, a static mixer, an orifice mixer, a stirring tank, a multistage tower type stirring tank, a non-stirring tank, piping, etc. can be used arbitrarily.
  • the polyorganosiloxane content in the polycarbonate-polyorganosiloxane copolymer is preferably set to be 0.1% by mass or more. As described above, when the polyorganosiloxane content is 0.1% by mass or more, the measurement result when measured using a fluorescent X-ray analyzer can be obtained with sufficient accuracy.
  • This step is a step of separating the polymerization liquid obtained in step (2) into an aqueous phase and a water-insoluble organic phase.
  • the resulting polymerization solution is appropriately diluted with an inert organic solvent such as methylene chloride.
  • the diluted solution is allowed to stand or centrifuged to separate the aqueous phase and the organic phase containing polycarbonate-polyorganosiloxane.
  • centrifugation there are no particular limitations on the centrifugation conditions, but it is usually preferable that the rotational speed be about 1,000 to 3,000 rpm.
  • the water-insoluble organic solvent phase is washed with an alkaline aqueous solution (hereinafter sometimes referred to as alkali washing).
  • alkali washing an alkaline aqueous solution
  • examples of the alkaline compound used in the alkaline aqueous solution include the same as those used in the step (1), and preferred ones are also the same.
  • After washing with an aqueous alkali solution it is separated into an aqueous phase and an organic phase. Also in this case, there is no particular limitation on the separation method, and it may be stationary separation or centrifugation.
  • the amount of the aqueous alkaline solution used for washing is not particularly limited, but is preferably about 5 to 40% by volume, more preferably 5 to 30% by volume in the total liquid, from the viewpoint of the washing effect and reduction of the amount of wastewater generated. More preferably, it is 10 to 20% by volume. If it is 40 volume% or less, a continuous phase will not convert into a water phase from an organic phase, but the extraction efficiency from an organic phase can be maintained highly. Since the aqueous phase obtained in the step (3) contains a dihydric phenol or an alkaline compound, the aqueous phase is used in the step (1) or (2), particularly the step (1) from the viewpoint of production cost. It is preferable to reuse it.
  • washing step (4) the water-insoluble organic solvent phase separated in step (3) is washed with an acidic aqueous solution (hereinafter sometimes referred to as acid washing), and then the aqueous phase and water-insoluble.
  • acid washing an acidic aqueous solution
  • This is a step of separating into an organic solvent phase.
  • a polymerization catalyst and a trace amount of an alkaline compound that can be contained in the organic phase separated in the step (3) can be removed.
  • separate, and stationary separation may be sufficient.
  • Examples of the acid used for the preparation of the acidic aqueous solution include hydrochloric acid, phosphoric acid, and the like, and hydrochloric acid is preferable, but is not particularly limited thereto.
  • the organic phase obtained by the separation tends to contain the acid or inorganic substance used in the washing, it is preferably washed with water once or more (hereinafter sometimes referred to as water washing).
  • the cleanliness of the water-insoluble organic solvent phase can be evaluated by the electrical conductivity of the water phase after washing.
  • the target electric conductivity is preferably 1 mS / m or less, more preferably 0.5 mS / m or less. After washing with water, it is separated into an aqueous phase and a water-insoluble organic solvent phase.
  • aqueous phase (including the aqueous phase after washing with water) separated in step (4) may contain a polycarbonate-polyorganosiloxane copolymer, this is extracted with an organic solvent, and a part of the extract or It is preferable to reuse the whole for the step (1) or (2), particularly the step (1) after appropriately passing through a devolatilization step for removing carbon dioxide and a distillation purification step.
  • a devolatilization step the method described in JP-A-2005-60599 can be employed.
  • Step (5) Concentration step In this step, the organic phase obtained through step (4) is concentrated. In the subsequent step (6), it is concentrated to a concentration range suitable for pulverization / granulation, preferably 10 to 45% by mass.
  • the water-insoluble organic solvent removed in the concentration step (5) can be reused in the step (1) or (2), or the polycarbonate-polyorganosiloxane copolymer or the like can be recovered from the aqueous phase separated in the washing step. It is preferably reused as a solvent for extracting organic substances.
  • the production method of the present invention preferably includes a distillation purification step of a water-insoluble organic solvent, a devolatilization step for removing carbon dioxide in the water-insoluble organic solvent, and the like.
  • the organic phase is Any polymerization solution obtained from the copolymerization step (2) to the concentration step (5) may be used.
  • Powdering / granulating step The organic phase containing the polycarbonate-polyorganosiloxane copolymer concentrated in the concentrating step (5) is subjected to the kneader method, hot water granulation in the powdering / granulating step (6).
  • a powder (flakes) or a granulated product can be obtained by a known method such as a method or a powder bed granulation method. After pulverization / granulation, it is usually preferable to dry the powder (flake) or granulated product obtained at about 80 to 160 ° C. under reduced pressure.
  • a polycarbonate-polyorganosiloxane copolymer having a small fluctuation range of the amount of polyorganosiloxane during the polycarbonate-polyorganosiloxane copolymerization can be obtained. Since the polycarbonate-polyorganosiloxane copolymer obtained by the production method of the present invention is excellent in quality, it can be used as a casing for mobile phones, mobile personal computers, digital cameras, video cameras, electric tools, and other daily necessities. Suitable.
  • the viscosity number and the viscosity average molecular weight (Mv) were determined by the following methods.
  • Example 1 A polycarbonate-polydimethylsiloxane copolymer was continuously produced using the production line shown in FIG. Specifically, it is as follows. (1) Bisphenol A sodium hydroxide aqueous solution and polycarbonate oligomer ⁇ Bisphenol A sodium hydroxide aqueous solution> In a bisphenol A dissolution tank 233, 2,000 mass ppm sodium dithionite was added to a 5.6 mass% sodium hydroxide aqueous solution with respect to bisphenol A to be dissolved later. In this aqueous sodium hydroxide solution, bisphenol A as an aromatic dihydric phenol was dissolved so that the concentration in the aqueous solution was 13.5% by mass to prepare an aqueous sodium hydroxide solution of bisphenol A.
  • PTBP pt-butylphenol
  • CF chloroformate
  • the weight average molecular weight (Mw) was determined using GPC [column: TOSOH TSK-GEL MULTIPORE HXL-M (2) + Shodex KF801 (1)], temperature 40 ° C., flow rate 1.0 ml / min. , Detector: RI], and measured as a standard polystyrene equivalent molecular weight (weight average molecular weight: Mw).
  • the reactor 222 (Rx-1) was a mixer “Pipeline Homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.) equipped with turbine blades and operated at a rotational speed of 4,400 rpm.
  • the reactor 223 (Rx-2) was a mixer “Pipeline Homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.) equipped with turbine blades and operated at a rotational speed of 4,400 rpm.
  • the polymerization reaction liquid exiting the reactor 223 (Rx-2) is sequentially led to the reactor 224 (Rx-3) and the reactor 225 (Rx-4) to complete the polymerization reaction while controlling the temperature to 38 ° C. or lower. I let you.
  • the reactor 224 (Rx-3) is a reactor having an orifice plate and a cooling jacket
  • the reactor 225 (Rx-4) is a column type five-stage reactor having a cooling jacket.
  • the polyorganosiloxane concentration was measured using a sample in which the polyorganosiloxane concentration was quantified in advance by NMR.
  • a calibration curve was created from the X-ray intensity of silicon atoms measured by the line analyzer 211, and the polyorganosiloxane concentration was measured from the X-ray intensity ratio obtained by measuring an actual sample.
  • the supply amount of the polyorganosiloxane was adjusted [feedback control (FB)] by automatically controlling the control valve 213 by the controller 212 based on the quantitative result by the fluorescent X-ray analyzer 211.
  • Table 3 shows the measurement results of 1 to 20 hours after the start of the production of the polycarbonate-polyorganosiloxane copolymer.
  • the NMR used for preparing the calibration curve was JEOL RESONANCE Co., Ltd. (model: ECA500), and the X-ray fluorescence analysis was performed using a PANalitical X-ray fluorescence analyzer (model: MagiX-PW2403).
  • Comparative Example 1 The polyorganosiloxane concentration of the polycarbonate-polyorganosiloxane copolymer powder obtained in Example 1 was measured by NMR. It took 3 hours from the collection of the polycarbonate-polyorganosiloxane copolymer powder to the measurement of the polyorganosiloxane concentration. Based on this measured value, the supply amount of the polyorganosiloxane was adjusted by a control device [feedback control (FB)].
  • FB feedback control
  • the polyorganosiloxane content in the polycarbonate-polyorganosiloxane copolymer is measured by fluorescent X-ray analysis, and the amount of polyorganosiloxane added to the reaction system based on the measured value
  • fluorescent X-ray analysis method a trace amount analysis in a short time is possible, and the amount of polyorganosiloxane added to the reaction system can be quickly controlled.
  • the polyorganosiloxane content in the polycarbonate-polyorganosiloxane copolymer is measured by fluorescent X-ray analysis, and the amount of polyorganosiloxane added to the reaction system is controlled based on the measured value.
  • a polycarbonate-polyorganosiloxane copolymer having a small fluctuation range of the amount of polyorganosiloxane in the copolymer can be stably obtained.

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Abstract

La présente invention concerne un procédé de production d'un copolymère polycarbonate-polyorganosiloxane consistant à ajouter un polyorganosiloxane dans un système réactionnel destiné à polymériser un phénol dihydrique et un précurseur de carbonate en vue de sa copolymérisation, le procédé de production d'un copolymère polycarbonate-polyorganosiloxane comprenant les étapes consistant à recueillir une partie du copolymère polycarbonate-polyorganosiloxane obtenu après la copolymérisation, à mesurer la teneur en polyorganosiloxane du copolymère par spectrométrie de fluorescence des rayons x et à réguler la quantité de polyorganosiloxane ajoutée au système réactionnel sur la base de la valeur mesurée.
PCT/JP2015/057008 2014-03-28 2015-03-10 Procédé de production d'un copolymère polycarbonate-polyorganosiloxane WO2015146575A1 (fr)

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CN115612108A (zh) * 2022-10-11 2023-01-17 沧州大化股份有限公司 一种聚硅氧烷共聚聚碳酸酯的连续化生产工艺及其生产装置

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US9334372B1 (en) * 2015-02-25 2016-05-10 Momentive Performance Materials Inc. Reactive polysiloxanes and copolymers made therefrom
EP4071196A4 (fr) 2019-12-06 2023-09-13 Idemitsu Kosan Co., Ltd. Copolymère polycarbonate/polyorganosiloxane et composition de résine comprenant ledit copolymère
KR20220113692A (ko) 2019-12-06 2022-08-16 이데미쓰 고산 가부시키가이샤 폴리카보네이트-폴리오가노실록세인 공중합체 및 해당 공중합체를 포함하는 수지 조성물
JPWO2021112257A1 (fr) 2019-12-06 2021-06-10
EP3957672A1 (fr) 2020-08-20 2022-02-23 Idemitsu Kosan Co.,Ltd. Copolymère de polycarbonate-polyorganosiloxane, son procédé de production et composition de résine comprenant le copolymère
EP3957673A1 (fr) 2020-08-20 2022-02-23 Idemitsu Kosan Co.,Ltd. Copolymère de polycarbonate-polyorganosiloxane, son procédé de production et composition de résine comprenant le copolymère
EP3957674A1 (fr) 2020-08-20 2022-02-23 Idemitsu Kosan Co.,Ltd. Copolymère de polycarbonate-polyorganosiloxane, son procédé de production et composition de résine comprenant le copolymère

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