CN102336899B - Control method for safely and continuously producing polycarbonate oligomer - Google Patents
Control method for safely and continuously producing polycarbonate oligomer Download PDFInfo
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- CN102336899B CN102336899B CN2011101715239A CN201110171523A CN102336899B CN 102336899 B CN102336899 B CN 102336899B CN 2011101715239 A CN2011101715239 A CN 2011101715239A CN 201110171523 A CN201110171523 A CN 201110171523A CN 102336899 B CN102336899 B CN 102336899B
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 69
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 36
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 150
- 239000007789 gas Substances 0.000 claims abstract description 90
- 239000007864 aqueous solution Substances 0.000 claims abstract description 36
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 35
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000460 chlorine Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 19
- NHYCGSASNAIGLD-UHFFFAOYSA-N chlorine monoxide Inorganic materials Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002341 toxic gas Substances 0.000 claims abstract description 12
- 239000011541 reaction mixture Substances 0.000 claims abstract description 8
- 238000012546 transfer Methods 0.000 claims abstract description 4
- 150000002989 phenols Chemical class 0.000 claims description 42
- 239000003513 alkali Substances 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- -1 phenol compound Chemical class 0.000 abstract description 10
- 238000010924 continuous production Methods 0.000 abstract description 3
- 230000005856 abnormality Effects 0.000 abstract 1
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 238000001784 detoxification Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 49
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 230000004907 flux Effects 0.000 description 9
- 239000000575 pesticide Substances 0.000 description 9
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 7
- 229930185605 Bisphenol Natural products 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000019634 flavors Nutrition 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001804 chlorine Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XLHUBROMZOAQMV-UHFFFAOYSA-N 1,4-benzosemiquinone Chemical compound [O]C1=CC=C(O)C=C1 XLHUBROMZOAQMV-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- XSXWOBXNYNULJG-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1O XSXWOBXNYNULJG-UHFFFAOYSA-N 0.000 description 1
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- LEDTWDICPMFGDW-UHFFFAOYSA-N 4-cyclodecylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCCCCCC1 LEDTWDICPMFGDW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- PFIMJZLHTUKTPH-UHFFFAOYSA-N OC1=CC=C([S])C=C1 Chemical compound OC1=CC=C([S])C=C1 PFIMJZLHTUKTPH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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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
- C08G64/20—General preparatory processes
- C08G64/36—General preparatory processes using carbon monoxide
-
- 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
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for safely producing a polycarbonate oligomer, in which harmful phosgene is automatically eliminated without leaking to the outside of the system even if an abnormality occurs. A method for controlling the continuous production of a polycarbonate oligomer, comprising a step (1) of continuously producing a phosgene gas containing unreacted carbon monoxide by supplying chlorine and carbon monoxide to a phosgene reactor, and a step (2) of continuously producing a reaction mixture containing a polycarbonate oligomer by continuously supplying the phosgene gas continuously produced in the step (1), an aqueous alkaline solution of a dihydric phenol, and an organic solvent to an oligomer reactor. The method for controlling the continuous production of a polycarbonate oligomer stops the supply of the phosgene and the carbon monoxide in the step (1) and stops the supply of the phosgene gas to the oligomer reactor when the following conditions (i) and/or (ii) are satisfied, and transfers the toxic gas containing the phosgene gas to a detoxifying device for detoxification. Condition (i): when the value of < F2/(F3 × a/100) > using the solvent flow rate (F2[ kg/h ]), the alkaline aqueous solution flow rate (F3[ kg/h ]), and the dihydric phenol compound concentration (a [% by mass ]) supplied to the oligomer reactor is 3.27 or less. Condition (ii): when the value of the parameter < (F3 × a/100)/F1> using the phosgene gas flow rate (F1[ kg/h ]), the alkaline aqueous solution flow rate of the dihydric phenol compound (F3[ kg/h ]), and the dihydric phenol compound concentration (a [% by mass ]) supplied to the oligomer reactor is 1.23 or less.
Description
Technical field
The present invention relates to for the control method of making continuously safely polycarbonate oligomer.
Background technology
Usually, manufacture method as polycarbonate, the known interfacial that has dihydric phenols of making (bisphenols) and carbonyl chloride directly to react, the ester-interchange method that bisphenols and diphenyl carbonate react under condition of no solvent, from obtaining the point of the good polycarbonate of quality, interfacial becomes main flow (for example consulting Japanese Patent Laid-Open 2004-331916 communique).
In interfacial, use the basic cpd such as bisphenols, sodium hydroxide and carbonyl chloride as the polycarbonate raw material, also can add as required end and stop agent (molecular weight regulator) etc.The industry manufacturing of polycarbonate is generally carried out as follows: being blown into carbonyl chloride in the bisphenols alkaline aqueous solution makes it to generate the polycarbonate oligomer with reactive chloroformyl, further when generating or polycarbonate oligomer and bisphenols alkali aqueous solution are reacted.
Disclose the liquid carbon acyl chlorides of storing distillation refining carbon acyl chlorides gained in the Japanese Patent Laid-Open 2001-261321 communique, re-use the method that this liquid carbon acyl chlorides is made polycarbonate.
But the toxicity of carbonyl chloride is high, and is undesirable from the viewpoint of storing stability, for example exists in the situation that liquid carbon acyl chlorides storagetank damages through corrosion the risk that carbonyl chloride leaks occurs.Although this risk can be removed equipment and reduces via carbonyl chloride is set, because the amount of carbonyl chloride is many, it is very time-consuming to remove carbonyl chloride, and on the other hand, wants the short period of time to remove, and needs again large-scale equipment, causes expense to increase.
The world discloses No. 2007/083721 and discloses the carbonyl chloride that does not liquefy by chlorine and reaction of carbon monoxide are obtained, and is directly used in the polycarbonate oligomer method for continuous production of making polycarbonate oligomer.According to this method, compare with the method for using the liquid carbon acyl chlorides, can reduce intrasystem carbonyl chloride recoverable amount.
Summary of the invention
Yet, in the above-mentioned patent documentation, whichsoever all do not have being caused that by the raw material supplying fault in the oligopolymer reactor oligopolymer separates out, stop up the accident of reactor etc. and carried out imagination, also openly harmful carbonyl chloride outside system, do not leak and the polycarbonate manufacture method of slowly being removed.
The problem that the present invention will solve is, provides a kind of and when making polycarbonate, makes continuously in the method for polycarbonate oligomer, even abnormal, also can auto-stop mechanism, and harmful carbonyl chloride method that can not be removed to system's external leakage.
Above-mentioned problem is resolved by the control method of following continuous manufacturing polycarbonate oligomer.
A kind of method of controlling continuous manufacturing polycarbonate oligomer, possess in the carbonyl chloride reactor and supply with chlorine and carbon monoxide, make continuously the operation (1) of the carbonyl chloride gas that contains unreacted carbon monoxide, and continuous supplying is given the carbonyl chloride gas of making continuously in the described operation (1), alkali aqueous solution and the organic solvent of dihydric phenol in the oligopolymer reactor, makes continuously the operation (2) of the reaction mixture that contains polycarbonate oligomer;
The method that polycarbonate oligomer is made in described control is continuously satisfying following condition (i) and/or lower time of situation (ii), stop supply chlorine and carbon monoxide in the described operation (1), stop simultaneously supplying with carbonyl chloride gas in the oligopolymer reactor, and the toxic gas that will contain carbonyl chloride gas transfer to carry out in the device of removing the evil innoxious;
Condition (i): when the parameter＜F2/ of the alkali aqueous solution flow that has used the solvent flux of supplying with the oligopolymer reactor (F2[kg/h]), dihydric phenolic compounds (F3[kg/h]) and dihydric phenolic compounds concentration (a[quality %]) (F3 * a/100)〉value become 3.27 when following.
Condition (ii): when the parameter of the alkali aqueous solution flow that has used the carbonyl chloride gas flow of supplying with the oligopolymer reactor (F1[kg/h]), dihydric phenolic compounds (F3[kg/h]) and dihydric phenolic compounds concentration (a[quality %])＜(F3 * a/100)/F1〉value become 1.23 when following.
Description of drawings
[Fig. 1] is the summary signal process picture sheet of a routine preferred implementation of the control method of continuous manufacturing polycarbonate oligomer of the present invention.
Embodiment
The method that polycarbonate oligomer is made in control of the present invention continuously is following method, when making polycarbonate oligomer continuously by interfacial, constantly the carbonyl chloride gas flow (F1) of oligopolymer reactor is supplied with in monitoring, solvent flux (F2), the alkali aqueous solution flow (F3) of dihydric phenolic compounds and dihydric phenolic compounds concentration (a[quality %]), when satisfying aftermentioned condition (i) and/or situation (ii), can automatically stop to supply with as chlorine and the carbon monoxide of carbonyl chloride raw material and in the oligopolymer reactor, supply with carbonyl chloride, simultaneously, can also automatically control intrasystem carbonyl chloride is transplanted in the device of removing the evil.
[manufacturing of polycarbonate]
The method that polycarbonate oligomer is made in control of the present invention continuously is applicable to make the interfacial of dihydric phenols and carbonyl chloride direct reaction, is applicable to the successive reaction mode.
The method that polycarbonate oligomer is made in control of the present invention continuously possesses in the carbonyl chloride reactor supplies with chlorine and carbon monoxide, make continuously the operation (1) of the carbonyl chloride gas that contains unreacted carbon monoxide, and continuous supplying is given the carbonyl chloride gas of making continuously in the described operation (1), alkali aqueous solution and the organic solvent of dihydric phenol in the oligopolymer reactor, makes continuously the operation (2) of the reaction mixture that contains polycarbonate oligomer.
＜operation 1 〉
Operation (1) is to supply with chlorine and carbon monoxide in the carbonyl chloride reactor, makes continuously the operation of the carbonyl chloride gas that contains unreacted carbon monoxide.
From the quality of polycarbonate oligomer, carbon monoxide can react to make the above refining thing of preferred purity 95 capacity % by making coke, oil, Sweet natural gas, alcohol and oxygen.Particularly preferably the content of sulphur composition is below 50ppm.In addition, chlorine: preferred 1: 1.01～1: 1.3 of the ratio of carbon monoxide (mol ratio), more preferably 1: 1.02～1: 1.2.
In addition, reaction can be carried out according to the known method that for example Japanese Patent examined patent publication 55-14044 communique is put down in writing.Catalyzer can use with the catalyzer of gac as main component.In addition, because this reaction is preferably cooled off the carbonyl chloride reactor for exothermic reaction, keep the inside reactor temperature below 350 ℃.
The carbonyl chloride gas that obtains in the operation (1) contains unreacted carbon monoxide usually.From the quality of cost and polycarbonate oligomer, preferred 1～30 capacity % of the content of the carbon monoxide in the carbonyl chloride gas, more preferably 2～20 capacity %.That is, preferred purity is the carbonyl chloride of 99～70 capacity %.
＜operation 2 〉
Operation (2) is that continuous supplying is made the operation of the reaction mixture that contains polycarbonate oligomer continuously to the carbonyl chloride gas of making continuously in the described operation (1), alkali aqueous solution and the organic solvent of dihydric phenol in the oligopolymer reactor.
The raw material of making polycarbonate can enumerate carbonyl chloride gas, dihydric phenols (bisphenols), in order to dissolve the employed basic cpd of dihydric phenols, organic solvent, can also use as required the monohydric phenol as molecular weight regulator, or other additives.
Carbonyl chloride gas uses the carbonyl chloride gas of making continuously in the described operation (1).
From the point of polycarbonate physical property, dihydric phenols is preferred 2,2-two (4-hydroxy phenyl) propane (common name dihydroxyphenyl propane; BPA).Dihydric phenols beyond the dihydroxyphenyl propane can be enumerated, for example, two (4-hydroxy phenyl) methane, 1,1-two (4-hydroxy phenyl) ethane, 1, two (4-hydroxy phenyl) alkane such as 2-two (4-hydroxy phenyl) ethane, 1,1-two (4-hydroxy phenyl) hexanaphthene, 1, two (4-hydroxy phenyl) naphthenic hydrocarbon such as 1-two (4-hydroxy phenyl) cyclodecane, 4,4 '-dihydroxybiphenyl, two (4-hydroxy phenyl) oxygen, two (4-hydroxy phenyl) sulphur, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) ketone, Resorcinol etc.These dihydric phenols can independent a kind of use, or more than two kinds and use.
The employed basic cpd of dissolving dihydric phenols is suitably sodium hydroxide.
The alkali aqueous solution of dihydric phenol is supplied with after being adjusted in advance normality again.At this moment, its concentration (a[quality %]) is monitored by online titrimetry machine.Measuring method is not particularly limited, and uses the salt acidometric titration to try to achieve the method etc. of its concentration such as enumerating.
Organic solvent can be enumerated so long as can get final product by the dissolved polycarbonate oligopolymer, such as the chlorine series solvents such as, methylene dichloride, ethylene dichloride, chloroform, chlorobenzene, tetracol phenixin, the epoxy compoundss such as dioxan etc.Preferred chlorine series solvent in the present invention is from the deliquescent point of polycarbonate oligomer, particularly preferably methylene dichloride.More than beyond the cited organic solvent, as long as in not reducing the deliquescent scope of polycarbonate oligomer, also can use the alkanes equal solvent that is called as Weak solvent.
Organic solvent can independent a kind of use, or two or more mixing is used.
Can enumerate as the monohydric phenol that molecular weight regulator uses, such as phenol, p-cresol, p-tert-butylphenol, to tert-octyl phenol, to cumyl phenol, nonylphenol etc.Wherein, from the viewpoint of cost or the easiness of starting with etc., preferred p-tert-butylphenol and phenol.
In the manufacturing of polycarbonate oligomer, can also use the polymerizing catalysts such as tertiary amine, quaternary ammonium as required.The preferred TEA of polymerizing catalyst (triethylamine).
The oligopolymer reactor uses the reactor of successive reaction mode, the preferred cast structure reactor that uses the hydrid component with reaction raw material.
In addition, the oligopolymer reactor is arranged in the structure, with external isolation.Constantly carry out air inerchange in the structure, the air of inner exchanging is delivered in the device of removing the evil by gas blower.
The feed rate of base feed in the oligopolymer reactor in the operation (2) and reaction conditions are according to decisions such as the scale of device or turnout.
For example, preferred condition is as follows when producing the polycarbonate oligomer of about 200kg in per 1 hour, but is not limited thereto.The flow (F1) of the carbonyl chloride gas of gained is preferably 3.7～4.1kg/h in the operation (1).The flow of the organic solvents such as methylene dichloride (F2) is preferably 20～24kg/h.The temperature of carbonyl chloride gas is preferably in the scope of the boiling point (7.8 ℃) of carbonyl chloride～90 ℃.The aqueous sodium hydroxide solution of the preferred dihydroxyphenyl propane of alkali aqueous solution of dihydric phenol is adjusted supply and is made it reach the concentration of predesignating.In the aqueous sodium hydroxide solution of dihydroxyphenyl propane, desirable bisphenol A concentration (a) is 12.5～14.0 quality %, and desirable naoh concentration is 5.1～6.1 quality %.The flow of the aqueous sodium hydroxide solution of dihydroxyphenyl propane (F3) is preferably 42～46kg/h.
Can obtain to contain the polycarbonate oligomer reaction mixture with chloroformyl in the operation (2).The proterties of above-mentioned polycarbonate oligomer is without special system limit, and the setting reaction conditions makes it reach best proterties and gets final product, but preferably it is about about 600～5000 by molecular weight that VPO (vapour pressure osmometer) measures.
In addition, the reaction mixture that contains polycarbonate oligomer has the organic phase that polycarbonate oligomer is dissolved in described organic solvent, and contains the mixture of the water of alkali aqueous solution.This reaction mixture is imported in the condensation reactor, make it to occur condensation reaction and make polycarbonate.
In addition, after condensation reaction finishes, can by known method to reaction soln clean, concentrate, powdered etc. obtains Powdered polycarbonate, further carries out granulating by processing such as extrusion machines.
[control method that polycarbonate oligomer is made continuously]
Continuous supplying is given in the oligopolymer reactor the carbonyl chloride gas of specified amount, alkali aqueous solution and the organic solvent of dihydric phenol.Inlet pressure in the supply pressure of carbonyl chloride gas and the oligopolymer reactor is suitably set according to the size of carbonyl chloride reactor and oligopolymer reactor, shape etc., but it is that 0.4～0.5MPaG, the interior inlet pressure (P2) of oligopolymer reactor are 0.15～0.35MpaG that common continuous operation makes the supply pressure (P1) of carbonyl chloride gas, and the value of both pressure differences (P1-P2) is the differential pressure of 0.105MPa～0.35Mpa.
In the control method that polycarbonate oligomer of the present invention is made continuously, for the carbonyl chloride gas flow (F1) of supplying with the oligopolymer reactor, solvent flux (F2), the alkali aqueous solution flow (F3) of dihydric phenolic compounds and dihydric phenolic compounds concentration (a[quality %]), can constantly monitor whether it satisfies following condition (i) and/or (ii), but when satisfying this condition, can stop to make and supplying with carbonyl chloride by automatic system, simultaneously, the obnoxious flavour that system is contained carbonyl chloride gas be transplanted on carry out in the device of removing the evil innoxious.
Condition (i): when the parameter＜F2/ of the alkali aqueous solution flow that has used the solvent flux of supplying with the oligopolymer reactor (F2[kg/h]), dihydric phenolic compounds (F3[kg/h]) and dihydric phenolic compounds concentration (a[quality %]) (F3 * a/100)〉value become 3.27 when following.
Condition (ii): when the parameter of the alkali aqueous solution flow that has used the carbonyl chloride gas flow of supplying with the oligopolymer reactor (F1[kg/h]), dihydric phenolic compounds (F3[kg/h]) and dihydric phenolic compounds concentration (a[quality %])＜(F3 * a/100)/F1〉value become 1.23 when following.
＜condition (i) 〉
Condition (i) for when the parameter＜F2/ of the alkali aqueous solution flow that use the solvent flux of supplying with the oligopolymer reactor (F2[kg/h]), dihydric phenolic compounds (F3[kg/h]) and dihydric phenolic compounds concentration (a[quality %]) (F3 * a/100)〉value become situation below 3.27.Balance between the solvent flux of this parametric representation supply oligopolymer reactor and the alkali aqueous solution flow of dihydric phenolic compounds.
Continuous supplying is to the carbonyl chloride gas of specified amount, alkali aqueous solution and the organic solvent of dihydric phenolic compounds in the oligopolymer reactor, but when causing the quantity of solvent undersupply by faults such as solvent supply pumps, the concentration of the polycarbonate oligomer that generates in the oligopolymer reactor uprises, and its result exists polycarbonate oligomer to separate out and stops up the possibility of oligopolymer reactor outlet.So pressure rise, solvent and oligopolymer raw material adverse current in the oligopolymer reactor in the carbonyl chloride reactor, solvent evaporation etc., causing thus running press be raised to set press more than, exist carbonyl chloride to the danger of system's external leakage.
Therefore, the present invention is for the angle on the safety, make parameter＜F2/ when the alkali aqueous solution flow that has used the solvent flux of supplying with the oligopolymer reactor (F2[kg/h]), dihydric phenolic compounds (F3[kg/h]) and dihydric phenolic compounds concentration (a[quality %]) (F3 * a/100)〉value become 3.27 automatic systems of startup when following.But, started continually the words of automatic system by transience fault etc., can make and operate expeditiously difficult, therefore, for guaranteeing security and the viewpoint that operates expeditiously, the condition that starts automatic system can be set as described parameter＜F2/ (F3 * a/100)〉value be below 2.52, further also to can be below 2.43.
In addition, when usually moving, from the viewpoint of productivity etc., above-mentioned parameter＜F2/ (F3 * a/100)〉value be preferably 3.30～4.60, more preferably 3.60～4.10.
＜condition (ii) 〉
Condition (ii) for when the parameter of the alkali aqueous solution flow that use the carbonyl chloride gas flow that supplies to the oligopolymer reactor (F1[kg/h]), dihydric phenolic compounds (F3[kg/h]) and dihydric phenolic compounds concentration (a[quality %])＜(F3 * a/100)/F1〉value become situation below 1.23.Balance between the carbonyl chloride gas flow of this parametric representation supply oligopolymer reactor and the alkali aqueous solution flow of dihydric phenolic compounds.
Continuous supplying is to the carbonyl chloride gas of specified amount, alkali aqueous solution and the organic solvent of dihydric phenol in the oligopolymer reactor, but when the alkali aqueous solution feed rate that is caused dihydric phenol by faults such as dihydric phenolic compounds supply pumps is not enough, the carbonyl chloride of a part has not been consumed in the oligopolymer reactor, to subsequent handling, there is the danger to system's external leakage with unreacted state flow.
Therefore, the present invention is for the angle on the safety, make parameter when the alkali aqueous solution flow that has used the carbonyl chloride gas flow of supplying with the oligopolymer reactor (F1[kg/h]), dihydric phenolic compounds (F3[kg/h]) and dihydric phenolic compounds concentration (a[quality %])＜(F3 * a/100)/F1〉value become 1.23 automatic systems of startup when following.But, started continually the words of automatic system by transience fault etc., can make and operate expeditiously difficult, therefore, for guaranteeing security and the viewpoint that operates expeditiously, the condition that starts automatic system can be set as above-mentioned parameter＜(F3 * a/100)/F1〉value become below 1.05, further also can be below 1.00.
In addition, when usually moving, from the viewpoint of productivity etc., above-mentioned parameter＜(F3 * a/100)/F1〉value be preferably 1.28～2.00, more preferably 1.40～1.80.
In the control method of the continuous manufacturing of polycarbonate oligomer of the present invention, satisfying above-mentioned condition (i) and/or (ii) time, automatically carry out (a), (b) and operation (c), when preventing poisonous carbonyl chloride to system's external leakage, carry out innoxious.
(a) chlorine and the carbon monoxide that stop to make continuously in the operation (1) of carbonyl chloride gas are supplied with.This is for the purpose that does not increase the amount of carbonyl chloride gas in the system, thereby ends to make the operation of carbonyl chloride gas.
(b) stop in the oligopolymer reactor, supplying with carbonyl chloride gas.This is not to be consumed in the oligopolymer reactor for the carbonyl chloride of a part, with the worry of unreacted state flow to subsequent handling, thereby prevents the operation that carbonyl chloride leaks.
(c) toxic gas that system is contained carbonyl chloride gas transfer to carry out in the device of removing the evil innoxious.This be add by above-mentioned (a) and operation (b) prevent the increase of carbonyl chloride and leakage, with its be closed in intrasystem, for the operation of carbonyl chloride gas in the innoxious system of greater security viewpoint.
＜the device of removing the evil 〉
The device of removing the evil is the innoxious equipment of toxic gas that will contain carbonyl chloride gas by pesticide, can use known device.Concrete example can be enumerated, be scattered with pesticide equipment, make absorption tower that obnoxious flavour contacts with pesticide etc.The tower that in addition, can also use Japanese patent laid-open 6-319946 communique or JP 2005-305414 communique the to put down in writing equipment of removing the evil.
For sour gas such as carbonyl chloride and chlorine, use alkaline matter as pesticide.Be not particularly limited as the employed alkaline matter of pesticide, generally can use sodium hydroxide, potassium hydroxide.In addition, usually use their aqueous solution.
When the device of removing the evil adopted and to remove the evil tower, the structure of the tower of removing the evil was not particularly limited, and can enumerate as typical example, and pesticide is the shower shape from the top of tower by shower nozzle etc. and sprays, the equipment of removing the evil that contacts with obnoxious flavour by underfeed.In order to improve the contact efficiency of pesticide and gas, can fill the weighting agents such as Lessing rings (ラ シ ヒ リ Application グ) between the jet orifice of pesticide and the influx of gas.In addition, the number of the tower of removing the evil is not particularly limited, and is designed to make the concentration of toxic gases in the disinfection gas to be reduced to below the concentration of the regulations such as environmental criteria, is preferably the degree that is not detected.
Remove the evil in the device, even without the leakage of toxic gas, also often keep running to make ready for accidents.In addition, the interior exchange of air of structure that is provided with the oligopolymer reactor is sent to the device of removing the evil, and is outside by innoxious rear discharges such as gas blowers.
For a desirable routine embodiment of the present invention, describe with reference to picture.Fig. 1 is the summary signal process picture sheet of a control of the present invention routine preferred implementation of making continuously the polycarbonate oligomer method.
Usually in the running, make raw material chlorine and the carbon monoxide of carbonyl chloride and supply with the carbonyl chloride reactor by variable valve, in the carbonyl chloride reactor, make carbonyl chloride gas.Because reaction is exothermic reaction, so by water quench carbonyl chloride reactor.
The carbonyl chloride gas (resultant of reaction) that contains the unreacted carbon monoxide is directed in the oligopolymer reactor by variable valve.In the oligopolymer reactor, except carbonyl chloride gas, the alkali aqueous solution of dihydric phenol (particularly, for example the aqueous sodium hydroxide solution of dihydroxyphenyl propane) and organic solvent (particularly for example methylene dichloride) also are imported into, and contain the emulsion of polycarbonate oligomer by their reaction manufacturing.
In addition, the variable valve that arranges at the supply route of chlorine and carbon monoxide is controlled their flow automatically, is controlling the supply pressure of supplying with carbonyl chloride gas in the oligopolymer reactor at the variable valve that supply route from carbonyl chloride gas to the oligopolymer reactor that supply with arranges.
The use traffic meter continues the alkali aqueous solution flow (F3) of the carbonyl chloride gas flow (F1) that supplies to the oligopolymer reactor, solvent flux (F2), dihydric phenolic compounds is monitored.In addition, for the alkali aqueous solution of dihydric phenol, in advance its dihydric phenolic compounds concentration (a) is adjusted to normality, the working concentration meter continues its concentration (a) is monitored.These values can be sent to automatic control device (dotted arrow among the figure), and automatic control device is calculated above-mentioned condition (i) and reached (ii) parameter of defined based on its data of receiving.
When the abnormal situation, namely, above-mentioned parameter satisfies above-mentioned condition (i) and/or (ii) time, automatic control device can be simultaneously variable valve, the carbonyl chloride gas that is arranged at the oligopolymer reactor on the supply route that is arranged at chlorine and carbon monoxide supply with the variable valve on the route and be arranged at variable valve transmitted signal (the heavy line arrow among the figure) on the runner that leads to the device of removing the evil.
According to the signal of sending from automatic control device, the variable valve that is arranged on the supply route of chlorine and carbon monoxide can be closed, and stops the supply of chlorine and carbon monoxide.Simultaneously, the variable valve that is arranged on the supply route of carbonyl chloride gas of oligopolymer reactor also can be closed, and stops to supply with carbonyl chloride gas in the oligopolymer reactor.
The variable valve that is arranged on the runner that leads to the device of removing the evil cuts out usually in the running, but opens when receiving the signal that automatic control device sends, and the toxic gas that system is included carbonyl chloride gas is transplanted in the device of removing the evil.In the device of removing the evil, carry out innoxious to the obnoxious flavour that contains carbonyl chloride gas.
More than to a desirable routine embodiment of the present invention, be illustrated with reference to picture, but the present invention is not limited to this.For example, although show among the figure, except variable valve, also can arrange and stop to supply with the shut off valve that each fluid is used.
The method according to this invention, when making polycarbonate oligomer continuously by interfacial, cause that by the raw material supplying fault in the oligopolymer reactor oligopolymer separates out even occur, the accidents such as the interior obstruction of reactor, also can automatically stop to supply with as chlorine and the carbon monoxide of carbonyl chloride raw material and stop in the oligopolymer reactor, supplying with carbonyl chloride, simultaneously, can also outside system, not leak, automatically control intrasystem carbonyl chloride is transplanted in the device of removing the evil, thereby can make safely polycarbonate oligomer.
Below the present invention is illustrated more specifically that but the present invention is not limited to this based on embodiment.
Embodiment
Embodiment 1-1
(automatic control device)
As shown in Figure 1, it is designed to automatically carry out the automatic control device of following operation.When having used the solvent flux (F2[kg/h) that supplies to the oligopolymer reactor, parameter＜the F2/ of the alkali aqueous solution flow (F3[kg/h) of dihydric phenolic compounds and dihydric phenolic compounds concentration (a[quality %]) (F3 * a/100)〉value become 3.27 when following (condition (i)), perhaps ought use the carbonyl chloride gas flow that supplies to the oligopolymer reactor (F1[kg/h]), the parameter of the alkali aqueous solution flow of dihydric phenolic compounds (F3[kg/h]) and dihydric phenolic compounds concentration (a[quality %])＜(F3 * a/100)/F1〉value become 1.23 when following (condition (ii)), be arranged at the variable valve on the supply route of chlorine and carbon monoxide and be arranged at the variable valve that the carbonyl chloride gas of oligopolymer reactor supplies with on the route and namely close, simultaneously, the variable valve that is arranged on the runner that leads to the device of removing the evil is unlocked.
(device of removing the evil)
As the device of removing the evil, use the tower diameter 600mm that has filled カ ス ケ one De ミ ニ リ Application ダ (CMR) (trade(brand)name, マ Star イ マ シ Application (strain) system), the tower of removing the evil of filling floor height 10m.Remove the evil in the tower, working concentration is that the aqueous sodium hydroxide solution of 10 quality % makes it with 2m as pesticide
3/ h circulates.Aqueous sodium hydroxide solution is supplied with from the top of tower, and toxic gas is from underfeed.
(manufacturing of carbonyl chloride)
As the carbonyl chloride reactor, use the shell and tube-type reactor of having filled the granular carbon (pulverizing the cocoanut active charcoal as diameter 1.2～1.4mm) of selling on the market in the pipe.
Supplying with the carbon monoxide of 1.2kg/h, the chlorine of 2.8kg/h, the carbonyl chloride gas of 3.9kg/h in the carbonyl chloride reactor makes.The water that passes into 90 ℃ at the shell position of carbonyl chloride reactor is removed reaction heat.
(manufacturing of polycarbonate oligomer)
The oligopolymer reactor uses the tube-type reactor of internal diameter 6mm, long 30m.With the oligopolymer reactor leaching in 20 ℃ cooling tank.Carbonyl chloride gas is supplied with in the oligopolymer reactor continuously by upper continuous carbonyl chloride manufacturing process, and the supply pressure of the carbonyl chloride gas of supplying with to the oligopolymer reactor is set as 0.45MPaG.
Supply with carbonyl chloride gas, concentration in the oligopolymer reactor and be the concentration (a) of dissolving dihydroxyphenyl propane (BPA) gained in the aqueous sodium hydroxide solution of 6 quality % and be the dichloromethane solution of the p-tert-butylphenol of the concentration 25 quality % that BPA aqueous sodium hydroxide solution, methylene dichloride, the molecular-weight adjusting of 13.5 quality % use, make polycarbonate oligomer solution.At this moment, the supply flow rate of carbonyl chloride gas (F1) is 3.9kg/h, the supply flow rate of BPA aqueous sodium hydroxide solution (F3) is 44kg/h, and the supply flow rate of methylene dichloride (F2) is 22kg/h, and the supply flow rate of the dichloromethane solution of p-tert-butylphenol is 0.46kg/h.(value of F3 * a/100) is 3.70 to F2/, and (value of F3 * a/100)/F1 is 1.52.In addition, the inlet pressure in the oligopolymer reactor is 0.20MPaG.
Herein, the flow (F2) of the methylene dichloride that will supply with in the oligopolymer reactor is reduced to 19.3kg/h, and (value of F3 * a/100) is 3.25 to make wittingly F2/.
Its result is, pass through automatic control device, stopped in the carbonyl chloride reactor, supplying with chlorine and carbon monoxide, also stopped simultaneously in the oligopolymer reactor, supplying with carbonyl chloride gas, and the carbonyl chloride gas that generates in the carbonyl chloride reactor has been transferred in the device of removing the evil.Exit expellant gas to the tower of removing the evil carries out composition measurement, does not detect carbonyl chloride, and namely it is by innoxious.
Embodiment 1-2
The flow (F2) of the methylene dichloride that will supply with in the oligopolymer reactor is reduced to 14.9kg/h, and (value of F3 * a/100) is 2.51, in addition, with embodiment 1-1, makes polycarbonate oligomer to make wittingly F2/.
Its result is with embodiment 1-1, pass through automatic control device, stopped in the carbonyl chloride reactor, supplying with chlorine and carbon monoxide, also stopped simultaneously in the oligopolymer reactor, supplying with carbonyl chloride gas, and the carbonyl chloride gas that generates in the carbonyl chloride reactor has been transferred in the device of removing the evil.Exit expellant gas to the tower of removing the evil carries out composition measurement, does not detect carbonyl chloride, and namely it is by innoxious.
Embodiment 1-3
The flow (F2) of the methylene dichloride that will supply with in the oligopolymer reactor is reduced to 14.4kg/h, and (value of F3 * a/100) is 2.42, in addition, with embodiment 1-1, makes polycarbonate oligomer to make wittingly F2/.
Its result is with embodiment 1-1, pass through automatic control device, stopped in the carbonyl chloride reactor, supplying with chlorine and carbon monoxide, also stopped simultaneously in the oligopolymer reactor, supplying with carbonyl chloride gas, and the carbonyl chloride gas that generates in the carbonyl chloride reactor has been transferred in the device of removing the evil.Exit expellant gas to the tower of removing the evil carries out composition measurement, does not detect carbonyl chloride, and namely it is by innoxious.
Comparative example 1-1
Do not use automatic control device, in addition, with embodiment 1-1, carry out the manufacturing of polycarbonate oligomer.
But in the lower time of situation of not using automatic control, the pressure in the oligopolymer reactor sharply rises.So, if continue aforesaid operations, it is contemplated that the reaction solution of oligopolymer inside reactor can blow back in the carbonyl chloride reactor, the pressure rise in methylene dichloride evaporation, the carbonyl chloride reactor, destruction carbonyl chloride reactor, cause carbonyl chloride to system's external leakage, so ended operation.
Embodiment 2-1
The flow (F3) of the BPA aqueous sodium hydroxide solution that will supply with in the oligopolymer reactor is reduced to 35.5k/gh, makes wittingly that (value of F3 * a/100)/F1 is 1.23, in addition, carries out the manufacturing of polycarbonate oligomer with embodiment 1-1.
Its result is with embodiment 1-1, pass through automatic control device, stopped in the carbonyl chloride reactor, supplying with chlorine and carbon monoxide, also stopped simultaneously in the oligopolymer reactor, supplying with carbonyl chloride gas, and the carbonyl chloride gas that generates in the carbonyl chloride reactor has been transferred in the device of removing the evil.Exit expellant gas to the tower of removing the evil carries out composition measurement, does not detect carbonyl chloride, and namely it is by innoxious.
Embodiment 2-2
The flow (F3) of the BPA aqueous sodium hydroxide solution that will supply with in the oligopolymer reactor is reduced to 30.1kg/h, makes wittingly that (value of F3 * a/100)/F1 is 1.04, in addition, carries out the manufacturing of polycarbonate oligomer with embodiment 2-1.
Its result is with embodiment 2-1, pass through automatic control device, stopped in the carbonyl chloride reactor, supplying with chlorine and carbon monoxide, also stopped simultaneously in the oligopolymer reactor, supplying with carbonyl chloride gas, and the carbonyl chloride gas that generates in the carbonyl chloride reactor has been transferred in the device of removing the evil.Exit expellant gas to the tower of removing the evil carries out composition measurement, does not detect carbonyl chloride, and namely it is by innoxious.
Embodiment 2-3
The flow (F3) of the BPA aqueous sodium hydroxide solution that will supply with in the oligopolymer reactor is reduced to 28.7kg/h, makes wittingly that (value of F3 * a/100)/F1 is 0.99, in addition, carries out the manufacturing of polycarbonate oligomer with embodiment 2-1.
Its result is with embodiment 2-1, pass through automatic control device, stopped in the carbonyl chloride reactor, supplying with chlorine and carbon monoxide, also stopped simultaneously in the oligopolymer reactor, supplying with carbonyl chloride gas, and the carbonyl chloride gas that generates in the carbonyl chloride reactor has been transferred in the device of removing the evil.Exit expellant gas to the tower of removing the evil carries out composition measurement, does not detect carbonyl chloride, and namely it is by innoxious.
Comparative example 2-1
Do not use automatic control device, in addition, with embodiment 2-1, carry out the manufacturing of polycarbonate oligomer.
But, in the lower time of situation of not using automatic control, it is contemplated that with respect to the carbonyl chloride gas flow that supplies in the oligopolymer reactor, the flow of BPA aqueous sodium hydroxide solution is very few, the amount of causing opinion has supplied in the oligopolymer reactor than above carbonyl chloride gas, it is not consumed in the oligopolymer reactor and completely namely flow in the lower continuous operation with unreacted state, and then to system's external leakage, so ended operation.
Utilizability on the industry
The method according to this invention can be made polycarbonate oligomer safely continuously.Especially, even raw material supplying fault by the oligopolymer reactor occurs to be caused when the accident of reactor etc. is separated out, stopped up to oligopolymer, also can be by automatically controlling the emergent stopping manufacturing and supplying with carbonyl chloride, simultaneously, the intrasystem toxic gas that contains carbonyl chloride gas is carried out innoxious, and not to system's external leakage toxic gas.
Claims (2)
1. control method of making continuously polycarbonate oligomer, possess: in the carbonyl chloride reactor, supply with chlorine and carbon monoxide, make continuously the operation (1) of the carbonyl chloride gas that contains unreacted carbon monoxide, and continuous supplying is given the carbonyl chloride gas of making continuously in the described operation (1), alkali aqueous solution and the organic solvent of dihydric phenol in the oligopolymer reactor, makes continuously the operation (2) of the reaction mixture that contains polycarbonate oligomer;
The control method of described continuous manufacturing polycarbonate oligomer is satisfying following condition (i) and/or (ii) time, stop the supply of the middle chlorine of described operation (1) and carbon monoxide, stop simultaneously supplying with carbonyl chloride gas in the oligopolymer reactor, and the toxic gas that will contain carbonyl chloride gas transfer to carry out in the device of removing the evil innoxious;
Condition (i): (value of F3 * a/100) becomes 3.27 when following when the parameter F 2/ of alkali aqueous solution flow F3 and the dihydric phenolic compounds concentration a of the flow F2 that has used the solvent that supplies in the oligopolymer reactor, dihydric phenolic compounds, wherein, the unit of described flow F2 and flow F3 is kg/h, the unit of described concentration a is quality %
Condition (ii): (value of F3 * a/100)/F1 becomes 1.23 when following when the parameter of alkali aqueous solution flow F3 and the dihydric phenolic compounds concentration a of the flow F1 that has used the carbonyl chloride gas that supplies in the oligopolymer reactor, dihydric phenolic compounds, wherein, the unit of described flow F1 and flow F3 is kg/h, and the unit of described concentration a is quality %.
2. the control method of continuous manufacturing polycarbonate oligomer according to claim 1, thus the described device of removing the evil is to make the toxic gas that contains carbonyl chloride gas contact innoxious device with alkali aqueous solution.
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| JPH06319946A (en) * | 1993-05-18 | 1994-11-22 | Mitsui Toatsu Chem Inc | Method for removing toxic gas in toxicity-removing tower |
| US6340736B1 (en) * | 1999-11-29 | 2002-01-22 | General Electric Company | Method and apparatus for the production of polycarbonates with brine recycling |
| JP4271485B2 (en) * | 2003-05-12 | 2009-06-03 | 出光興産株式会社 | Method for producing polycarbonate |
| DE102004041777A1 (en) * | 2004-08-28 | 2006-03-02 | Bayer Materialscience Ag | Process and apparatus for the production of phosgene |
| JP2006137669A (en) * | 2005-12-05 | 2006-06-01 | Sumitomo Chemical Co Ltd | Method for producing phosgene |
| JPWO2007083721A1 (en) * | 2006-01-17 | 2009-06-11 | 帝人化成株式会社 | Continuous production method of polycarbonate oligomer |
| JP5235082B2 (en) * | 2008-02-25 | 2013-07-10 | 日本曹達株式会社 | Chlorination method and detection method of reaction end point |
| JP5319327B2 (en) * | 2009-02-26 | 2013-10-16 | 帝人株式会社 | Method for producing carbonyl chloride |
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| TW201239000A (en) | 2012-10-01 |
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