CN102286145B - 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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- CN102286145B CN102286145B CN 201110171562 CN201110171562A CN102286145B CN 102286145 B CN102286145 B CN 102286145B CN 201110171562 CN201110171562 CN 201110171562 CN 201110171562 A CN201110171562 A CN 201110171562A CN 102286145 B CN102286145 B CN 102286145B
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- carbonyl chloride
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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 34
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 153
- 239000007789 gas Substances 0.000 claims abstract description 89
- 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 27
- 239000000460 chlorine Substances 0.000 claims abstract description 27
- 239000003960 organic 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
- 239000002341 toxic gas Substances 0.000 claims abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011541 reaction mixture Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 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 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 12
- 239000000575 pesticide Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 7
- 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
- -1 chloroformyl Chemical group 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
- 239000002904 solvent Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- 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
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 230000006378 damage Effects 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
- 230000002411 adverse Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 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 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
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation 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
- 238000000935 solvent evaporation 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
- 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
- 238000010924 continuous production Methods 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
- 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
- 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
- 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
- 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
Images
Classifications
-
- 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
Abstract
A method for safely producing a polycarbonate oligomer, which is a control method for automatically detoxifying harmful phosgene without leaking to the outside of a system even if an abnormality occurs, 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 control method for continuously producing the polycarbonate oligomer stops the supply of chlorine and carbon monoxide in the step (1) and simultaneously stops the supply of the phosgene gas to the oligomer reactor when the following conditions (i) and/or (ii) are met, and transfers toxic gas containing the phosgene gas to a detoxifying device for detoxification; condition (i): when the value of the pressure difference (P1-P2) between the supply pressure (P1) for supplying phosgene gas to the oligomer reactor and the inlet pressure (P2) in the oligomer reactor is 0.1MPa or less, the condition (ii): when the inlet pressure (P2) in the oligomer reactor became 0.13MPaG 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 the 2007/083721st 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 separate out to abnormal reaction or by the oligopolymer that the organic solvent supply accident in the oligopolymer reactor causes; the accident that pressure anomaly in the oligopolymer reactors such as reactor plugs causes was 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 control method of continuous manufacturing 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 from the pressure difference (P1-P2) between the inlet pressure (P2) in the oligopolymer reactor to the oligopolymer reactor that supply with the supply pressure (P1) of carbonyl chloride gas and becomes 0.1MPa when following,
Condition (ii): the inlet pressure in the oligopolymer reactor (P2) becomes 0.13MPaG 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 monitor pressure (P1) and the interior inlet pressure (P2) of oligopolymer reactor of the carbonyl chloride gas of supplying with in the oligopolymer reactor, 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.
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 suitably determine according to the scale of device or turnout etc.
Have 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 desirable flow of the carbonyl chloride gas of gained is 3.7～4.1kg/h in the operation (1).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 is 12.5～14.0 quality %, and desirable naoh concentration is 5.1～6.1 quality %.The desirable flow of the aqueous sodium hydroxide solution of dihydroxyphenyl propane is 42～46kg/h.The flow of the organic solvents such as methylene dichloride is preferably 20～24kg/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 (P2) in the supply pressure of carbonyl chloride gas (P1) 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 pressure (P1) of the carbonyl chloride gas of in the oligopolymer reactor, supplying with and the inlet pressure (P2) in the oligopolymer reactor, 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): supply with the value of the supply pressure (P1) of carbonyl chloride gas and the pressure difference (P1-P2) between the inlet pressure (P2) in the oligopolymer reactor when 0.1MPa is following to the oligopolymer reactor.
Condition (ii): the inlet pressure in the oligopolymer reactor (P2) becomes 0.13MPaG when following.
＜condition (i) 〉
Condition (i) is to the supply pressure (P1) of the carbonyl chloride gas of oligopolymer reactor supply and the situation of value below 0.1MPa of the pressure difference (P1-P2) between the inlet pressure (P2) in the oligopolymer reactor.
For example, the pump of the supply organic solvent that is caused by certain fault can't be supplied with organic solvent, in the situation that perhaps this feed rate reduces, in the oligopolymer reactor, the polycarbonate oligomer that the concentration of polycarbonate oligomer uprises, generates is separated out when stopping up the oligopolymer reactor outlet, and the pressure in the oligopolymer reactor can rise.Its result causes solvent and oligopolymer raw material adverse current, solvent evaporation etc. in the carbonyl chloride reactor, causing thus running press be raised to set to 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, makes value when the pressure difference (P1-P2) of the inlet pressure (P2) in the supply pressure (P1) of carbonyl chloride gas and the oligopolymer reactor become 0.1MPa startup automatic system when following.But, started continually the words of automatic system by transience fault etc., operate expeditiously is difficult, therefore, for guaranteeing security and the viewpoint that operates expeditiously, the value that the condition of startup automatic system can be set as described pressure difference (P1-P2) is 0.09MPa, further also can be below the 0.049MPa.
＜condition (ii) 〉
Condition (ii) becomes the following situation of 0.13MPaG for the inlet pressure (P2) in the oligopolymer reactor.
Entrance pressure drop in the oligopolymer reactor it is contemplated that by the supply of organic solvent or dihydric phenol alkali aqueous solution bad, poor responses etc. cause, cause thus the carbonyl chloride of a part in the oligopolymer reactor, not to be consumed, with unreacted state flow to subsequent handling, demonstrate to the danger of system's external leakage, or the polycarbonate oligomer that generates is separated out and is stopped up the oligopolymer reactor outlet, make organic solvent and oligopolymer raw material adverse current in the carbonyl chloride reactor, solvent evaporation etc., causing thus running press be raised to set to press more than, have the danger to system's external leakage carbonyl chloride.
Therefore, the present invention makes the inlet pressure (P2) in the oligopolymer reactor start automatic system when becoming 0.13MPaG for the angle on the safety.But, started continually the words of automatic system by transience fault etc., operate expeditiously is difficult, therefore, for guaranteeing security and the viewpoint that operates expeditiously, the inlet pressure (P2) that the condition of startup automatic system can be set as in the oligopolymer reactor becomes below the 0.12MPaG, further also can be below the 0.049MPaG.
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 pressure (P1) of the carbonyl chloride gas of supplying with to the oligopolymer reactor constantly monitors to them that with inlet pressure (P2) the working pressure meter in the oligopolymer reactor its value is sent to automatic control device (dotted arrow among the figure).
When the abnormal situation, namely, above-mentioned pressure (P1) and (P2) satisfy 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 Fig. 1, 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; unusual or cause that by the organic solvent supply accident in the oligopolymer reactor oligopolymer separates out even react; 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.Monitor by the pressure (P1) of pressure warning unit subtend oligopolymer reactor supply carbonyl chloride gas and the inlet pressure (P2) in the oligopolymer reactor, when the value of the pressure difference (P1-P2) of the inlet pressure (P2) in supply pressure (P1) from carbonyl chloride gas to the oligopolymer reactor that supply with and the oligopolymer reactor becomes 0.1Mpa when following (condition (i)), perhaps the inlet pressure (P2) in the oligopolymer reactor becomes 0.13MPaG 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 (P1) of the carbonyl chloride gas of supplying with to the oligopolymer reactor is set as 0.45MPaG.
Supply with 3.9kg/h carbonyl chloride gas, 44kg/h concentration in the oligopolymer reactor and be the concentration 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, 22kg/h methylene dichloride, the 0.46kg/h molecular-weight adjusting of 13.5 quality % use, make polycarbonate oligomer solution.At this moment, the inlet pressure (P2) in the oligopolymer reactor is 0.20MPaG.
Herein, outlet valve by twisting oligopolymer reactor, make wittingly the pressure rise in the oligopolymer reactor, make the inlet pressure (P2) in the oligopolymer reactor be 0.35MPaG, the value of the supply pressure (P1) of oligopolymer reactor supply carbonyl chloride gas and the pressure difference (P1-P2) of the inlet pressure (P2) in the oligopolymer reactor is 0.1MPa.
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
Outlet valve by twisting oligopolymer reactor, make wittingly the pressure rise in the oligopolymer reactor, make the inlet pressure (P2) in the oligopolymer reactor be 0.36MPaG, the value of the supply pressure (P1) of oligopolymer reactor supply carbonyl chloride gas and the pressure difference (P1-P2) of the inlet pressure (P2) in the oligopolymer reactor is 0.09MPa, in addition, with embodiment 1-1, make polycarbonate oligomer.
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
Outlet valve by twisting oligopolymer reactor, make wittingly the pressure rise in the oligopolymer reactor, make the inlet pressure (P2) in the oligopolymer reactor be 0.41MPaG, the value of the supply pressure (P1) of oligopolymer reactor supply carbonyl chloride gas and the pressure difference (P1-P2) of the inlet pressure (P2) in the oligopolymer reactor is 0.04MPa, in addition, with embodiment 1-1, make polycarbonate oligomer.
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, simultaneously by twisting the outlet valve of oligopolymer reactor, make wittingly the pressure rise in the oligopolymer reactor, make the inlet pressure (P2) in the oligopolymer reactor be 0.40MPaG, the value of the supply pressure (P1) of oligopolymer reactor supply carbonyl chloride gas and the pressure difference (P1-P2) of the inlet pressure (P2) in the oligopolymer reactor is 0.05MPa, in addition, with embodiment 1-1, carry out the manufacturing of polycarbonate oligomer.
Yet when slowly twisting the outlet valve of oligopolymer reactor, the pressure in the oligopolymer reactor sharply rises.Then, continue the words of the outlet valve of twisting oligopolymer reactor, the reaction solution that it is contemplated that the oligopolymer inside reactor can blow back in the carbonyl chloride reactor, 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
Use variable valve by the supply of twisting methylene dichloride, reduce wittingly the pressure in the oligopolymer reactor, make the inlet pressure (P2) in the oligopolymer reactor be 0.13MPaG, in addition, carry 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
Use variable valve by the supply of twisting methylene dichloride, reduce wittingly the pressure in the oligopolymer reactor, make the inlet pressure (P2) in the oligopolymer reactor be 0.12MPaG, in addition, carry 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
Use variable valve by the supply of twisting methylene dichloride, reduce wittingly the pressure in the oligopolymer reactor, make the inlet pressure (P2) in the oligopolymer reactor be 0.045MPaG, in addition, carry 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, supply with by the twisting methylene dichloride simultaneously and use variable valve, reduce wittingly the pressure in the oligopolymer reactor, make the inlet pressure (P2) in the oligopolymer reactor be 0.13MPaG, in addition, with embodiment 2-1, carry out the manufacturing of polycarbonate oligomer.
Yet, use variable valve by the supply of twisting methylene dichloride, although make the inlet pressure (P2) in the oligopolymer reactor be reduced to 0.13MpaG, afterwards, oligopolymer is separated out and is caused pressure to begin to rise.Then, if continue twisting methylene dichloride supply variable valve, it is contemplated that oligopolymer can continue to separate out, the reaction solution of oligopolymer inside reactor can blow back in the carbonyl chloride reactor, methylene dichloride evaporation, destruction carbonyl chloride reactor, cause carbonyl chloride 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 when occuring to induce reaction the unusual accident of reactor pressure such as oligopolymer such as obstructions grade in the device by separating out of 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 from the pressure difference P1-P2 between the inlet pressure (P2) in the oligopolymer reactor to the oligopolymer reactor that supply with the supply pressure (P1) of carbonyl chloride gas and becomes 0.1MPa when following,
Condition (ii): the inlet pressure in the oligopolymer reactor (P2) becomes 0.13MPaG when following.
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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| JP2011080969A JP5775345B2 (en) | 2011-03-31 | 2011-03-31 | Control method for continuous production of polycarbonate oligomer |
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| CN1388812A (en) * | 2000-09-05 | 2003-01-01 | 出光石油化学株式会社 | Process for production of polycarbonate |
| CN101585961A (en) * | 2008-05-23 | 2009-11-25 | 出光兴产株式会社 | Flame-retardant polycarbonate resin composition and light-reflecting member |
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| JPS58108226A (en) * | 1981-12-21 | 1983-06-28 | Idemitsu Kosan Co Ltd | Continuous preparation of polycarbonate oligomer |
| JPH06319946A (en) * | 1993-05-18 | 1994-11-22 | Mitsui Toatsu Chem Inc | Method for removing toxic gas in toxicity-removing tower |
| CN1281655C (en) * | 2001-09-27 | 2006-10-25 | 出光兴产株式会社 | Polycarbonate resin and method for producing same |
| US7132498B2 (en) * | 2004-09-27 | 2006-11-07 | General Electric Company | Process to make polycarbonate from bismethylsalicylcarbonate (BMSC) |
| 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 |
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| CN1388812A (en) * | 2000-09-05 | 2003-01-01 | 出光石油化学株式会社 | Process for production of polycarbonate |
| CN101585961A (en) * | 2008-05-23 | 2009-11-25 | 出光兴产株式会社 | Flame-retardant polycarbonate resin composition and light-reflecting member |
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| WO2012132029A1 (en) | 2012-10-04 |
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| JP5775345B2 (en) | 2015-09-09 |
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