CN102286144A - 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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- CN102286144A CN102286144A CN201110171495A CN201110171495A CN102286144A CN 102286144 A CN102286144 A CN 102286144A CN 201110171495 A CN201110171495 A CN 201110171495A CN 201110171495 A CN201110171495 A CN 201110171495A CN 102286144 A CN102286144 A CN 102286144A
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- carbonyl chloride
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- gas
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 70
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 70
- 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 206
- 239000007789 gas Substances 0.000 claims abstract description 76
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 39
- 239000000498 cooling water Substances 0.000 claims abstract description 34
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000460 chlorine Substances 0.000 claims abstract description 31
- 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 13
- 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 10
- 239000011541 reaction mixture Substances 0.000 claims abstract description 8
- 238000012546 transfer Methods 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 10
- 239000002826 coolant Substances 0.000 abstract description 4
- 230000005856 abnormality Effects 0.000 abstract 1
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 230000003247 decreasing effect Effects 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
- 238000006243 chemical reaction Methods 0.000 description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 239000000575 pesticide Substances 0.000 description 9
- -1 chloroformyl Chemical group 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 150000002989 phenols Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- 239000002994 raw material Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003054 catalyst Substances 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
- 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
- 239000006227 byproduct Substances 0.000 description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 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
- 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
- 230000008859 change Effects 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
- 238000013461 design Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction 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
- 230000000630 rising effect Effects 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
- 238000005660 chlorination reaction Methods 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002939 deleterious effect Effects 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
- 230000035611 feeding Effects 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
- 230000001939 inductive effect Effects 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
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 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
- 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
- 239000007921 spray Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 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
- C08G64/36—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)
Abstract
Provided is 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. Specifically disclosed is a control method for continuously producing a polycarbonate oligomer, which is provided with: 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 phosgene reactor coolant flow F1 decreased by more than 25% from steady state, condition (ii): when the outlet temperature T1 of the phosgene reactor cooling water increased from steady state by more than 5 ℃.
Description
Technical field
The present invention relates to be used for making continuously safely the control method of 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 consult the Japanese Patent spy and open the 2004-331916 communique).
In interfacial, use basic cpd such as bisphenols, sodium hydroxide and carbonyl chloride as the polycarbonate raw material, also can add end as required and stop agent (molecular weight regulator) etc.The industry manufacturing of polycarbonate is generally carried out as follows: be blown into carbonyl chloride and make it to generate the polycarbonate oligomer with reactive chloroformyl in the bisphenols alkaline aqueous solution, further when generating or polycarbonate oligomer and bisphenols alkali aqueous solution are reacted.
The Japanese Patent spy opens and discloses the liquid carbon acyl chlorides of storing distillation refining carbon acyl chlorides gained in the 2001-261321 communique, re-uses the method that this liquid carbon acyl chlorides is made polycarbonate.
But, the toxicity height of carbonyl chloride, undesirable from the viewpoint of storing stability, for example exist the risk that carbonyl chloride leaks takes place under the situation that liquid carbon acyl chlorides storagetank damages through corrosion.Though 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 large-scale equipment again, 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
When generating carbonyl chloride gas by chlorine and reaction of carbon monoxide in the carbonyl chloride reactor, because reaction is inner thermopositive reaction takes place, so need be from the outside to cooling off in the carbonyl chloride reactor so that it remains on certain temperature.When becoming insufficient by any fault cooling, the temperature of reaction in the carbonyl chloride reactor promptly becomes out of contior state, and the local temperature of carbonyl chloride reactor uprises, and there is the possibility to system's external leakage in breakage.In addition, when the temperature in the reactor further became too high, its result caused generating a large amount of tetracol phenixin by products, and this tetracol phenixin is blended in the polycarbonate products.Can cause like this, for example when its during as the substrate of CD etc., recording film is produced bad influence, thereby undesirable.
Yet, in the above-mentioned patent documentation, whichsoever all not carrying out imagination when producing these problems, also openly harmful carbonyl chloride does not leak outside system and the polycarbonate manufacture method of slowly being removed.
The problem that the present invention will solve is, provide a kind of and when making polycarbonate, make continuously in the method for polycarbonate oligomer, even take place unusual, can auto-stop mechanism, and the deleterious carbonyl chloride method that can not be removed to system's external leakage yet.
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 the operation (1) of the carbonyl chloride gas that contains unreacted carbon monoxide continuously, and in the oligopolymer reactor, supply with the carbonyl chloride gas of making continuously in the described operation (1), the alkali aqueous solution and the organic solvent of dihydric phenol continuously, make the operation (2) of the reaction mixture that contains polycarbonate oligomer continuously;
The control method of described continuous manufacturing polycarbonate oligomer is satisfying following condition (i) and/or (ii) the time, stop the chlorine in the described operation (1) and the supply of carbon monoxide, stop simultaneously in the oligopolymer reactor supplying with carbonyl chloride gas, 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 cooling water flow F1 of carbonyl chloride reactor reduces by 25% when above from steady state,
Condition is (ii): when the temperature out T1 of carbonyl chloride reactor cooling water when steady state rises more than 5 ℃.
Description of drawings
[Fig. 1] is the summary signal process picture sheet of a control of the present invention routine preferred implementation of making the polycarbonate oligomer method continuously.
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 the cooling water flow (F1) and the carbonyl chloride reactor cooling water outlet temperature (T1) of carbonyl chloride reactor, satisfying aftermentioned condition (i) and/or (ii) the time, can stop to supply with as the chlorine and the carbon monoxide of carbonyl chloride raw material automatically and in the oligopolymer reactor, supply with carbonyl chloride, simultaneously, can also control automatically intrasystem carbonyl chloride is transplanted in the device of removing the evil.
In addition,, it is desirable to a plurality of thermometers are set, particularly directly the temperature of catalyst layer is measured at the carbonyl chloride inside reactor from monitoring the viewpoint that has or not local temperature to rise in the carbonyl chloride reactor.But, in the carbonyl chloride reactor, especially when catalyst layer is provided with a plurality of thermometer, not only can produces cost and increase or increase problems such as maintenance burden, and have the danger that the carbonyl chloride gas leakage takes place in the set place of thermometer, therefore reality goes up infeasible.Therefore, the present invention constantly monitors the cooling water flow (F1) and the carbonyl chloride reactor cooling water outlet temperature (T1) of carbonyl chloride reactor, has or not the disengaging steady state by the affirmation condition, thereby has N/R temperature to rise in the monitoring carbonyl chloride reactor.
[manufacturing of polycarbonate]
The method that polycarbonate oligomer is made in control of the present invention continuously is applicable to the interfacial that makes 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 supply chlorine and carbon monoxide in the carbonyl chloride reactor, make the operation (1) of the carbonyl chloride gas that contains unreacted carbon monoxide continuously, and in the oligopolymer reactor, supply with the carbonyl chloride gas of making continuously in the described operation (1), the alkali aqueous solution and the organic solvent of dihydric phenol continuously, make the operation (2) of the reaction mixture that contains polycarbonate oligomer continuously.
＜operation 1 〉
Operation (1) is to supply with chlorine and carbon monoxide in the carbonyl chloride reactor, makes the operation of the carbonyl chloride gas that contains unreacted carbon monoxide continuously.
From the quality of polycarbonate oligomer, carbon monoxide can be made by coke, oil, Sweet natural gas, alcohol and oxygen are reacted, the above refining thing of preferred purity 95 capacity %.The content of preferred especially 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 the special public clear 55-14044 communique of for example Japanese Patent is put down in writing.Catalyzer can use with the catalyzer of gac as main component.
Because carbonyl chloride manufacturing reaction is for thermopositive reaction, so need cool off the carbonyl chloride reactor.Preferably the temperature with inside reactor remains on below 350 ℃.
Carbonyl chloride in the operation (1) is created conditions and is suitably selected according to the scale and the output of device.
For example, the ideal conditions when producing the carbonyl chloride of about 4kg in per 1 hour is as follows, but is not limited thereto.The flow of carbon monoxide is preferably 1.1～1.3kg/h, and the preferred flow of chlorine is 2.7～2.9kg/h.The preferred flow of water coolant is 78～82kg/h, and preferred temperature is 89～91 ℃, and preferred pressure is 0.18～0.22MPaG.The temperature out of water coolant is preferably 92～94 ℃.Herein, water coolant is being prerequisite carrying out liquor charging by the phosphinylidyne chlorination reaction heat under not by the ebullient condition.
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 to supply with the carbonyl chloride gas of making continuously in the described operation (1), the alkali aqueous solution and the organic solvent of dihydric phenol in the oligopolymer reactor continuously, makes the operation of the reaction mixture that contains polycarbonate oligomer continuously.
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 monohydric phenol as required, or other additives as molecular weight regulator.
Carbonyl chloride gas uses the carbonyl chloride gas of making continuously in the described operation (1).
From the point of polycarbonate rerum natura, 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, for example, chlorine series solvent such as methylene dichloride, ethylene dichloride, chloroform, chlorobenzene, tetracol phenixin, and epoxy compoundss such as dioxan etc.Preferred in the present invention chlorine series solvent, from the deliquescent point of polycarbonate oligomer, preferred especially 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, for example phenol, p-cresol, p-tert-butylphenol, to tert-octyl phenol, to cumyl phenol, nonylphenol etc.Wherein, from the viewpoint of the cost or the easiness of starting with etc., preferred p-tert-butylphenol and phenol.
In the manufacturing of polycarbonate oligomer, can also use 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 and the reaction conditions of base feed in the oligopolymer reactor in the operation (2) suitably determines according to scale of installing or turnout etc.
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, the ideal bisphenol A concentration is 12.5～14.0 quality %, and the ideal 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 organic solvents such as methylene dichloride is preferably 20～24kg/h.
Can obtain to contain polycarbonate oligomer reaction mixture in the operation (2) with chloroformyl.The proterties of above-mentioned polycarbonate oligomer does not have 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 mixture that polycarbonate oligomer is dissolved in the organic phase of described organic solvent and contains the water of alkali aqueous solution.This reaction mixture is imported in the condensation reactor, make it to take place condensation reaction and make polycarbonate.
In addition, after condensation reaction finishes, can by known method to reaction soln clean, concentrate, powdered waits and obtains Powdered polycarbonate, further carries out granulating by processing such as extrusion machines.
[control method that polycarbonate oligomer is made continuously]
In the oligopolymer reactor, supply with continuously the carbonyl chloride gas of specified amount, the alkali aqueous solution and the organic solvent of dihydric phenol are arranged.Inlet pressure (P2) in 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, temperature out (T1) for the cooling water flow (F1) and the carbonyl chloride reactor cooling water of carbonyl chloride 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): when the cooling water flow (F1) of carbonyl chloride reactor reduces by 25% when above from steady state.
Condition is (ii): when the temperature out (T1) of carbonyl chloride reactor cooling water when steady state rises more than 5 ℃.
＜condition (i) 〉
Condition (i) is that the cooling water flow (F1) of carbonyl chloride reactor reduces situation more than 25% from steady state.
In the carbonyl chloride reactor, supply with the carbon monoxide and the chlorine of specified amount continuously, but because the carbonyl chloride formation reaction is thermopositive reaction, so need cool off the carbonyl chloride reactor.Even equaling steady state, output, reaction conditions, temperature of cooling water begin not change, but when causing the cooling-water flowing quantity not sufficient by the fault of cooling-water pump etc., remove heat reduction, the rising of carbonyl chloride reactor temperature, cause generating a large amount of tetracol phenixin by products thus, this tetracol phenixin is blended in the polycarbonate products, and is undesirable.In addition, when the temperature of reaction in the carbonyl chloride reactor became out of contior state, the local temperature of carbonyl chloride reactor uprised, and there is the possibility to system's external leakage carbonyl chloride in the breakage of carbonyl chloride reactor.
Therefore, the present invention is for the angle on the safety, makes when the cooling water flow (F1) of carbonyl chloride reactor to reduce by 25% automatic system of startup when above from steady state.But, start the words of automatic system continually by transience fault etc., can make and operate the difficulty that becomes expeditiously, therefore, for guaranteeing security and the viewpoint of operating expeditiously, the cooling water flow (F1) that the condition that starts automatic system can be set at the carbonyl chloride reactor reduces by 49% when above from steady state, further also can be from steady state reduction by 54% when above.
＜condition (ii) 〉
Condition (ii) is that the temperature out (T1) of carbonyl chloride reactor cooling water is from rise situation more than 5 ℃ of steady state.
Think to supply with continuously in the carbonyl chloride reactor carbon monoxide and the chlorine of specified amount, but because the carbonyl chloride formation reaction is thermopositive reaction, so need cool off the carbonyl chloride reactor.Even output, reaction conditions, temperature of cooling water begin not change in steady state, when causing that by the carbonyl chloride abnormal reaction cooling water outlet temperature rises, the carbonyl chloride reactor temperature raises, cause generating a large amount of tetracol phenixin by products thus, this tetracol phenixin is blended in the polycarbonate products, and is undesirable.In addition, when the temperature of reaction in the carbonyl chloride reactor became out of contior state, the local temperature of carbonyl chloride reactor uprised, and there is the possibility to system's external leakage carbonyl chloride in the breakage of carbonyl chloride reactor.
Therefore, the present invention makes the temperature out (T1) when the carbonyl chloride reactor cooling water start automatic system when steady state rises more than 5 ℃ for the angle on the safety.But, start the words of automatic system continually by transience fault etc., can make and operate the difficulty that becomes expeditiously, therefore, for guaranteeing security and the viewpoint of operating expeditiously, the temperature out (T1) that the condition that starts automatic system can be set at the carbonyl chloride reactor cooling water further also can be when steady state rises more than 25 ℃ when steady state rises more than 10 ℃.
In the control method of the continuous manufacturing of polycarbonate oligomer of the present invention,, prevent that poisonous carbonyl chloride from the time of system's external leakage, carrying out innoxious satisfying above-mentioned condition (i) and/or (ii) the time, carrying out (a) and (b) and operation (c) automatically.
(a) chlorine and the carbon monoxide that stops to make continuously in the operation (1) of carbonyl chloride gas 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, to supply 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 to adopt the innoxious equipment of toxic gas that will contain carbonyl chloride gas by pesticide, can use known devices.Concrete example can be enumerated, be scattered with pesticide equipment, make absorption tower that obnoxious flavour contacts with pesticide etc.In addition, can also use Japanese patent laid-open 6-319946 communique or special tower that the 2005-305414 communique the put down in writing equipment of removing the evil of opening.
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, use their aqueous solution usually.
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 Lessing rings weighting agents such as (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 regulations such as environmental criteria, is preferably the degree that is not detected.
Remove the evil in the device,, also keep running to make ready for accidents often even without the leakage of toxic gas.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 discharges outside by innoxious backs such as gas blowers.
At ideal one 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 the polycarbonate oligomer method continuously.
Usually in the running, make the raw material chlorine and the carbon monoxide of carbonyl chloride and supply with the carbonyl chloride reactor, in the carbonyl chloride reactor, make carbonyl chloride gas by variable valve.Because reaction is thermopositive 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, 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 is provided with on 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 is provided with on the supply route of oligopolymer reactor supply carbonyl chloride gas.
The flow of carbonyl chloride reactor cooling water (F1) is constantly monitored by under meter, and the temperature out of carbonyl chloride reactor (T1) is constantly monitored by thermometer, and its value is sent to (dotted arrow among the figure) in the automatic control device.
When abnormal conditions take place, promptly, the temperature out (T1) of flow of carbonyl chloride reactor cooling water (F1) and carbonyl chloride reactor satisfies above-mentioned condition (i) and/or (ii) the time, and the automatic control device variable valve on the supply route that is arranged at chlorine and carbon monoxide, the carbonyl chloride gas that is arranged at the oligopolymer reactor is simultaneously supplied with the variable valve on the route and the variable valve that is arranged on the runner that leads to the device of removing the evil sends signal (the heavy line arrow among the figure).
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 in the oligopolymer reactor carbonyl chloride gas.
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 ideal one routine embodiment of the present invention, be illustrated with reference to picture, but the present invention is not limited to this.For example, though show among Fig. 1,, also can be provided with and stop to supply with the shut off valve that each fluid is used except variable valve.
The method according to this invention, when making polycarbonate oligomer continuously by interfacial, even the cooling failure by the carbonyl chloride reactor causes that carbonyl chloride reactor internal reaction is unusual, also can not cause accidents such as carbonyl chloride reactor breakage, automatically stop to supply with as the 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, control automatically intrasystem carbonyl chloride is transplanted in the device of removing the evil, thereby can make polycarbonate oligomer safely.
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 carry out automatically the automatic control device of following operation.When the cooling water flow (F1) of carbonyl chloride reactor reduces by 25% temperature out (T1) (condition (ii)) when the steady state rising is more than 5 ℃ of (condition (i)) or carbonyl chloride reactor cooling water when above from steady state, 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 promptly 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 of selling on the market (pulverizing cocoanut active charcoal) in the pipe as diameter 1.2～1.4mm.
The carbon monoxide of supply 1.2kg/h, the chlorine of 2.8kg/h, the carbonyl chloride gas of 3.9kg/h are made in the carbonyl chloride reactor.Reaction heat is removed with the water of 90 ℃ of 80kg/h feedings in shell position at the carbonyl chloride reactor, and this moment, the reactor outlet temperature of water was 93 ℃, and pressure is 0.2MPaG.
(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 last continuous carbonyl chloride manufacturing process, and the supply pressure of the carbonyl chloride gas of supplying with to the oligopolymer reactor is set at 0.45MPaG.
In the oligopolymer reactor, supply with 3.9kg/h carbonyl chloride gas, 44kg/h concentration 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.
, make the flow (F1) of carbonyl chloride reactor cooling water descend 25% wittingly herein, be 60kg/h.
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 promptly it is by innoxious.In addition, also N/R temperature rises in the carbonyl chloride reactor.
Embodiment 1-2
Flow (F1) with the carbonyl chloride reactor cooling water descends 50% wittingly, is 40kg/h, in addition, with embodiment 1-1, makes 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 promptly it is by innoxious.In addition, also N/R temperature rises in the carbonyl chloride reactor.
Embodiment 1-3
Flow (F1) with the carbonyl chloride reactor cooling water descends 55% wittingly, is 36kg/h, in addition, with embodiment 1-1, makes 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 promptly it is by innoxious.In addition, also N/R temperature rises in the carbonyl chloride reactor.
Comparative example 1-1
Do not use automatic control device, in addition,, carry out the manufacturing of polycarbonate oligomer with embodiment 1-1.
But, under the situation that does not have control automatically, it is contemplated that local temperature rises in the carbonyl chloride reactor, if continue operation, local temperature rises to more than the design temperature in the carbonyl chloride reactor, cause the breakage of carbonyl chloride reactor, cause carbonyl chloride to system's external leakage, so ended operation.
Embodiment 2-1
Temperature out (T1) with the carbonyl chloride reactor cooling water rises 5 ℃ wittingly, 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 promptly it is by innoxious.In addition, also N/R temperature rises in the carbonyl chloride reactor.
Embodiment 2-2
Temperature out (T1) with the carbonyl chloride reactor cooling water rises 10 ℃ wittingly, 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 promptly it is by innoxious.In addition, also N/R temperature rises in the carbonyl chloride reactor.
Embodiment 2-3
Temperature out (T1) with the carbonyl chloride reactor cooling water rises 25 ℃ wittingly, 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 promptly it is by innoxious.In addition, also N/R temperature rises in the carbonyl chloride reactor.
Comparative example 2-1
Do not use automatic control device, in addition,, carry out the manufacturing of polycarbonate oligomer with embodiment 2-1.
But, under the situation that does not have control automatically, it is contemplated that local temperature rises in the carbonyl chloride reactor, if continue operation, local temperature rises to more than the design temperature in the carbonyl chloride reactor, cause the breakage of 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 the breakage of carbonyl chloride reactor taking place inducing reaction the accident of device cooling failure etc., also can promptly stop to make and supplying with carbonyl chloride, simultaneously by automatic control, 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 the operation (1) of the carbonyl chloride gas that contains unreacted carbon monoxide continuously, and in the oligopolymer reactor, supply with the carbonyl chloride gas of making continuously in the described operation (1), the alkali aqueous solution and the organic solvent of dihydric phenol continuously, make the operation (2) of the reaction mixture that contains polycarbonate oligomer continuously;
The control method of described continuous manufacturing polycarbonate oligomer is satisfying following condition (i) and/or (ii) the time, stop the chlorine in the described operation (1) and the supply of carbon monoxide, stop simultaneously in the oligopolymer reactor supplying with carbonyl chloride gas, 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 cooling water flow F1 of carbonyl chloride reactor reduces by 25% when above from steady state,
Condition is (ii): when the temperature out T1 of carbonyl chloride reactor cooling water when steady state rises more than 5 ℃.
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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| KR20240014072A (en) * | 2021-05-27 | 2024-01-31 | 바스프 에스이 | How to make phosgene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388812A (en) * | 2000-09-05 | 2003-01-01 | 出光石油化学株式会社 | Process for production of polycarbonate |
| WO2003029324A1 (en) * | 2001-09-27 | 2003-04-10 | Idemitsu Petrochemical Co., Ltd. | Polycarbonate resin and process for producing the same |
| US20060069228A1 (en) * | 2004-09-27 | 2006-03-30 | General Electric Company | Process to make polycarbonate from bismethylsalicylcarbonate (BMSC) |
| 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 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| DE19848668A1 (en) * | 1998-10-22 | 2000-04-27 | Bayer Ag | Phosgene with a low tetrachloro-carbon content for production of poly-carbonate or polyester-carbonate, made by ensuring that the gas leaves the phosgene generator at relatively low temperature and pressure |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388812A (en) * | 2000-09-05 | 2003-01-01 | 出光石油化学株式会社 | Process for production of polycarbonate |
| WO2003029324A1 (en) * | 2001-09-27 | 2003-04-10 | Idemitsu Petrochemical Co., Ltd. | Polycarbonate resin and process for producing the same |
| US20060069228A1 (en) * | 2004-09-27 | 2006-03-30 | General Electric Company | Process to make polycarbonate from bismethylsalicylcarbonate (BMSC) |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107075102A (en) * | 2014-11-07 | 2017-08-18 | 出光兴产株式会社 | Process for the production of branched polycarbonates |
| CN107075102B (en) * | 2014-11-07 | 2019-06-11 | 出光兴产株式会社 | Process for the production of branched polycarbonates |
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| KR101823724B1 (en) | 2018-01-30 |
| KR20140009405A (en) | 2014-01-22 |
| WO2012132031A1 (en) | 2012-10-04 |
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| JP2012214633A (en) | 2012-11-08 |
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