WO2001021302A1 - Procede et dispositif permettant de conduire des reactions de polymerisation-fusion - Google Patents

Procede et dispositif permettant de conduire des reactions de polymerisation-fusion Download PDF

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Publication number
WO2001021302A1
WO2001021302A1 PCT/US2000/024537 US0024537W WO0121302A1 WO 2001021302 A1 WO2001021302 A1 WO 2001021302A1 US 0024537 W US0024537 W US 0024537W WO 0121302 A1 WO0121302 A1 WO 0121302A1
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WIPO (PCT)
Prior art keywords
reaction vessel
reaction
block
optical analyzer
reaction mixture
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PCT/US2000/024537
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English (en)
Inventor
Gregory Lee Warner
William Patrick Flanagan
John Patrick Lemmon
Radislav Alexandrovich Potyrailo
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General Electric Company
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Publication date
Application filed by General Electric Company filed Critical General Electric Company
Priority to AU71211/00A priority Critical patent/AU7121100A/en
Publication of WO2001021302A1 publication Critical patent/WO2001021302A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/205—General preparatory processes characterised by the apparatus used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0073—Sealings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00054—Controlling or regulating the heat exchange system
    • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00058—Temperature measurement
    • B01J2219/00063—Temperature measurement of the reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00083—Coils
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    • B01J2219/00094—Jackets
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    • B01J2219/00132—Controlling the temperature using electric heating or cooling elements
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    • B01J2219/0015—Controlling the temperature by thermal insulation means
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00162—Controlling or regulating processes controlling the pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00252—Formation of deposits other than coke
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/00277—Apparatus
    • B01J2219/00279—Features relating to reactor vessels
    • B01J2219/00281—Individual reactor vessels
    • B01J2219/00283—Reactor vessels with top opening
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00306—Reactor vessels in a multiple arrangement
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00479—Means for mixing reactants or products in the reaction vessels
    • B01J2219/00481—Means for mixing reactants or products in the reaction vessels by the use of moving stirrers within the reaction vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00495—Means for heating or cooling the reaction vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/0072—Organic compounds
    • B01J2219/00722—Nucleotides
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • This invention relates to chemical reactors.
  • the present invention is directed to a method and apparatus for conducting melt- polymerization reactions.
  • the apparatus includes a reaction vessel having an interior portion adapted to receive a reaction mixture.
  • An agitator is disposed relative to the reaction vessel such that the agitator is capable of agitating the reaction mixture.
  • a conduit is placed in fluid communication with the interior portion of the reaction vessel.
  • a temperature probe is placed in thermal communication with the reaction vessel, and an optical analyzer adapted to perform real-time in situ analysis of the reaction mixture is placed proximate or within the reaction vessel.
  • the reaction is monitored and reaction conditions are adjusted, if necessary, to maintain the reaction within pre-determined parameters.
  • the reactor can be used for the development and optimization of melt polymerization reactions, particularly the formation of polycarbonates, or other reactions in which Fries rearrangement products are present.
  • FIG. 1 is a cross sectional view of an aspect of an embodiment of the invention
  • FIG. 2 shows a top view and a side view of an aspect of an embodiment of the invention
  • FIG. 3 is a cross-sectional view of an aspect of an embodiment of the invention.
  • FIG. 4 is a cross-sectional view along line 4-4 of FIG. 3;
  • FIG. 5 is cross-sectional view along line 5-5 of FIG. 3;
  • FIG. 6 is an excitation-emission spectrum of solid LX melt polycarbonate
  • FIG. 7 is a graphical representation of fluorescence spectra of various concentrations of Fries product in polycarbonate
  • FIG. 8 is a graphical representation of fluorescence spectra of various concentrations of Fries product in polycarbonate
  • FIG. 9 is a schematic view of an apparatus capable of performing an aspect of an embodiment of the present invention.
  • FIG. 10 is a schematic view of a portion of an apparatus capable of performing an aspect of an embodiment of the present invention.
  • FIG. 11 is a cross-sectional view of a portion of an apparatus capable of performing an aspect of an embodiment of the present invention.
  • FIG. 12 is a schematic view of an apparatus capable of performing an aspect of an embodiment of the present invention.
  • an exemplary embodiment of the present invention includes a block 1, preferably formed of a heat-conductive metal or material (e.g., aluminum), which defines an internal cavity adapted to receive a reaction vessel 2.
  • the reaction vessel may be a glass or quartz tube, or any other material suitable for the particular reaction to be run therein.
  • the block is at least partly surrounded by an electrical heating band (not shown) which is capable of controlling and maintaining the temperature of reaction vessel 2.
  • an electrical heating band (not shown) which is capable of controlling and maintaining the temperature of reaction vessel 2.
  • cooling coils may be embedded inside the heating band so that cooled fluid, such as water or the like, may be directed through the coils.
  • a water jacket 3 may be provided through which hot or cold water can be passed to heat or cool the reaction vessel.
  • Reactor cap 4 can be constructed " of a heat-conductive metal or material (e.g., aluminum) and is secured to the block.
  • One way of securing the cap is with a plurality of Allen bolts 5, though any known means of sacrament is acceptable so long as it is effective in maintaining the selected reaction pressure within the reaction vessel.
  • a hermetic seal 7 is provided that is effective in holding the desired vacuum/pressure in the reaction vessel.
  • An o-ring may suitable for this purpose, preferably made of a halogen-elastomer, more preferably a flouroelastomer such as VITONTM or KALREZTM fiuoroelastomers, available from Dupont-Dow.
  • a halogen-elastomer more preferably a flouroelastomer such as VITONTM or KALREZTM fiuoroelastomers, available from Dupont-Dow.
  • cap 4 can be preferably adapted to fit over an upper portion of the reaction vessel 2.
  • FIG. 2 Depicted in FIG. 2 are a plurality of grooves 12 adapted to accept a beaded quartz reactor tube.
  • the top of the quartz tube that is inserted into the reaction vessel will preferably have beads that fit into the grooves located in cap 4. In this manner, the quartz tube is prevented from rotating due to the viscous drag when agitated or stirred.
  • other configurations for preventing the tube insert from rotating may be employed, such as using fitted o-rings pressed between the outside of the tube and the inside of the bored-out reactor chamber.
  • Cap 4 can be provided with a plurality of openings 6 that are in communication with reaction vessel 2, including a central opening 16 that is adapted to receive a shaft or shaft sleeve 8 of an agitator 10, depicted here as having a rotating blade 9.
  • the design of rotating blade(s) is such that they provide adequate mixing of low and high viscosity mediums both in the radial and axial directions.
  • an agitator fitted with elastomeric wiper blades to continuously wipe the inside of the quartz tube may be provided to ensure uniform mixing throughout the vessel and thereby avoid the sticking and accumulation of viscous material on and near the inside wall of the tube. This is also advantageous when utilizing optional viewing windows for optically analyzing the contents of quartz tube, because a wiper design will keep the optical view through the viewports clear of stagnant material not representative of the major contents of the reaction vessel.
  • openings 6 found in the reactor cap can be used to receive the following components (a) a conduit 11, preferably formed of stainless steel, for introducing or removing matter from the reaction vessel; (b) a temperature probe 13, such as a thermocouple or RTD, for measuring the temperature inside the reaction vessel; (c) a conduit (not shown) for controlling the pressure in the reaction vessel, either by providing pressurized gas or providing vacuum; and (d) an invasive optical probe (not shown) for real-time analysis of a reaction mixture within the reaction vessel.
  • a conduit 11 preferably formed of stainless steel, for introducing or removing matter from the reaction vessel
  • a temperature probe 13 such as a thermocouple or RTD, for measuring the temperature inside the reaction vessel
  • a conduit not shown
  • an invasive optical probe for real-time analysis of a reaction mixture within the reaction vessel.
  • an optical probe 20, or probes, for real-time analysis can be disposed in one or both of the openings 14, 15.
  • an appropriate seal 21 should be used with the probe in these openings if a desired reactor pressure is to be maintained.
  • the bottom opening 14 is shown open in FIG. 1, it should generally be sealed if one wishes to run the reaction at elevated pressures.
  • a method of sealing the openings involves providing a tapered thread (female NPT) and inserting a screw-in plug (male NPT), or to provide a straight machine thread with a screw-in plug holding a rubber o-ring seal, gasket, or the like.
  • FIGs. 3, 4, and 5 another alternative embodiment has lower sealed window ports 17 and upper sealed window ports 18.
  • lower window ports 17 are equipped with quartz windows 19 which can be used for the analysis without having to use an adapter fitting for mounting and sealing a probe against the pressure. That is, the analysis probe simply rests against the outside of the window for analysis while the openings 14, 15 are sealed off.
  • quartz is preferred to obtain improved optical analysis. Also, quartz can be used to maximize optical transmittance in the ultraviolet region of the spectrum while minimizing fluorescence background.
  • An agitator having elastomeric wiper blades 22 can be provided as discussed above.
  • the blades serve to keep the viewports clean as well as alleviating stagnant buildup on the inside quartz tube wall.
  • the blades shown in FIG. 3 are relatively short, but it is to be understood that they may extend upward for up to the entire height of the reaction vessel.
  • reaction vessel diameter must nevertheless be large enough to accommodate inserts such as an agitator, thermocouple, and an addition port.
  • the height of the reaction vessel is chosen to provide adequate head space above the reaction mixture to avoid possible spillover due to boiling or foaming of the mixture while heating and/or applying a vacuum to the reaction. Additional upper viewing ports 18 and windows 19 are shown in FIG. 3, which can be used to monitor such foaming events. Additional optical techniques may be used with feedback control strategies to prevent such spillovers.
  • the block is provided with a horizontal viewport 15 and/or a vertical viewport 14 drilled up from the bottom of the block, to provide viewing access for a portion of an optical analyzer (e.g., a fluorescence probe) to reaction vessel 2.
  • the purpose of the optical analyzer is to provide real-time monitoring of characteristic reaction or process conditions without the need to physically remove samples of the reaction mixture from the reaction vessel.
  • An optical method for direct measurement of Fries concentration in melt polycarbonate permits determination of Fries product during the melt polymerization process in presence of fluorescent, absorbing, and scattering, interfering species.
  • the method involves the use of multiple reaction vessels in which reactions are carried out in parallel with real-time monitoring of reaction progress in each of the multiple reaction vessels.
  • R 6 is an aromatic organic radical and, more preferably, a radical of the formula (II):
  • each of A 1 and A 2 is a monocyclic divalent aryl radical and Y 1 is a bridging radical having one or two atoms which separate A 1 from A 2 .
  • one atom separates A 1 from A 2 .
  • Illustrative non-limiting examples of radicals of this type are -O-, -S-, -S(O)- or -S(O 2 )-, -C(O)-, methylene.
  • the bridging radical Y 1 can be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene or isopropylidene.
  • Polycarbonates can be derived from dihydroxy compounds in which only one atom separates A 1 and A 2 .
  • dihydroxy compound includes, for example, bisphenol compounds representative of general formula (III) as follows:
  • R a and R b each represent a halogen atom or a monovalent hydrocarbon group and may be the same or different.
  • the p and q variables represent integers from 0 to 4.
  • the X a variable represents one of the following groups:
  • Variables R c and R d each independently represent a hydrogen atom or a monovalent hydrocarbon group. Variables R and R d may form a ring structure. Variable R e is a divalent hydrocarbon group.
  • dihydroxy-substituted aromatic hydrocarbons disclosed by name or formula (generic or specific) in U.S. Patent 4,217,438, which is incorporated herein by reference.
  • a nonexclusive list of specific examples of the types of bisphenol compounds that may be represented by formula (III) includes the following:
  • BPA 2,2-bis(4-hydroxyphenyl) propane
  • bis(hydroxyaryl) alkanes such as 2,2-bis(4-hydroxy-3-bromophenyl) propane
  • bis(hydroxyaryl) cycloalkanes such as 1 , 1 -bis(4-hydroxyphenyl) cyclohexane.
  • Preferred LX polycarbonates are bisphenol A polycarbonates, in which each of A 1 and A 2 is p-phenylene and Y 1 is isopropylidene.
  • the average molecular weight of the initial polycarbonate ranges from about 5,000 to about 100,000; more preferably from about 10,000 to about 65,000, and most preferably from about 15,000 to about 35,000.
  • Fries and “Fries product” denote a repeating unit in polycarbonate having the following formula:
  • X a is a bivalent radical as described in connection with Formula (III) supra.
  • the optical analyzer is capable of directly determining the concentration of a target species (e.g., Fries product) in a composition comprising aromatic carbonate chain units.
  • the optical analytical method includes the steps of irradiating a portion of the composition with electromagnetic radiation at an excitation wavelength sufficient to cause the target species to emit a fluorescence spectrum; detecting at least a portion of the fluorescence spectrum; and determining the concentration of the target species from the fluorescence spectrum.
  • the composition is preferably irradiated at an excitation wavelength that allows the target species to fluoresce at a detectable level that provides differential emission between the target species and interfering species.
  • the disclosed analytical method permits quantification of Fries product during a melt polymerization reaction in the presence of fluorescent, absorbing, and scattering interfering species.
  • the conditions used allow for selective excitation of the Fries product in the polycarbonate material; collection of its fluorescence emission; and relation of the measured fluorescence signal to Fries concentration.
  • the range of excitation wavelengths for quantification of Fries product is preferably selected to satisfy at least two criteria: (1) appreciable absorbance of the selected excitation wavelengths by Fries product and (2) minimal absorbance of the selected excitation wavelengths by interfering species.
  • the range of emission wavelengths for quantification of Fries product is preferably selected to satisfy at least two criteria: (1) Fries product emits fluorescence and (2) interfering species do not appreciably emit fluorescence.
  • interfering species include non-branched Fries end-groups, non-Fries end-groups, and cyclics. Also, different contaminant species may potentially emit fluorescence.
  • a typical excitation- emission spectrum of a solid LX material (119 ppm of Fries product) is presented in FIG. 6 to illustrate the complexity of the fluorescence spectrum of a solid LX material obtained after a melt polymerization reaction.
  • a suitable excitation wavelength is between about 250 nm and about 500 nm; preferably between about 300 nm and about 400 nm; more preferably between about 320 nm and about 350 nm; and most preferable about 340 nm.
  • Other portions of the excitation and emission fluorescence spectra can be collected for calibration, normalization, and scaling purposes. Compensation for the variation in absorbance and scattering effects of the measured regions at the excitation and emission wavelengths can be accomplished by at least two compensation methods.
  • the first compensation method comprises measuring the abso ⁇ tion spectrum of the probed region of polycarbonate over the spectral range that covers the excitation and emission wavelengths.
  • the second compensation method comprises using second order Rayleigh scattering effects in the emission and excitation spectra for scaling the spectral features.
  • the collected fluorescence intensity can be affected by a number of instrumental and sample parameters not related to the concentration of the fluorescent product.
  • various embodiments of the disclosed method allow for compensation to provide reproducible signals from single or multiple polymerization reactors during monitoring of the progress of, e.g., a polycarbonate melt polymerization reaction.
  • Second-order Rayleigh scattering effects are typically undesirable in conventional spectrometers for general applications because they distort the true spectral features of the measured samples.
  • These second order effects in the emission and excitation spectra can be eliminated by various techniques. For example, it is common to use excitation and emission filters that block the respective spectral portion of radiation from entering the measurement device (spectrometer). However, in various alternative embodiments, second order effects can be used to scale spectral features.
  • An example of second-order effects is shown in FIG. 7, where the peaks at 680 nm in both recorded spectra of solid polycarbonate samples are second-order effects resulting from excitation at 340 nm. These second order peaks are measured and used as reference excitation intensity. As shown in FIG.
  • the intensities of these peaks are different due to different excitation conditions of the two samples.
  • FIG. 8 after scaling both second- order peaks to the same height, the resulting spectra for two different concentrations of Fries product can be readily compared. In this manner a measurement taken during or after a reaction can be compared to a standard measurement or to a measurement taken earlier in the reaction cycle.
  • the present analytical method can be used to directly determine the concentration of a target species in parallel polycarbonate reactor systems having multiple reaction zones.
  • the method includes the steps of disposing an optical probe proximate each of the reaction zones and conducting a melt polymerization reaction within each of the reaction zones such that each zone contains a composition having aromatic carbonate chain units.
  • Electromagnetic radiation is passed through each of the optical probes at an excitation wavelength sufficient to cause the target species to emit a fluorescence spectrum. At least a portion of the fluorescence spectrum is detected from each of the reaction zones in order to determine the concentration of the target species in each zone.
  • FIG. 9 An apparatus for parallel monitoring of Fries product in multiple polymerization reactors is presented in FIG. 9. It is contemplated that the apparatus shown can be useful for combinatorial screening of catalysts and the like.
  • the apparatus includes a white light source 23, a collimator 25, an excitation optical filter 24, a beam splitter 26, a focusing lens 28, a fiber optic bundle 30, a plurality of polymerization reactors 1, a plurality of optical probes 34, an emission optical filter 36, a second focusing lens 38, and an imaging photo-detector 40.
  • both excitation optical filter 24 and emission optical filter 36 preferably comprise two filter elements 42,
  • each of the filter elements having a continuous linear variation of either cut-on or cut-off wavelength.
  • Such optical filter elements are commercially available, for example, from Coherent, Inc. of Auburn, CA.
  • White light 46 can be converted to colored light by using an opposed pair of these filter elements.
  • the bandwidth of white light 46 can be adjusted by counter rotating the elements, while coordinated rotation changes the center wavelength. In this manner, incoming white light 46 can be converted to constant- bandwidth, variable wavelength output light 48.
  • the filtered light passes through beam splitter 26 and is focused onto the tip of fiber-optic bundle 30.
  • the fiber-optic bundle is comprised of individual fibers or sub-bundles arranged together at one end and positioned at each reactor 1 at the other end.
  • Light is delivered to the reaction zone via optical probes 34.
  • Each optical probe can comprise a single optical fiber or a bifurcated fiber-optic bundle.
  • melt polycarbonate in a reaction vessel is a highly absorbing and scattering medium at the excitation and emission wavelengths of Fries products, it may be advantageous to utilize a probe having a central fiber or set of fibers for carrying the excitation light.
  • FIG. 11 An example of a cross-section of such a probe is shown in FIG. 11 wherein a plurality of collection fibers 52 are disposed around an excitation fiber 54 to collect fluorescence and deliver the same to photo-detector 40 (FIG. 9).
  • a third fiber 56 is used to deliver white light to the measurement location while a fourth fiber 58 is used to deliver the back propagated portion of light to the detector.
  • inner filter effect includes the significant abso ⁇ tion of the excitation or emission radiation as the radiation travels through the medium where the target species is located. More specifically, “primary inner filter effect” denotes significant abso ⁇ tion of the excitation radiation, and “secondary inner filter effect” denotes significant abso ⁇ tion of the emission radiation. As known to those skilled in the art, inner filter effects can affect the relationship between luminescence signal and analyte concentration, and correction factors can be calculated from absorbance and scatter at the excitation and emission wavelengths in order to compensate for the loss of optical signal at these wavelengths. Use of the probe shown in FIG. 11 can also compensate for variations in the refractive index of the optical medium.
  • excitation-emission fluorescence matrices can be collected simultaneously from each reactor 1.
  • excitation optical filter 24 is set to transmit white light
  • the absorbance/reflectance spectra are collected from each reactor 1 by the coordinated rotation of emission filter elements 42, 44.
  • Imaging photo-detector 40 is used for monitoring the fluorescence or absorbance/reflection changes at each of the multiple measurement locations.
  • the apparatus includes a multichannel spectrometer 60 having an absorbance/reflectance channel 62, a fluorescence-excitation channel 64, and a fluorescence-emission channel 66.
  • a fiber-optic bundle 30 is placed in optical commumcation with spectrometer 60 and a plurality of optical probes 34 (as described above), which can be located proximate reactors 1 (non- invasive) or immersed in reactors 1 (invasive, as shown).
  • Two of the channels 64, 66 are provided with optical filters 24, 36 (described supra).
  • multichannel spectrometer 60 is capable of measuring the excitation and emission fluorescence spectra and absorbance/reflectance from each reactor 1 in rapid sequence. Measurements in multiple reactors can be accomplished using the art- recognized time-domain multiplexing approach or having a miniature spectrometer for each of the reactors.
  • melt polymerizations include the synthesis of polyetherimide and poly(butyl)terephalate.
  • the present method and apparatus may be applied to the production of soft-segment polycarbonates and high-heat polycarbonates.
  • Such polycarbonates can be prepared by many methods, including transesterification in a solvent-free reaction mixture with diphenylcarbonate and a bisphenol, and the diphasic/interface process with phosgene and a bisphenol.
  • Soft-segment polycarbonates are copolyestercarbonates having reduced glass- transition temperatures. Such materials can be polymerized by art-recognized methods, such as those found in U.S. Patents Nos. 3,030331 and 3,169,121, both issued to Goldberg; and in U.S. Patents Nos. 4,130,548 and 4,286,083, both issued to Kochanowski, the disclosures of all of which are inco ⁇ orated by reference herein in their entirety.
  • High-heat polycarbonates can be prepared by a number of art-recognized methods, such as those disclosed by Mark et al. in U.S. Patent No. 4,576,996; St. Clair et al. in U.S. Patent No.
  • the present method and apparatus can form a part of a combinatorial strategy.
  • the method and apparatus can be applied as the second phase of a three-phase research program by providing multiple reactors in an array so as to be able to carry out multiple parallel reactions.
  • the first phase would involve a sequence of primary screening experiments to elicit basic information regarding fundamental catalytic activity.
  • the second phase using the present method, would elicit additional catalytic as well as process condition data for promising catalysts identified in phase 1.
  • the last phase would comprise the traditional scale-up experiments for the most promising catalysts identified in phase 2.
  • the most promising catalysts would be those with reduced Fries reaction activity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

Dans un mode de réalisation, ce dispositif comprend une cuve (2) à réaction comportant une partie interne conçue pour recevoir un mélange réactionnel. Un agitateur (10) est disposé de manière à pouvoir agiter le mélange réactionnel contenu dans la cuve (2) de réaction. Un conduit (11) se trouve en communication fluidique avec la partie intérieure de la cuve (2) de réaction. Une sonde (13) thermique est en communication thermique avec la cuve (2) à réaction, et un analyseur (20) optique capable de réaliser une analyse in situ en temps réel du mélange réactionnel est disposé à proximité de la cuve (2) à réaction ou à l'intérieur de celle-ci. Pendant le fonctionnement, ce dispositif assure une surveillance de la réaction et une adaptation des conditions de réaction le cas échéant, afin de maintenir la réaction dans des limites correspondant à des paramètres prédéterminés. Ce réacteur peut être utilisé pour une détection parallèle de réactifs et de conditions de traitement potentiels.
PCT/US2000/024537 1999-09-20 2000-09-08 Procede et dispositif permettant de conduire des reactions de polymerisation-fusion WO2001021302A1 (fr)

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WO2002081076A2 (fr) * 2001-04-05 2002-10-17 Symyx Technologies, Inc. Systeme de reacteur chimique combinatoire
WO2003026790A2 (fr) * 2001-09-24 2003-04-03 Symyx Technologies, Inc. Appareil et procede permettant de melanger de petits volumes de matieres reactives
WO2022202978A1 (fr) * 2021-03-25 2022-09-29 日本ペイントコーポレートソリューションズ株式会社 Procédé et appareil de production de résine

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
WO2002081076A2 (fr) * 2001-04-05 2002-10-17 Symyx Technologies, Inc. Systeme de reacteur chimique combinatoire
WO2002081076A3 (fr) * 2001-04-05 2003-04-24 Symyx Technologies Inc Systeme de reacteur chimique combinatoire
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WO2003026790A2 (fr) * 2001-09-24 2003-04-03 Symyx Technologies, Inc. Appareil et procede permettant de melanger de petits volumes de matieres reactives
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WO2003026790A3 (fr) * 2001-09-24 2003-07-10 Symyx Technologies Inc Appareil et procede permettant de melanger de petits volumes de matieres reactives
US6834990B2 (en) 2001-09-24 2004-12-28 Symyx Technologies, Inc. Impeller for mixing small volumes of reaction materials
WO2022202978A1 (fr) * 2021-03-25 2022-09-29 日本ペイントコーポレートソリューションズ株式会社 Procédé et appareil de production de résine

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