EP1248807A1 - Procede continu de fabrication de polymeres dans du dioxyde de carbone - Google Patents

Procede continu de fabrication de polymeres dans du dioxyde de carbone

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Publication number
EP1248807A1
EP1248807A1 EP00978446A EP00978446A EP1248807A1 EP 1248807 A1 EP1248807 A1 EP 1248807A1 EP 00978446 A EP00978446 A EP 00978446A EP 00978446 A EP00978446 A EP 00978446A EP 1248807 A1 EP1248807 A1 EP 1248807A1
Authority
EP
European Patent Office
Prior art keywords
reaction vessel
monomer
separator
reaction
tert
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00978446A
Other languages
German (de)
English (en)
Inventor
Paul A. Charpentier
Joseph M. Desimone
George W. Roberts
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of North Carolina at Chapel Hill
North Carolina State University
University of California
Original Assignee
University of North Carolina at Chapel Hill
North Carolina State University
University of California
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of North Carolina at Chapel Hill, North Carolina State University, University of California filed Critical University of North Carolina at Chapel Hill
Publication of EP1248807A1 publication Critical patent/EP1248807A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • 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
    • B01J19/18—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
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/008—Processes carried out under supercritical conditions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C08F14/22—Vinylidene fluoride
    • 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
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • 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
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00033—Continuous 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00105—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling
    • B01J2219/00114—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling involving reactant slurries
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • CO 2 is cheap ($100-200/ton), of low toxicity, non-flammable, and environmentally and chemically benign.
  • CO technology has several significant advantages as it will allow for the elimination of: a) expensive polymer drying steps; (b) expensive wastewater treatment and disposal steps where significant amounts of monomer, surfactants and emulsifiers are generated (Baker, R.T. and W. Tumas, Toward Greener Chemistry. Science, 1999. 284: p.
  • a continuous system in scCO can also be exploited to incorporate in situ steps to purify the resultant polymer by supercritical fluid extraction (SFE) (McHugh, M.A., Krukonis V.J. Supercritical Fluids Extraction: Principles and Practice. Butterworth-Heineman, Stoneham, 1993).
  • SFE supercritical fluid extraction
  • a first aspect of the present invention is, accordingly, a method for carrying out the continuous polymerization of a monomer in a carbon dioxide reaction medium. The method comprises the steps of:
  • the combining of the monomer, the initiator, and the carbon dioxide reaction medium as recited by step (b) is preferably carried out by continuously feeding the monomer, the initiator, and the carbon dioxide reaction medium to the reaction vessel.
  • a purge is positioned downstream of the reaction vessel (described in detail herein) so as to remove an amount of the effluent stream as deemed appropriate by one skilled in the art.
  • the at least a portion of effluent that is returned to the reaction vessel is typically a fraction less than one.
  • VF2 The points are experimental data.
  • the points are experimental data and the line is a linear least-squares regression fit to the points.
  • Fig. 5 Effect of inlet initiator concentration, [I] IN , on the monomer conversion (X).
  • the points are experimental data.
  • Fig. 6. Plot of R p /[VF2]ou ⁇ versus [I]ou ⁇ ° '5 to show square root dependence of polymerization rate on initiator concentration.
  • the points are experimental data and the line is a linear least-squares regression fit to the points.
  • the polymerization conditions were the same as Figure 5.
  • Fig. 17 is a schematic diagram of a continuous loop reactor which may be employed in accordance with the invention.
  • a number of unsaturated acid monomers may be used in the continuous polymerization.
  • Exemplary monomers of this type include, but are not limited to, unsaturated mono- or dicarboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and the like. Derivatives, blends, and mixtures of the above may be used.
  • Initiators that may be used in the invention are numerous and known to those skilled in the art. Examples of initiators are set forth in U.S. Patent No. 5,506,317 to DeSimone et al., the disclosure of which is incorporated by reference herein in its entirety.
  • example polymers that may be used in the present invention include but are not limited, those formed from any of the above monomers.
  • vinylidene fluoride (VF2) and acrylic acid (AA) are polymerized, alone or in combination, utilizing diethyl peroxydicarbonate (DEPDC) as the free-radical initiator for VF2, and 2,2'-azobis(isobutyronitrile) (AIBN) as the free-radical initiator for AA.
  • DEPDC diethyl peroxydicarbonate
  • AIBN 2,2'-azobis(isobutyronitrile)
  • the initiator may be one that provides the end groups for the polymer chain, and can provide stable end groups to the polymer if desired.
  • the invention may encompass polymerizing monomers not limited to those set forth herein, either by themselves to form homopolymers, or in combination to form, for example, copolymers or terpolymers.
  • Fig. 13 refers to an embodiment in which the separator is present in the form of a plurality of parallel filters, in this example, denoted as 100a and 100b. Additional filters may be employed as deemed necessary by one skilled in the art.
  • effluent stream 120 from the continuous reaction vessel is passed into one of the filters 100a or 100b by virtue of the flow being diverted to the desired filter.
  • Polymer is collected in either of the filters and the resulting outgoing stream 130 comprises primarily liquid or supercritical fluid, unreacted initiator (if any), and unreacted monomer (if any).
  • Stream 130 is then repressurized by compressor 110 and the resulting stream 135 is recycled back to the reaction vessel.
  • a rotating device 220 with drive 225 may be present in various configurations is present in the separator and serves to continuously remove the polymer that collects on the inside surface of the walls 260.
  • the rotating device 220 is present in the form of a screw, although other types of devices can be employed within the scope of the invention.
  • the screw 220 removes the polymer from the wall 260 and conveys the polymer through the bottom 250 of the separator.
  • a solid wall 290 surrounds the bottom of the screw as depicted in Fig. 14.
  • the screw 220 is designed to melt the polymer and form a seal in the screw 220.
  • the molten polymer is conveyed through exit 250 from the high pressure region of the device to an essentially ambient pressure region, where it is cooled and processed by techniques known to one skilled in the art.
  • the separator 200 may operate in a continuous fashion.
  • FIG. 15 A preferred embodiment for a cyclone-type separator 300 is depicted in FIG. 15.
  • cyclone 310 is in fluid communication with parallel filters 320a and 320b positioned downstream of the cyclone 310.
  • Incoming effluent stream 330 containing liquid or supercritical fluid, unreacted monomer (if any), and unreacted initiator (if any) enters the cyclone 310 which results in the formation of a bottom stream 340 containing a relatively high percentage of polymer and a top stream 350 containing primarily liquid or supercritical fluid, unreacted monomer (if any), and unreacted initiator (if any), along with polymer.
  • step (d) is followed by the step of: (e) repeating the withdrawing step (c) while concurrently removing the solid polymer separated in the second separator during the withdrawing step (d).
  • an initiator is employed in step (b).
  • a purge is located in a return polymerization line between the separator(s) and the reaction vessel so as to remove an amount of the effluent stream as deemed appropriate by one skilled in the art.
  • the at least a portion of effluent that is returned to the reaction vessel is typically a fraction less than one.
  • Any suitable system or apparatus may be used as the control means for maintaining said reaction medium as a liquid or supercritical fluid in the separator and the return line (and preferably at a pressure not more than 50 or 100 psi different from the pressure in said reaction vessel during polymerization of monomer therein).
  • Examples include, but are not limited to, charging fluid into the system wherein the charging may be controlled through the use of a computer which may be analog or digital, removing reaction medium from the system wherein the removing may be controlled through the use of a computer which may be analog or digital, adding heat to the system, wherein adding the heat may be controlled through the use of a computer which may be analog or digital, removing heat from the system, wherein removing the heat may be controlled through the use of a computer which may be analog or digital, or pumping the reaction medium, wherein pumping may be controlled through the use of a computer which may be analog or digital.
  • the experimental system consists of an intensely mixed, continuous stirred tank reactor (CSTR), followed by two high-pressure filters in parallel, where the polymer is collected.
  • CSTR continuous stirred tank reactor
  • This method is widely applicable to various monomers in heterogeneous polymerizations, both with and without surfactants.
  • VF2 vinylidene fluoride
  • VF2 vinylidene fluoride
  • the poly(vinylidene fluoride) polymer (PVDF) was collected as a dry "free-flowing" powder, and has been characterized by gel permeation chromatography (GPC).
  • VF2 monomer was donated by Solvay Research, Belgium and SFE/SFC grade CO 2 was donated by Air Products & Chemicals, Inc. All other chemicals were obtained from Aldrich Chemical Company.
  • the DEPDC (diethylperoxydicarbonate) initiator was synthesized as previously reported, using water as a reaction medium and extracting the initiator into Freon 113 (Mageli, O.L.; Sheppard, C.S.; In Organic Peroxides, Vol. /, Swern D, Eds.; Wiley-Interscience, New York, 1970 pp. 1-104; Hiatt, R. In Organic Peroxides, Vol. II, Swern D, Eds.; Wiley-Interscience, New York, 1970 pp. 799-929; Strain, F.;.
  • FIG. 1 A schematic of the equipment used for the polymerization is shown in Fig. 1.
  • Carbon dioxide 14 and monomer 15 are pumped continuously by Isco syringe pumps 16 and 17 in constant flow mode and mixed by an 8-element static mixer 8, before entering the reactor 18.
  • the initiator solution is also pumped continuously by an Isco syringe pump 19 in constant flow mode, and enters the reactor 18 as a separate stream. All feed lines have check-valves to prevent back-flow, thermocouples, and rupture disks for safety in case of overpressurization.
  • the CSTR is an 800 mL Autoclave Engineers (AE) autoclave with a magnedrive to provide mixing of ingredients with an AE dispersimax impeller.
  • AE Autoclave Engineers
  • Fig. 1 depicts a continuous stirred tank reactor 18. It should be appreciated that other reactors can be employed in the system depicted in Fig. 1 such as, without limitation, a continuous loop reactor as referred to herein.
  • the effluent stream leaves the CSTR 18 through the bottom, and is directed by a 3-way ball-valve 10 (HIP) to one of two 280 mL filter housings (Headline) containing 1 ⁇ m filters where the solid polymer is collected. Unreacted monomer, initiator and CO 2 pass through the filters and flow through a heated control valve 12 (Badger). This control valve functions as a back-pressure regulator, which controls the reactor pressure at the desired set-point.
  • the effluent stream passes through a water bath to remove unreacted peroxide, while the gaseous CO 2 and monomer is safely vented into a fume-hood. Very low levels of polymer were found in the water bath, so essentially all precipitated polymer was collected on the 1 ⁇ m filters.
  • the entire polymerization apparatus 20 was computer controlled and monitored.
  • the supervisory control and data-acquisition (SCAD A) system consists of National Instruments BridgeVIEW software and Fieldpoint input/output modules. Input modules were utilized for reading pressure transducers and thermocouples. Output modules were utilized to control the reactor furnace, and the control valve. All control functions were performed utilizing PID algorithms.
  • the reactor was first heated to the desired temperature and the agitator was set to 1800 revolutions per minute (RPM). The system was then purged with N 2 . After about 2 hours, the control valve was closed and the system was pressurized with CO 2 to the desired reactor pressure. The desired CO 2 flow rate was set and the temperature and pressure of the system were allowed to stabilize. Temperature control was ⁇ 0.2 °C, while pressure control was ⁇ 1 bar. When the system had stabilized, the initiator flowrate was set and initiator was allowed to flow through the system for at least 3 residence times in order to remove impurities. Monomer flow was then started.
  • RPM revolutions per minute
  • Table 2 provides the polymerization results and GPC data for the poly(vinylidene fluoride) (PVDF) polymer produced in these experiments.
  • the rate of polymerization (R p ) for the CSTR system reached a maximum of 19 x 10 "5 mol/L-s, at a feed monomer concentration of 1.7 mol/L. This rate will increase as the concentration of monomer is increased.
  • This example describes a system for the continuous polymerization of various monomers in scCO 2 .
  • the feasibility of the continuous precipitation polymerization of VF2 and AA has been demonstrated using an intensely-agitated, continuous stirred tank reactor (CSTR). Rates of polymerization of VF2 in the CSTR are significantly higher than the average rates of batch polymerization, under similar conditions.
  • PVDF Poly(vinylidene fluoride)
  • VDF Poly(vinylidene fluoride)
  • emulsion or suspension batch techniques at polymerization conditions of between 10-200 bar at temperatures from 10-130 °C
  • Russo S., M. Pianca
  • G. Moggi Poly (vinylidene fluoride), in Polymeric Materials Encyclopedia, J.C. Salamone, Editor.
  • the emulsion technique requires that the final polymer latex be first coagulated, thoroughly washed, then spray-dried before a free-flowing powder is obtained.
  • the suspension technique requires separation of the polymer from the water phase, thorough washing, then drying.
  • Vinylidene fluoride monomer normally contains no inhibitors and PVDF polymer does not require additives for stabilization during melt-processing, thereby qualifying this polymer for applications such as ultrapure water systems where high purity materials are required. Due to the inherent disadvantages of the traditional techniques for preparing PVDF, such as additives required for polymerization and difficult to treat waste streams, a continuous environmentally-friendly process is attractive.
  • This example also describes the kinetics and mechanism of VF2 polymerization initiated by the organic peroxide, diethyl peroxydicarbonate
  • VF2 monomer was provided by Solvay Research, Belgium and SFE/SFC grade CO 2 was provided by Air Products & Chemicals, Inc. All other chemicals were obtained from Aldrich Chemical Company.
  • GPC gel permeation chromatography
  • FIG. 2 shows a GC analysis used to determine the attainment of steady-state for a typical polymerization run.
  • the effluent VF2 concentration is measured as a function of time, in units of the reactor residence time, ⁇ .
  • steady-state was attained after about 5 ⁇ .
  • Polymer collection was normally initiated after 5 ⁇ 's by switching to the SS collector. After SS polymer collection was complete, the exit stream was turned back to the non-SS filter such that SS polymer was not mixed with non-SS polymer. After the reactor had been on stream for at least 5 ⁇ 's, collection of polymer for varying time lengths was found to give identical polymer weight/collection time ratios, confirming the results from the GC analysis.
  • RTD decomposition kinetics of the DEPDC free-radical initiator
  • Fig. 3 provides the effect of stirring rate and agitator type on monomer conversion (X).
  • This type of agitator provides mainly radial flow (Geankoplis, C.J., Transport Processes and Unit Operations. Third ed. 1993, Englewood Cliffs, New Jersey: Prentice Hall). It is clear that the conversion is not affected by the stirring rate for the region investigated.
  • an in-house designed pitched-blade turbine agitator For the lowest stirring rate investigated, 1300 rpm, an in-house designed pitched-blade turbine agitator also was investigated.
  • This agitator is a 4-bladed, 45° pitch, upward pumping agitator designed to provide a combination of axial and radial flow in order to suspend precipitated particles.
  • This agitator was studied at the lowest rpm to minimize bearing wear in case of any offset in manufacture.
  • the conversion obtained with this agitator is identical to that obtained with the DispersimaxTM impeller, indicating that no effect of agitator geometry was obtained on conversion, for the conditions studied.
  • the reactor concentrations are the same as the outlet concentrations (Levenspiel, O., Chemical Reaction Engineering. Second ed. 1972, New York: John Wiley & Sons).
  • the outlet monomer concentration was determined by mass-balance (gravimetrically by weighing the polymer collected at steady-state) and confirmed by on-line GC analysis. This allows us to determine R p experimentally, as both the inlet monomer concentration and the mean residence time of the reactor ⁇ are known.
  • Fig. 4 provides the plot of R p versus [VF2] 1 0 which illustrates that this polymerization is first-order with respect to monomer. First-order dependency is generally obtained in free-radical kinetics for monomer consumption (Odian, G., Principles of Polymerization. 3rd ed. 1991, New York: John Wiley & Sons, Inc).
  • Fig. 5 provides the plot of monomer conversion (X) versus the inlet initiator concentration, i.e. [I] IN - It is evident that the conversion increases with an increase in initiator concentration, as more free radicals are generated to initiate polymer chains.
  • Fig. 6 provides the plot of R p versus [I]ou ⁇ ° 5 , which shows that the order of the reaction with respect to initiator is 0.5. However, note that a small offset error occurred, [I-I*]° 5 For future calculations, [I-I*] 0'5 , is used to account for this error. For subsequent experiments, initiator inlet concentrations of 3 mM were used.
  • Equation 12 is hereafter referred to as the model equation for determining the R p .
  • Equation 12 we must first determine experimental values for the ratio, which should only depend on the reactor temperature for a given
  • Fig. 7 provides the plot of equation 14, which is linear indicating that this system follows the Arrhenius relationship in the region investigated.
  • An E p -(E t /2) value of 69 kj/mol was determined from this plot.
  • Table 4 provides the k p /k° 5 values determined for the 4 temperatures studied.
  • Fig. 8 shows the effect of reactor temperature on the experimentally determined R p (determined from equation 2) and compares these values to those predicted from model equation 12. The agreement with the model equation is excellent. As expected, R p increases rapidly with temperature.
  • Fig. 11 shows how the number and weight average molecular weights (M n and M ) increase with increasing outlet monomer concentration and provides a comparison to model equations.
  • PVDF poly(vinylidene fluoride)
  • a scaled-up apparatus for implementing the present invention is described in Fig. 12.
  • Initiator is transported continuously to a reactor, along with, and at a separate location from, carbon dioxide and monomer, which are introduced via a recirculation line through a recirculation pump.
  • Make-up CO 2 and monomer may be introduced through the top of the reactor if so desired as depicted.
  • the effluent stream is cooled and is transported to a separator (e.g., a filter or cylcone configuration).
  • Polymer product exits through the bottom of the reactor and is collected in the separator.
  • Carbon dioxide either through the top or bottom of the reactor, may be employed to assist with transporting the polymer to a low pressure bag filter or extruder hopper.
  • An effluent stream comprising carbon dioxide, unreacted monomer (if any), and unreacted initiator (if any) is recycled back to the reactor as shown in Fig. 12.
  • a purge is bled off from as a portion of the effluent stream.
  • a liquid stream may optionally be collected through the bottom of the condenser if so desired.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)

Abstract

L'invention concerne un procédé permettant de réaliser la polymérisation continue d'un monomère dans un milieu de réaction au dioxyde de carbone. Ce procédé comprend les étapes consistant: (a) à fournir un appareil comprenant une cuve de réaction continue et un séparateur; (b) à réaliser une réaction de polymérisation dans la cuve de réaction en combinant un monomère et un milieu de réaction au dioxyde de carbone (de préférence, en combinant également un déclencheur), le milieu de réaction étant un liquide ou un fluide supercritique, et la réaction produisant un produit polymère solide dans la cuve de réaction; puis, (c) à extraire un flux d'effluents continu de ladite cuve pendant la réaction de polymérisation, ce flux étant maintenu à l'état de liquide ou de fluide supercritique; puis (d) à passer ce flux continu à travers le séparateur et à séparer le polymère solide de celui-ci tout en maintenant au moins une partie dudit flux à l'état de liquide ou de fluide supercritique; puis (e) à renvoyer au moins une partie du flux continu dans la cuve tout en le maintenant à l'état de liquide ou de fluide supercritique. De ce fait, il n'est pas absolument nécessaire de procéder à une recompression significative du flux d'effluents continu avant de le renvoyer dans la cuve de réaction. L'invention concerne également un dispositif permettant de réaliser ces procédés.
EP00978446A 1999-11-12 2000-11-10 Procede continu de fabrication de polymeres dans du dioxyde de carbone Withdrawn EP1248807A1 (fr)

Applications Claiming Priority (3)

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US16517799P 1999-11-12 1999-11-12
US165177P 1999-11-12
PCT/US2000/030765 WO2001034667A1 (fr) 1999-11-12 2000-11-10 Procede continu de fabrication de polymeres dans du dioxyde de carbone

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Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1191042A1 (fr) * 2000-09-26 2002-03-27 Atofina Procédé de polymérisation du 1,1-difluoroéthylène sous haute pression
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WO2004020476A1 (fr) * 2002-08-28 2004-03-11 Daikin Industries, Ltd. Procede de production de polymere fluore
AU2002324369A1 (en) * 2002-09-20 2004-04-08 Avantium International B.V. Method and apparatus for performing chemical experiments
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JP2006233146A (ja) * 2005-02-28 2006-09-07 Sanyo Chem Ind Ltd アルキレンオキシド重合体の製造方法
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FR2953843B1 (fr) * 2009-12-16 2012-02-24 Solvay Procede de preparation d'un polymere halogene et dispositif pour sa mise en oeuvre
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JP2013194177A (ja) * 2012-03-21 2013-09-30 Sumitomo Chemical Co Ltd 連続重合の停止方法
JP2014159539A (ja) * 2013-01-28 2014-09-04 Ricoh Co Ltd ポリマー製造装置
JP6515466B2 (ja) * 2013-11-20 2019-05-22 株式会社リコー ポリマー製造装置及びポリマーの製造方法
CN106604778B (zh) * 2014-06-24 2018-12-18 诺瓦化学品(国际)股份有限公司 控制搅拌反应器中的局部流体年龄

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5328972A (en) * 1992-09-28 1994-07-12 Rohm And Haas Company Process for preparing low molecular weight polymers
DE4418149A1 (de) * 1994-05-25 1995-11-30 Bayer Ag Verfahren zur Herstellung von Styrol-Acrylnitril-Copolymerisaten
EP0776341A1 (fr) * 1994-08-18 1997-06-04 The University Of North Carolina At Chapel Hill Polymerisation cationique en presence de dioxyde de carbone
EP0813548B1 (fr) * 1995-03-10 2000-07-05 UNIVERSITY OF NORTH CAROLINA AT CHAPEL HILL ; Office of Research Services Polymerisation non aqueuse de fluoromonomeres
US6051682A (en) * 1996-12-23 2000-04-18 E. I. Du Pont De Nemours And Company Polymerization of fluoropolymers in carbon dioxide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0134667A1 *

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