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WO2008135211A1 - Procédé de polymérisation en continu pour la production de polymères à étroite distribution de masse molaire, et réacteur taylor-couette pour la mise en oeuvre de ce procédé - Google Patents

Procédé de polymérisation en continu pour la production de polymères à étroite distribution de masse molaire, et réacteur taylor-couette pour la mise en oeuvre de ce procédé Download PDF

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Publication number
WO2008135211A1
WO2008135211A1 PCT/EP2008/003489 EP2008003489W WO2008135211A1 WO 2008135211 A1 WO2008135211 A1 WO 2008135211A1 EP 2008003489 W EP2008003489 W EP 2008003489W WO 2008135211 A1 WO2008135211 A1 WO 2008135211A1
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WO
WIPO (PCT)
Prior art keywords
reactor
taylor
couette
rotor
polymerization
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.)
Ceased
Application number
PCT/EP2008/003489
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German (de)
English (en)
Inventor
Markus Oberhoff
Werner-Alfons Jung
Edeltraud Hagemeister
Ursula Heimeier
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BASF Coatings GmbH
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BASF Coatings GmbH
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Publication of WO2008135211A1 publication Critical patent/WO2008135211A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B01J19/1806—Stationary reactors having moving elements inside resulting in a turbulent flow of the reactants, such as in centrifugal-type reactors, or having a high Reynolds-number
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/27—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices
    • B01F27/272—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices with means for moving the materials to be mixed axially between the surfaces of the rotor and the stator, e.g. the stator rotor system formed by conical or cylindrical surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/50—Pipe mixers, i.e. mixers wherein the materials to be mixed flow continuously through pipes, e.g. column mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B01F27/94—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with rotary cylinders or cones
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1812—Tubular reactors
    • 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
    • B01J19/1887—Stationary reactors having moving elements inside forming a thin film
    • 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
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • 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
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/185—Details relating to the spatial orientation of the reactor vertical
    • 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
    • B01J2219/19—Details relating to the geometry of the reactor
    • B01J2219/194—Details relating to the geometry of the reactor round
    • B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
    • B01J2219/1943—Details relating to the geometry of the reactor round circular or disk-shaped cylindrical
    • 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
    • B01J2219/19—Details relating to the geometry of the reactor
    • B01J2219/194—Details relating to the geometry of the reactor round
    • B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
    • B01J2219/1946—Details relating to the geometry of the reactor round circular or disk-shaped conical

Definitions

  • the invention relates to a Taylor Couette reactor for carrying out bulk polymerizations using at least one olefinically unsaturated monomer, wherein in the polymerization, a change in the kinematic viscosity v of the reaction medium occurs.
  • the invention further provides a process for the continuous bulk polymerization of monomers in this Taylor-Couette reactor.
  • Taylor-Couette reactors consist of two coaxial, concentrically arranged cylinders, of which the outer one is stationary and the inner one rotates.
  • the reaction space is the annular gap between the inner peripheral surface of the outer cylinder and the outer peripheral surface of the inner cylinder.
  • Taylor number Ta With increasing angular velocity of the inner cylinder, a number of different flow forms occur, which are characterized by a dimensionless index, the so-called Taylor number Ta.
  • the Taylor number is in addition to the angular velocity of the inner cylinder forming the rotor also dependent on the kinematic viscosity of the fluid in the reaction volume and the geometric parameters, the outer radius of the inner cylinder Ri, the inner radius of the outer cylinder, according to the following formula:
  • the laminar Couette flow a simple shear flow, forms.
  • a critical value alternately opposite rotating (contrasting) vortices with axes along the circumferential direction.
  • Taylor vortices are rotationally symmetric, have the geometric shape of a torus (Taylor vortex rings) and have a diameter that is approximately as large as the gap width. Two adjacent vertebrae form a vortex pair or a vortex cell.
  • Taylor Couette reactor If the Taylor Couette reactor is provided with an inlet and outlet and operated continuously, a Taylor vortex flow results with a small axial flow. Each vortex pair moves through the gap, with only a small mass transfer between adjacent vortex pairs occurs. The mixing within such vortex pairs is very high, whereas the axial mixing beyond the pair boundaries is only very small. A vortex pair can therefore be regarded as a thoroughly mixed stirred tank.
  • the flow system thus behaves like an ideal flow tube in that the vortex pairs travel through the gap with a constant residence time like ideal stirred tanks.
  • Taylor-Couette reactors are also known with partial or entirely conical geometry of the shell or stirrer along the reactor axis.
  • the best known reactor forms are a reactor with a completely conical jacket and a reactor with a jacket in organ pipe form.
  • Taylor Couette reactor with an organ pipe-shaped geometry is known from WO 2004/039491 A1.
  • This Taylor-Couette reactor is used for the continuous polymerization, in particular bulk polymerization.
  • High conversions can be achieved at high solids levels, however, the resulting polymers often have a broad molecular weight distribution and thus high polydispersity, i. have low uniformity.
  • Polymers with broader molecular weight distributions have a higher weight-average molecular weight average Mn and thus a higher viscosity for an equal number-average molecular weight average Mn.
  • Higher viscosity polymerizations suffer from metering difficulties of the feed pumps and insufficient homogenization within the reactor, which can lead to very different and still unstable reactor temperatures. Sometimes such polymerizations must be prematurely terminated due to the instabilities occurring. This is particularly undesirable in continuous processes, since the Advantages of the continuous process of low dead times and high space-time yields are thereby nullified.
  • the object of the invention is therefore to provide a Taylor-Couette reactor and a method for carrying out continuous polymerization, the
  • the reactor and the method should also allow to produce polymers with a low viscosity and to ensure a stable temperature control in the reactor.
  • a Taylor-Couette reactor for carrying out bulk polymerizations
  • the reactor has an outer reactor wall and a concentrically arranged rotor, a reactor bottom and a reactor cover, which together define the annular gap-shaped reactor volume, at least one Apparatus for metered addition of educts and a device for the product flow, and - wherein the reactor wall and / or the rotor is geometrically designed such that on substantially the entire reactor length in the reactor volume, the conditions for the Taylor vortex flow are met and wherein at the polymerization occurs a change in the kinematic viscosity v of the reaction medium, characterized in that the device for metering the educts above the reactor bottom is arranged in the lower two-thirds of the reactor shell.
  • the object is achieved by a process for the continuous polymerization of monomers in bulk in a Taylor Couette reactor according to the invention, wherein in the polymerization, a change in the kinematic viscosity v of the reaction medium occurs, characterized in that at least a portion of the starting materials to be polymerized Use of at least one olefinically unsaturated monomer via a device for metering the Starting materials, which is located above the reactor bottom in the lower two-thirds of the reactor shell, are metered into the Taylor Couette reactor.
  • polymer By polymer are referred to in summary homopolymer, copolymer, block (co) polymer and graft copolymers. Accordingly, the term polymerization is used to summarize homopolymerizations, copolymerizations, block and graft copolymerizations. Under the term
  • Bulk polymerization is polymerization with a high solids content, i.
  • the Taylor Couette reactor comprises an annular gap-shaped reaction volume, which preferably has a circular circumference.
  • the annular gap-shaped reaction volume is defined by an outer reactor wall, a rotor arranged concentrically therein, and a reactor bottom.
  • the outer reactor wall and the rotor have, viewed in cross-section over the entire length of the reaction volume, a circular circumference.
  • the term circular is strictly circular, oval, elliptical or polygonal with rounded corners to understand. For reasons of ease of manufacture, ease of construction, and significantly easier maintenance of constant conditions over the entire length of the annular gap-shaped reaction volume, a strictly circular circumference is advantageous.
  • the inner wall of the outer reactor wall and / or the surface of the rotor is smooth, or rough, ie, the surfaces in question have a low or high surface roughness.
  • the inner wall of the outer reactor wall and / or the surface of the rotor may have a relief-like radial and / or axial, preferably radial, surface profile, as for example in the US patent US 4,174, 907 A or the British patent GB 1 358 157 is described. If a radial surface profile is present, it is advantageously dimensioned approximately or exactly as the Taylor vortex rings. According to the invention, it is advantageous if the inner wall of the outer reactor wall and the surface of the rotor are smooth and profile-free in order to avoid blind spots in which gas bubbles or educts, process substances and products could settle.
  • the Taylor-Couette reactor according to the invention is stored vertically, horizontally or in a position between these two directions viewed in the longitudinal direction.
  • Advantageously according to the invention is the vertical storage. If the Taylor Couette reactor according to the invention is not stored horizontally, the reaction medium can flow through it from the bottom to the top against gravity or from top to bottom by gravity. According to the invention it is advantageous if the reaction medium is moved against gravity.
  • the annular gap-shaped reaction volume widened continuously or discontinuously in the direction of flow, in particular continuously, according to suitable mathematical functions.
  • suitable mathematical functions are straight lines, at least two straight lines which meet at an obtuse angle, parabolas, hyperbolas, e-functions or combinations of these functions, which merge continuously or discontinuously, in particular continuously.
  • the mathematical functions are straight lines, i. h., That the annular gap-shaped
  • Reaction medium in the flow direction can be estimated by the skilled person using the Taylor formula I and / or determined by simple preliminary tests.
  • the outer reactor wall can be cylindrical and the rotor can be conically shaped, the rotor having the largest diameter at its supported end.
  • the outer reactor wall may be conically shaped and the rotor may be cylindrical, ie, its cross section is constant over the entire rotor length.
  • the Taylor-Couette reactor is designed such that the cross-section of the reaction volume initially increases from the reactor foot to the reactor head, but the cross-sectional increase does not increase over at least part of the length of the rotor.
  • Such a reactor can, for example, have a conically widening reactor wall in a lower partial area and a cylindrical reactor wall in an adjoining area, so that the reactor jacket takes the form of an organ pipe, as in WO 2004/039491 A1.
  • the rotor is rotatably mounted in the reactor bottom or in the reactor head, preferably in the reactor bottom. He and his out to a drive device reaching drive shaft is sealed with a seal. At its other end, the rotor is not stored. The free end of the rotor may be planar, rounded or conical. Preferably, the seal is a mechanical seal.
  • the drive device may be a continuously variable electric motor or a pneumatically driven motor, which is connected via a transmission to the drive shaft.
  • the power of the motor depends on the maximum kinematic viscosity v of the reaction medium.
  • the connection to the drive shaft can be done by means of a magnetic coupling.
  • the device for metering (feed) for the starting materials in particular for the olefinically unsaturated monomers, and for suitable process materials, such as catalysts and initiators.
  • the feed goes through the reactor jacket.
  • the device for metering the starting materials in the middle third of the total height of the reactor shell based on the length of the entire reactor, preferably at a level of 40% - 50% of the total height of the reactor shell, arranged, viewed in the flow direction.
  • the Taylor Couette reactor according to the invention preferably has exactly one device for metering in the educts, ie an inlet.
  • the starting materials can be fed to the feed by means of customary and known methods and devices, such as metering pumps.
  • the devices may be equipped with conventional and known mechanical, hydraulic, optical and electronic measuring and control devices.
  • one of the mixing devices as described, for example, in German Patent Application DE 199 60 389 A1, column 4, line 55, to column 5, line 34, may be connected upstream of the inlet.
  • a pressure-maintaining valve is arranged, which builds up and regulates the pressure in the Taylor-Couette reactor according to the invention and through which the reaction products, in particular the polymers, are discharged continuously.
  • the pressure-holding valve can be followed by collecting and storage containers, mixing devices, such as devices for melt emulsification, cooling belts for the production of granules or other reactors.
  • the reactor wall in the inlet area, in the area of the annular gap-shaped reaction volume and in the outlet area and the inlet or inlets and the product outlet can be equipped with a heating or cooling jacket, so that they can be heated or cooled in cocurrent or countercurrent.
  • the Taylor-Couette reactor according to the invention may contain conventional and known mechanical, hydraulic, optical and electronic measuring and control devices, such as temperature sensors, pressure gauges, flow meters, optical or electronic sensors and devices for measuring substance concentrations, viscosities and other physical chemical quantities who forward their measurements to a data processing system that controls the entire process.
  • the Taylor Couette reactor according to the invention is designed pressure-tight, so that the reaction medium is preferably under a pressure of 1 to 100 bar can stand.
  • the Taylor Couette reactor according to the invention may consist of a wide variety of materials, as long as they are not attacked by the starting materials and the reaction products and withstand higher pressure. Preference is given to using metals, preferably steel, in particular stainless steel.
  • the Taylor Couette reactor according to the invention can be supplied for a wide variety of uses. It is preferably used for material conversions under the conditions of the Taylor flow, in which the kinematic viscosity v in the reaction medium increases in the direction of flow.
  • the feeds are preferably at the same level offset along the reactor circumference.
  • a very particular advantage of the Taylor-Couette reactor according to the invention is that the local succession in the Taylor-Couette reactor can be linked to the temporal succession of discontinuous or semi-continuous (metering) processes.
  • the Taylor Couette reactor according to the invention thus offers the advantage of a continuous quasi "one-stage" process so that a first reaction can take place in the section of the Taylor Couette reactor through which flow is first and in a second or further section in an axial flow direction after a further feed to the addition of educts, catalysts, initiators and / or other suitable process materials a second, third, etc. reaction.
  • Further examples of such conversions are: - polymer analogous reactions such as the esterification, amidation or urethanization of polymers containing pendant groups suitable for such reactions, - the preparation of olefinically unsaturated, electron beam or ultraviolet light curable materials, - the preparation of polyurethane resins and modified polyurethane resins such as acrylated polyurethanes, - the production of (poly) ureas or modified (poly) ureas, - the molecular weight of compounds which are terminated with isocyanate groups, or reactions which lead to the formation of mesophases, as described, for example, by Antonietti and Göltner in the article "superstructure of functional colloids: a chemistry in the nanometer range"
  • the process of the invention is used for the polymerization of olefinically unsaturated monomers in bulk, because in this case the particular advantages of the Taylor Couette reactor according to the invention particularly come to the fore.
  • the Taylor Couette reactor according to the invention is particularly preferably used for the preparation of chemically uniformly composed polymers and copolymers.
  • the faster polymerizing comonomer or the more rapidly polymerizing comonomers can be metered in via feeds arranged in the axial direction in succession, so that the comonomer ratio can be kept constant over the entire length of the reactor.
  • the Taylor Couette reactor is also used with particular advantage for the graft copolymerization.
  • the so-called backbone polymer can be prepared separately and metered via a separate feed or in admixture with at least one monomer in the Taylor Couette reactor according to the invention.
  • the backbone polymer can also be produced in a first section of the Taylor-Couette reactor according to the invention, after which at least one additional feed added in the axial direction is metered in via at least one monomer which forms the graft branches.
  • the monomer or the comonomers can then be grafted onto the backbone polymer in at least one further section of the Taylor-Couette reactor according to the invention.
  • comonomers can be added individually via one feed or as a mixture through one feed or several feeds. If at least two comonomers are added individually and in succession by at least two additions, it is even possible to produce graft branches which are block copolymers themselves, in a particularly simple and elegant manner. Of course, this concept described above can also serve to prepare block copolymers as such.
  • the production of core-shell latexes can be realized in a particularly simple and elegant manner with the aid of the Taylor-Couette reactor according to the invention.
  • the core is first prepared by polymerizing at least one monomer. Via at least one further feed, at least one further comonomer is metered in and the shell is grafted onto the core in at least one further section. In this way, several shells can be applied to the core.
  • the Taylor Couette reactor according to the invention has the particular advantage of a large specific cooling surface, which allows a particularly safe reaction.
  • Suitable monomers which are suitable for the process according to the invention are acyclic and cyclic, optionally functionalized monoolefins and diolefins, vinylaromatic compounds, vinyl ethers, vinyl esters, vinylamides, vinyl halides, allyl ethers and allyl esters, acrylic acid, and methacrylic acid and their esters, amides and nitriles and maleic acid, fumaric acid and itaconic acid and their esters, amides, imides and anhydrides.
  • Suitable monoolefins are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclobutene, cyclopentene, dicyclopentene and cyclohexene.
  • Suitable diolefins are butadiene, isoprene, cyclopentadiene and cyclohexadiene.
  • suitable vinylaromatic compounds are styrene, alpha-methylstyrene, 2-, 3- and 4-chloro, -methyl, -ethyl, -propyl- and -butyl- and tert-butylstyrene and -alpha-methylstyrene.
  • An example of a suitable vinyl compound or a functionalized olefin is vinylcyclohexanediol.
  • Suitable vinyl ethers are methyl, ethyl, propyl, butyl and pentyl vinyl ethers, allyl monopropoxylate and trimethylolpropane mono, di- and triallyl ethers.
  • Suitable vinyl esters are vinyl acetate and propionate and the vinyl esters of versatic acid and other quaternary acids.
  • Suitable vinylamides are N-methyl-, N, N-dimethyl-, N-ethyl-, N-propyl-, N-butyl-, N-amyl-, N-cyclopentyl- and N-cyclohexylvinylamide as well as N-vinylpyrrolidone and epsilon-caprolactam.
  • Suitable vinyl halides are vinyl fluoride and chloride.
  • vinylidene halides examples include vinylidene fluoride and chloride.
  • Suitable allyl ethers are methyl, ethyl, propyl, butyl, pentyl, phenyl and glycidyl monoallyl ethers.
  • Suitable allyl esters are allyl acetate and propionate.
  • esters of acrylic acid and methacrylic acid are methyl, ethyl, propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, 2-ethylhexyl, isodecyl, decyl, cyclohexyl , t-butylcyclohexyl, norbonyl, isobornyl, 2- and 3-hydroxypropyl, 4-hydroxybutyl, trimethylolpropane mono, pentaerythritol mono and
  • Glycidyl (meth) acrylate also suitable are the di-, tri- and tetra (meth) acrylates of ethylene glycol, di-, tri- and tetraethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, dibutylene glycol, glycerol, trimethylolpropane and pentaerythritol. However, they are not used alone, but always in minor amounts together with the monofunctional monomers.
  • Suitable amides of acrylic acid methacrylic acid are (meth) acrylamide and (meth) acrylic acid-N-methyl, -N 1 -N-dimethyl, -N-ethyl, -N-propyl, -N-butyl, - N-amyl, -N-cyclopentyl and -N-cyclohexylamide.
  • Suitable nitriles are acrylonitrile and methacrylonitrile.
  • esters, amides, imides and anhydrides of maleic acid, fumaric acid and itaconic acid are maleic, fumaric and itaconic acid dimethyl, diethyl, dipropyl and dibutyl esters, maleic, fumaric and itaconic diamides, maleic acid, fumaric acid and Itaconic acid N, N'-dimethyl, N, N, N, N'-N'-tetamethyl, N, N'-diethyl, N, N'-dipropyl, N, N-dibutyl, N, N-diamyl, -N, N'-dicyclopentyl and -NN-dicyclohexyldiamide, maleic, fumaric and itaconic acid imides and maleic, fumaric and itaconic acid N-methyl, N-ethyl, N-propyl, -N-butyl, -N-amyl, -N-N-
  • the monomers described above can be polymerized free-radically, cationically or anionically.
  • they are free-radically polymerized.
  • the customary and known inorganic radical initiators or initiators such as hydrogen peroxide or potassium peroxodisulfate or the customary and known organic radical initiators or initiators such as dialkyl peroxides, z.
  • Cumene hydroperoxide and tertiary butyl hydroperoxide Peresters, for example tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3, 5,5-trimethylhexanoate and tert-butyl per-2-ethylhexanoate; Bisazo compounds such as azobisisobutyronitrile; or C-C starters such as 2,3-dimethyl-2,3-diphenyl-butane or hexane.
  • Peresters for example tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3, 5,5-trimethylhexanoate and tert-butyl per-2-ethylhexanoate
  • Bisazo compounds such as azobisisobutyronitrile
  • C-C starters such as 2,3-dimethyl-2,3-diphenyl-butan
  • the monomer or monomers are polymerized in the annular gap-shaped reaction volume at least partially under the conditions of the Taylor flow.
  • the resulting liquid polymer is conveyed from the annular gap-shaped reaction volume into the outlet region and from there into the product outlet and discharged via the pressure-holding valve.
  • the conditions for the Taylor flow are met.
  • the reaction zone is not limited to the annular gap above the inlet, but preferably solvent is displaced in the reaction volume below the inlet.
  • the temperature of the reaction medium can vary widely in the process according to the invention and depends in particular on the monomer having the lowest decomposition temperature, the temperature at which the depolymerization is used, and the reactivity of the monomer (s) and initiators.
  • the polymerization is carried out at temperatures of 100 to 200, preferably 130 to 180 and in particular 150 to 180 C.
  • the polymerization can be carried out under pressure.
  • the pressure is preferably 1 to 100, preferably 1 to 25 and in particular 1 to 15 bar.
  • the throughput time can vary widely and depends in particular on the reactivity of the monomers and the size, in particular the length, of the Taylor-Couette reactor according to the invention.
  • the cycle time is 15 minutes to 2 hours, especially 20 minutes to 1 hour.
  • the conversion of the monomers is> 70 mol%.
  • conversions> 80, preferably> 90, particularly preferably> 95 and in particular> 96.5 mol% can be achieved without problems.
  • the kinematic viscosity v at least tenfold, in particular at least hundredfold.
  • acrylic monomers in mixtures with styrene and / or with methacrylates are higher conversions achieved than in the polymerization of only (methyl) acrylic monomers.
  • the molecular weight of the polymers produced by the process according to the invention can vary widely and is essentially limited only by the maximum kinematic viscosity v at which the TCR according to the invention can maintain the conditions of the Taylor flow.
  • the number average molecular weights of the polymers prepared in accordance with the invention are from 800 to 50. 000, preferably 1,000 to 25,000 and in particular 1,000 to 10,000 g / mol.
  • the nonuniformity of the molecular weight is ⁇ 5, in particular ⁇ 3.5.
  • the polymers prepared by the procedure according to the invention have further particular advantages. So they are ideal for all applications, as they are usually intended for polymers, such as the production of moldings and films. Above all, however, they come as components of coating materials, adhesives and sealants into consideration.
  • binders are used in particular as binders, because the coating materials, adhesives and sealants which contain or consist of the binders prepared in accordance with the method of the invention have particularly excellent performance properties.
  • these coating materials are physically drying or are cured thermally, with actinic light, in particular UV light, or by electron radiation. They are present as powder coatings, powder slurry paints, paints dissolved in organic media, aqueous paints or as essentially or completely free solvent and water-free, liquid paints (100% systems). In this case, they can contain color and / or effect pigments. They are used as architectural paints for indoor and Exterior, used as paint for furniture, doors, windows, glass sinkholes, coils, containers, white goods and other industrial applications, as automotive OEM or automotive refinish paints. When used in the automotive sector, they are suitable as electrodeposition paints, fillers, solid-color topcoats, basecoats and clearcoats.
  • the Taylor Couette reactor according to the invention and the process according to the invention are surprisingly suitable for all substance conversions in which the kinematic viscosity v of the reaction medium in the direction of flow changed greatly.
  • the Taylor-Couette reactor according to the invention and the process according to the invention allowed the free-radical, anionic and cationic polymerization of olefinically unsaturated monomers in bulk with conversions of> 70 mol%. It was even more surprising that conversions> 98 mol% could be achieved without any problems, without any fluctuations in the course of the temperature or formation of interfering deposits of the polymers in the Taylor Couette reactor according to the invention.
  • the molecular weight distribution of the polymers produced is significantly narrower than in polymerizations in which the reactants, as hitherto known by a
  • Valve can be metered into the base of the Taylor Couette reactor or through a valve in the upper third of the shell into the Taylor Couette reactor.
  • a narrower molecular weight distribution is synonymous with a greater uniformity of
  • the polymers produced in the process according to the invention also have a low viscosity due to the lower polydispersity. That's why it works Tempering reaction medium more uniformly along the entire reactor length, temperature fluctuations observed at high polydispersities and viscosities can thus be avoided. Accordingly, the inventive method surprisingly allows a more stable temperature and reaction than previous methods in Taylor-Couette reactors. In the process according to the invention, substantially homogeneous temperature profiles along the reactor length can be produced.
  • the Taylor Couette reactor according to the invention and the process according to the invention therefore make it possible to carry out the polymerization in bulk in a particularly reliable and stable manner, which is why the polymers could be prepared reliably and reproducibly.
  • FIG. 1 shows a preferred embodiment of the Taylor Couette reactor according to the invention.
  • the jacket (2) of the TCR (1) in Fig. 1 has the geometry of an organ pipe, i. the lower part (3) of the shell is conically shaped, with the smaller diameter at the bottom, and the upper part (4) is cylindrically shaped.
  • a cylindrical rotor (5) with a small cone tip rotates.
  • the heating of the reactor takes place via the jacket, wherein two zones (conical or cylindrical part) can be heated independently of each other.
  • To measure the reactor temperature several temperature sensors (6 a-e) are placed in the reactor.
  • the temperature sensors 6 a and 6 c are used to measure the temperature directly in the region of the lateral surfaces, while the temperature sensors 6 b, 6 d and 6 e measure the temperature of the reactor contents in the annular gap.
  • the TCR (1) is provided with three valves for the addition of educts and / or for sampling: a valve (7) in the reactor foot (10), a valve in the lower jacket area (8) and a valve in the upper jacket area (9).
  • the rotor (5) is mounted at the bottom of the reactor base (10). The discharge of the resulting polymer takes place via the reactor head (11).
  • the monomer mixtures were forcibly conveyed in all examples from a non-tempered storage vessel via piston stroke pumps and mixed shortly before entering the reactor in a micromixer with the promoted in the same manner initiator.
  • the reactor was filled with butylglycol as solvent before the beginning of the polymerization. The solvent is displaced from the TCR by the supplied reactants.
  • a monomer mixture was used which was composed of 55.0% n-butyl methacrylate, 3.3% isobutyl methacrylate, 40.5% hydroxyethyl methacrylate and 1.2% methacrylic acid.
  • the inner cylinder was stirred at 500 rpm in all examples.
  • the average residence time in the reactor was controlled by the volume flow of the reactants and was 30 minutes in all examples.
  • a reactor pressure of 2 bar was set by means of a pressure-holding valve in the outlet.
  • the lower jacket zone was tempered in all examples to 170 0 C, the upper to 160 0 C.
  • the temperatures were observed at various points of the reactor with PT100 probes.
  • the rod probes on the reactor head, in the valves in the upper and lower shell part and in the reactor bottom were each guided to the middle of the reactor gap.
  • Wall-mounted temperature sensors were also installed in the upper and lower shell halves. When dosing through the valves in the upper or lower shell half, there were no temperature sensors installed there. When metered into the reactor bottom by a valve, the temperature sensor was installed in an opposing valve.
  • the temperature values were stored every 5 seconds in a spreadsheet program. In the examples, the average temperatures of each probe during the second, third and fourth hour and the standard deviation during these intervals are respectively documented.
  • the conversion of the individual monomers was determined from the determination of the residual monomers by HPLC and the other volatile constituents, such as solvents, initiator decomposition products, via GC.
  • the molecular weight determination was carried out by GPC analysis with THF (+ 0.1% acetic acid) as eluent (1 ml / min) a styrene-divinylbenzene column combination (Waters HR4, HR3, HR2). Calibration was performed using polystyrene standards.
  • Example 1 The polymerization reaction was carried out in a TCR with the geometry of an organ pipe, as shown in FIG. The polymer produced was removed via the reactor head
  • the reactor had a total height of 364.5 mm (inside), the two heating zones each had a height of 164 mm.
  • the inside diameter was 76.4 mm at the bottom and 116 mm at half height.
  • a valve for supplying the educts is positioned at a height of 159.5 mm (43.7% of the total height).
  • a mixture of monomer mixture, initiator and chain transfer agent was metered through the valve in the conical part of the reactor. Based on the sum of the monomers, 5% of di-tert-amyl peroxide as initiator and 0.4% mercaptoethanol as chain transfer agent were added. After a test period of 4 hours, the acrylate has a solids content of 96.7% and a viscosity of 2.24 Pas.
  • the polymerizations were terminated by stopping the metered addition of the monomers and initiators while the jacket heating was on, and feeding butyl glycol through the reactor. After an amount of solvent was pumped through the reactor, which is twice the reactor volume, the production and the jacket heaters were turned off.
  • the polymerization reaction was carried out with the same parameters and in the same TCR as in Example 1 except that the reactants were metered in through a valve in the bottom of the reactor (*). After a test period of 4 hours, the acrylate had a solids content of 97.6% and a viscosity of 5.44 Pas. Total turnover was 97.3%.
  • the temperatures measured during the reaction as described above are shown in Table 2.
  • GPC data Mw: 11,400 g / mol, Mn: 3,100 g / mol, d: 3,7.
  • Table 2 Temperature profile Example 2 in [ 0 C]
  • the polymerization reaction was carried out in a conical TCR having a total height of 333 mm (inside).
  • the two heating zones each had a height of 164 mm.
  • the inside diameter of the reactor was 76.4 mm at the bottom, 116 mm at half height and 146 mm at the top.
  • the rotor was cylindrical with a diameter of 56 mm, had a height of 360 mm, was closed with a 28 mm high cone tip, which protruded into the reactor head, which has the shape of an inverted funnel, and was mounted in the reactor bottom.
  • a valve for supplying the educts is positioned at a height of 299.5 mm (47.9% of the total height).
  • Example 5 (Comparative Example 3):
  • the polymerizations ran stable and therefore allow it to perform a continuous mass polymerization over a longer period of time.
  • dosing into another region of the reactor shell, as in Example 5 no stable temperature conditions in the reactor could be achieved and the reaction had to be stopped early.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention a pour objet un réacteur Taylor-Couette pour l'exécution de polymérisations en masse, ledit réacteur comprenant une paroi extérieure et un rotor monté concentriquement à l'intérieur, un fond de réacteur et un couvercle de réacteur définissant le volume de réacteur en forme d'espace annulaire, au moins un dispositif de dosage de produits de départ, et un dispositif de décharge de produits. Le dispositif de dosage de produits de départ est disposé au-dessus de la base du réacteur, dans les deux tiers inférieurs de l'enveloppe du réacteur; durant la polymérisation, il se produit une modification de la viscosité cinématique v du milieu réactionnel. L'invention a également pour objet un procédé de polymérisation en continu de monomères en masse dans le réacteur Taylor-Couette précité, procédé dans lequel une modification de la viscosité cinématique v du milieu réactionnel se produit lors de la polymérisation.
PCT/EP2008/003489 2007-05-04 2008-04-30 Procédé de polymérisation en continu pour la production de polymères à étroite distribution de masse molaire, et réacteur taylor-couette pour la mise en oeuvre de ce procédé Ceased WO2008135211A1 (fr)

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DE102007021012A DE102007021012A1 (de) 2007-05-04 2007-05-04 Kontinuierliches Polymerisationsverfahren zur Erzeugung von Polymeren mit enger Molmassenverteilung und Taylor-Couette-Reaktor für seine Durchführung

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
KR101084226B1 (ko) 2009-04-10 2011-11-17 경희대학교 산학협력단 다중 쿠에트-테일러 와류 반응장치
US8097219B2 (en) 2008-05-28 2012-01-17 Ut-Battelle Llc Integrated reactor and centrifugal separator and uses thereof
JP5765345B2 (ja) * 2010-10-26 2015-08-19 株式会社ニコン 検査装置、検査方法、露光方法、および半導体デバイスの製造方法

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CN115551626A (zh) * 2020-04-07 2022-12-30 V·E·麦克卢尔 用于聚合物的液相催化热解的反应容器

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EP0498583A1 (fr) * 1991-02-05 1992-08-12 Nippon Paint Co., Ltd. Méthode de polymérisation en continue et appareil
EP0677326A1 (fr) * 1992-12-28 1995-10-18 Kao Corporation Procede et appareil permettant de produire de fines particules de ceramique
DE19828742A1 (de) * 1998-06-27 1999-12-30 Basf Coatings Ag Taylorreaktor für Stoffumwandlungen, bei deren Verlauf einer Änderung der Viskosität v des Reaktionsmediums eintritt
WO2002076609A1 (fr) * 2001-03-22 2002-10-03 Ceramic Fuel Cells Limited Reacteur en phase liquide
WO2004039491A1 (fr) * 2002-10-30 2004-05-13 Basf Coatings Ag Reacteur de taylor pour transformations de matieres

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DE19960389B4 (de) 1999-12-15 2009-01-15 Basf Coatings Ag Verfahren zur Polymerisation olefinisch ungesättigter Monomere mittels eines Taylorreaktors
DE10149015B4 (de) 2001-10-04 2005-04-14 Basf Coatings Ag Verfahren zur kontinuierlichen Polymerisation in Masse und Taylorreaktor für seine Durchführung

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Publication number Priority date Publication date Assignee Title
EP0498583A1 (fr) * 1991-02-05 1992-08-12 Nippon Paint Co., Ltd. Méthode de polymérisation en continue et appareil
EP0677326A1 (fr) * 1992-12-28 1995-10-18 Kao Corporation Procede et appareil permettant de produire de fines particules de ceramique
DE19828742A1 (de) * 1998-06-27 1999-12-30 Basf Coatings Ag Taylorreaktor für Stoffumwandlungen, bei deren Verlauf einer Änderung der Viskosität v des Reaktionsmediums eintritt
WO2002076609A1 (fr) * 2001-03-22 2002-10-03 Ceramic Fuel Cells Limited Reacteur en phase liquide
WO2004039491A1 (fr) * 2002-10-30 2004-05-13 Basf Coatings Ag Reacteur de taylor pour transformations de matieres

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8097219B2 (en) 2008-05-28 2012-01-17 Ut-Battelle Llc Integrated reactor and centrifugal separator and uses thereof
KR101084226B1 (ko) 2009-04-10 2011-11-17 경희대학교 산학협력단 다중 쿠에트-테일러 와류 반응장치
JP5765345B2 (ja) * 2010-10-26 2015-08-19 株式会社ニコン 検査装置、検査方法、露光方法、および半導体デバイスの製造方法

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