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EP1432509A1 - Procede de polymerisation continue en masse et reacteur de taylor permettant de mettre en oeuvre ce procede - Google Patents

Procede de polymerisation continue en masse et reacteur de taylor permettant de mettre en oeuvre ce procede

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Publication number
EP1432509A1
EP1432509A1 EP02777274A EP02777274A EP1432509A1 EP 1432509 A1 EP1432509 A1 EP 1432509A1 EP 02777274 A EP02777274 A EP 02777274A EP 02777274 A EP02777274 A EP 02777274A EP 1432509 A1 EP1432509 A1 EP 1432509A1
Authority
EP
European Patent Office
Prior art keywords
reactor
taylor
annular gap
reaction volume
rotor
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Withdrawn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
EP02777274A
Other languages
German (de)
English (en)
Inventor
Werner-Alfons Jung
Heinz-Peter Rink
Heinrich Meinecke
Josef Krull
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.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
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 BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1432509A1 publication Critical patent/EP1432509A1/fr
Withdrawn legal-status Critical Current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
    • B01F27/50—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
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/40—Mounting or supporting mixing devices or receptacles; Clamping or holding arrangements therefor
    • B01F35/41—Mounting or supporting stirrer shafts or stirrer units on receptacles
    • B01F35/411—Mounting or supporting stirrer shafts or stirrer units on receptacles by supporting only one extremity of the shaft
    • B01F35/4112—Mounting or supporting stirrer shafts or stirrer units on receptacles by supporting only one extremity of the shaft at the bottom of the receptacle, e.g. by studs
    • 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
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation 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
    • 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
    • B01J2219/182—Details relating to the spatial orientation of the reactor horizontal
    • 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
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/187—Details relating to the spatial orientation of the reactor inclined at an angle to the horizontal or to the vertical plane
    • 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

Definitions

  • the present invention relates to a new process for the continuous production of (co) polymers, block copolymers and graft copolymers of at least one olefinically unsaturated monomer by the (co) polymerization block copolymerization and graft copolymerization in bulk.
  • the present invention also relates to a new Taylor reactor for carrying out this process.
  • polymerization the (co) polymerization, block mixed polymerization and graft mixed polymerization is collectively referred to as "polymerization”. Accordingly, the (co) polymers, the block copolymers and graft copolymers are collectively referred to as "polymers”.
  • olefinically unsaturated monomers are polymerized radically, anionically or cationically in the presence of small amounts of organic solvents, ie up to 25% by weight of the reaction mixture, or in their absence.
  • the kinematic viscosity v changes in the course of the reaction by at least a factor of 10, so that the handling of the polymers becomes difficult. It is therefore often necessary to carry out the polymerization only up to a comparatively low conversion, for example a maximum of 70 mol%, so that the reaction mixtures of polymers and monomers can still be thoroughly mixed and discharged from the reactors.
  • German patent application DE 198 28 742 A1 proposes to carry out the polymerization of olefinically unsaturated monomers in bulk in a Taylor reactor under the conditions of the Taylor vortex flow.
  • Taylor reactors which are used to convert substances under the conditions of the Taylor vortex flow, have long been known. They essentially consist of two coaxial, concentrically arranged
  • the reaction space is the volume that is formed by the gap between the cylinders.
  • ⁇ of the inner cylinder With increasing angular velocity ⁇ of the inner cylinder, a number of different flow forms occur, which are characterized by a dimensionless characteristic number, the so-called Taylor number Ta.
  • the Taylor number is in addition to
  • the angular velocity of the stirrer or rotor also depends on the kinematic viscosity v of the fluid in the gap and on the geometric parameters, the outer radius of the inner cylinder n, the inner radius of the outer cylinder r a and the gap width d
  • the laminar Couette flow a simple shear flow, forms. If the speed of rotation of the inner cylinder is further increased, opposite rotating (counter-rotating) vortices with axes along the circumferential direction occur alternately above a critical value. These so-called Taylor vortices are rotationally symmetrical, 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 pair of vertebrae or a vertebral cell.
  • This behavior is based on the fact that when the inner cylinder rotates with the outer cylinder at rest, the fluid particles near the inner cylinder are subjected to a stronger centrifugal force than those which are further away from the inner cylinder. This difference in the acting centrifugal forces pushes the fluid particles from the inner to the outer cylinder. The centrifugal force counteracts the viscosity force, since the friction has to be overcome when the fluid particles move. If the rotational speed increases, then the centrifugal force also increases. The Taylor vortices arise when the centrifugal force becomes greater than the stabilizing viscosity force.
  • Taylor reactor If the Taylor reactor is provided with an inlet and outlet and operated continuously, a Taylor vortex flow results with a low axial flow.
  • Each pair of vertebrae moves through the gap, with only a small mass exchange between adjacent pairs of vertebrae.
  • the mixing within such vortex pairs is very high, whereas the axial mixing beyond the pair boundaries is only very low.
  • a pair of vertebrae can therefore be mixed well.
  • Stirred kettles are considered.
  • the flow system thus behaves like an ideal flow tube in that the vortex pairs move through the gap like ideal stirred tanks with a constant dwell time.
  • the annular-shaped reactor volume is defined by the concentrically arranged rotor, the reactor base and the reactor cover.
  • the product outlet must be arranged on the side of the Taylor reactor or in the reactor cover and cannot be designed without edges.
  • a trouble-free product outlet can only be realized with difficulty because edges and dead volumes cause polymer deposits.
  • the Taylor flow still present in the highly viscous reaction medium can easily break down in this area, so that the intermixing of monomers and polymers deteriorates and the tendency to deposit on edges and in dead volumes is increased.
  • the drive shaft for the rotor is located in the reactor cover, ie the rotor is driven in the area in which the kinematic viscosity v is highest, which exposes the seals and connections to a particularly high mechanical load.
  • the known Taylor reactor on the one hand is not yet able to solve all safety and process engineering problems that occur in mass polymerization, and on the other hand it is not yet possible to increase the conversion of the monomers so much that extensive freedom from monomers and a narrow molecular weight distribution and non-uniformity in the molecular weight of the polymers is achieved.
  • Taylor reactor is known in which the rotor is rotatably mounted in the inlet area of the starting materials.
  • the rotor is not supported at its other end, but essentially ends in front of the outlet area, which at its widest point has the same diameter as the outer reactor wall.
  • the outlet area narrows in a funnel shape to form an outlet pipe.
  • the well-known Taylor reactor is used to mix liquids of different viscosities and electrical conductivity. It can also be used to react polyisocyanates with polyols. The extent to which it can be used in bulk for the polymerization of olefinically unsaturated monomers is not apparent from the American patent.
  • the drive shaft is passed through the reactor floor and the connection to the rotor in the inlet area of the educts.
  • the rotor in the inlet area of the educts does not have the diameter that would be necessary to set the Taylor flow in this area.
  • the ring-shaped reaction volume does not widen in the direction of flow. While in the U.S. patent at column 10, lines 29-33, it is stated that the concentric portions may have configurations other than cylindrical, for example essentially spherical or conical, which configurations are particularly advantageous for bulk polymerization, but will not taught.
  • the object of the present invention is to provide a new Taylor reactor which no longer has the disadvantages of the prior art, but which is particularly well suited for the polymerization of olefinically unsaturated monomers in bulk, in which the kinematic viscosity v in the reaction medium changes in the course the response at least tenfold.
  • the new Taylor reactor should easily allow the production of polymers with a conversion> 70 mol%, without the formation of gas bubbles and / or polymer deposits in the annular reaction volume and / or in the outlet area.
  • the new Taylor reactor should have a particularly long service life and service life.
  • Rotor (4) has at its end (4.1) the * largest diameter or the same diameter as at its end (4.2) which is not supported, and 1.1.3 a reactor base (5) with a seal (6) for the
  • the 4.1 opens at its largest diameter towards the outlet area (9) and
  • the new Taylor reactor is referred to below as the “Taylor reactor according to the invention”.
  • Graft copolymers by radical, anionic or cationic (co) polymerization, block copolymerization or graft copolymerization (polymerization) of at least one olefinically unsaturated monomer found in bulk in a Taylor reactor, in which
  • the inlet region (8 ) is located in the narrowest area of the ring-shaped reaction volume (2) above the reactor floor (5), and (II) in the ring-shaped reaction volume (2) at least partially (co) polymerized, block-mixed polymerized or graft-polymerized under the conditions of the Taylor flow (polymers 4), the ring-shaped reaction volume (2)
  • Pressure maintaining valve (11) discharges.
  • the new process for the continuous production of (co) polymers, block copolymers and graft copolymers by the radical, anionic or cationic polymerization of at least one olefinically unsaturated monomer in bulk in a Taylor reactor is referred to as the “process according to the invention”.
  • the Taylor reactor according to the invention due to its advantageous construction, in particular its advantageous configuration in the inlet region (8), in the outlet region (9) and in the product outlet (10) as well as the seal (6) of the drive shaft (7) of the rotor (4) in the area of the annular gap-shaped reaction volume (2), in which the reaction medium had the lowest kinematic viscosity v, had a particularly long operating and service life.
  • the Taylor reactor according to the invention and the method according to the invention allowed a particularly reliable reaction control of the polymerization in bulk, which is why the polymers could be produced very safely, reliably and reproducibly. Due to the very low monomer content of the polymers, they could be used for a wide variety of purposes without further purification, without this Safety-related, procedural, toxicological and ecological problems and unpleasant odors occurred.
  • the Taylor reactor according to the invention comprises a reaction volume in the form of an annular gap, which preferably has a circular circumference.
  • the annular gap-shaped reaction volume is defined by or is formed by an outer reactor wall, a rotor arranged concentrically therein and a reactor base with a seal for the drive shaft of the rotor.
  • the outer reactor wall and the rotor have a circular circumference over the entire length of the reaction volume, as seen in cross section.
  • the term "circular” is to be understood as strictly circular, oval, elliptical or polygonal with rounded corners.
  • a strictly circular circumference is advantageous for reasons of simplicity of manufacture, simple construction and significantly easier maintenance of constant conditions over the entire length of the annular gap-shaped reaction volume.
  • 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 can have a relief-like radial and / or axial, preferably radial, surface profile, as described, for example, in US Pat. No. 4,174,907 A or British Pat. No. 1,358,157 becomes. If a radial surface profile is present, it is advantageously approximately or exactly dimensioned like the Taylor swirl 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 without any profile, in order to avoid blind spots in which gas bubbles or starting materials, process materials and products could settle.
  • the Taylor reactor according to the invention is - seen in the longitudinal direction - vertically, horizontally or in a position between these two directions. Vertical storage is advantageous according to the invention. If the Taylor reactor according to the invention is not mounted horizontally, the reaction medium can flow from bottom to top against the force of gravity or from top to bottom with the force of gravity. According to the invention, it is advantageous if the reaction medium is moved against gravity.
  • the annular-shaped reaction volume widens continuously or discontinuously, in particular continuously, in the flow direction according to suitable mathematical functions.
  • suitable mathematical functions are straight lines, at least two straight lines that meet at an obtuse angle, parabolas, hyperbolas, e-functions or combinations of these functions that merge continuously or discontinuously, in particular continuously.
  • the mathematical functions are straight lines, i.e. that is, the ring-shaped reaction volume widens conically in the direction of flow. The extent of the broadening depends on the expected increase in the viscosity of the reaction medium in the direction of flow and can be estimated by a person skilled in the art using Taylor formula I and / or determined using simple preliminary tests.
  • the outer reactor wall can be cylindrical and the rotor be conical, the rotor having the largest diameter at its supported end.
  • the outer reactor wall can be shaped conically and the rotor can be cylindrical, ie its cross-section is constant over the entire rotor length. According to the invention, it is advantageous if the outer reactor wall is conical and the rotor is cylindrical.
  • the rotor is rotatably mounted in the reactor floor. He and his drive shaft reaching outward to a drive device are sealed with a seal.
  • the rotor is not supported at its other end. The free end of the rotor can be planar, rounded or conical.
  • the seal is preferably a mechanical seal.
  • the drive device can be an infinitely variable electric motor or a pneumatically operated motor which is connected to the drive shaft via a gear.
  • the performance of the motor depends on the maximum kinematic viscosity v of the reaction medium.
  • the connection to the drive shaft can be made using a magnetic coupling.
  • the inlet for the starting materials, in particular for the olefinically unsaturated monomers, as well as for suitable process materials, such as catalysts and initiators, above the reactor base.
  • the inlet can be arranged on the side or go through the reactor floor.
  • the starting materials can be fed to the feed using customary and known methods and devices, such as metering pumps.
  • the devices can be equipped with the aid of customary 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, can be connected upstream of the feed.
  • an outlet area free of dead volumes is provided above the non-supported end of the rotor and the annular gap-shaped reaction volume.
  • the outlet area widens in the flow direction beyond the annular gap-shaped reaction volume and then tapers towards a product flow.
  • the broadening can be described by the mathematical functions listed above, with straight lines being preferred. Accordingly, the outlet area preferably widens conically.
  • the taper is preferably conical.
  • the outlet area and the product outlet are defined by the outer reactor wall.
  • the product flow opens at its largest diameter
  • Outlet area and tapers in the other direction Preferably, the product flow is strictly circular
  • the opening of the product drain can be concentric above the be arranged at the top end of the rotor or laterally offset from it.
  • the taper can be described by the mathematical functions listed above, with straight lines being preferred. Accordingly, the product flow preferably tapers conically. After the tapering, the product flow preferably changes into a cylinder-shaped tube.
  • a pressure holding valve which builds up and regulates the pressure in the Taylor reactor according to the invention and through which the reaction products, in particular the polymers, are continuously discharged.
  • the pressure holding valve can be followed by collecting and storage containers, mixing devices, such as devices for melt emulsification, cooling belts for producing granulate or other reactors.
  • 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 in countercurrent. Furthermore, the invention
  • Taylor reactor conventional and known mechanical, hydraulic, optical and electronic measuring and control devices, such as temperature sensors,
  • the Taylor reactor according to the invention is preferably designed to be pressure-tight so that the reaction medium can preferably be under a pressure of 1 to 100 bar.
  • the Taylor reactor according to the invention can consist of a wide variety of materials, as long as these are not attacked by the starting materials and the reaction products and can withstand higher pressures. Metals, preferably steel, in particular stainless steel, are preferably used.
  • the Taylor reactor according to the invention can be used for a wide variety of purposes. 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.
  • a very particular advantage of the Taylor reactor according to the invention is that the local successive sequence in the Taylor reactor can be linked to the temporal successive sequence of discontinuous or semi-continuous (metering) processes.
  • the Taylor 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 reactor through which flow first and in a second or further section - seen in the axial direction of flow - after a further feed for metering in educts , Catalysts, initiators and / or other suitable process materials a second, third, etc. reaction.
  • material conversions that can be carried out in the Taylor reactor according to the invention with particular advantages are the build-up or breakdown of oligomeric and high-molecular substances, such as the polymerization of monomers in bulk, solution, emulsion or suspension or by precipitation polymerization.
  • Other examples of such material conversions are
  • polymer-analogous reactions such as the esterification, amidation or urethanization of polymers which contain side groups which are suitable for such reactions, the production of olefinically unsaturated materials curable with electron beams or ultraviolet light, the production of polyurethane resins and modified polyurethane resins such as acrylated polyurethanes, the production of (poly) ureas or modified
  • Isocyanate groups are terminated, or reactions which lead to the formation of mesosphases, as described, for example, by Antonietti and Göltner in the article
  • the process according to the invention is used with very particular advantage for the polymerization of olefinically unsaturated monomers in bulk, because the particular advantages of the Taylor reactor according to the invention are particularly open.
  • the Taylor reactor according to the invention is particularly preferred for the production of chemically uniformly composed polymers r
  • the faster polymerizing comonomer or the faster polymerizing comonomers can be metered in via feeds arranged one behind the other in the axial direction, so that the comonomer ratio can be kept constant over the entire length of the reactor.
  • the Taylor reactor is also used with particular advantage for the graft copolymerization.
  • the so-called backbone polymer can be prepared separately and metered into the Taylor reactor according to the invention via a separate feed or in a mixture with at least one monomer.
  • the backbone polymer can also be produced in a first section of the Taylor reactor according to the invention, after which at least one monomer which forms the graft branches is metered in via at least one further feed which is offset in the axial direction.
  • the monomer or the comonomers can then be grafted onto the backbone polymer in at least one further section of the Taylor reactor according to the invention. If several comonomers are used, they can be metered in individually via one feed or as a mixture through one feed or several feeds. If at least two comonomers are metered in individually and in succession by at least two feeds, graft branches, which are block copolymers in themselves, can even be produced in a particularly simple and elegant manner.
  • the manufacture of core-shell latices can be realized particularly simply and elegantly with the aid of the Taylor reactor according to the invention.
  • the core is first produced by polymerizing at least one monomer.
  • At least one further comonomer is metered in via at least one further feed and the shell is polymerized onto the core in at least one further section. In this way, several shells can be applied to the core.
  • Polymer dispersions can also be produced with the aid of the Taylor reactor according to the invention.
  • at least one monomer in the homogeneous phase, in particular in solution is polymerized in a first section of the Taylor reactor (co) according to the invention, after which a precipitant is metered in via at least one further device (6), resulting in the polymer dispersions.
  • the Taylor reactor according to the invention has the particular advantage of a large specific cooling surface, which allows a particularly reliable reaction to be carried out.
  • the Taylor reactor according to the invention is very particularly preferred for the continuous production of (co) polymers, block copolymers and graft copolymers by free radical, anionic or cationic, in particular free radical, (co) polymerization, block mixed polymerisation or
  • Graft copolymerization of at least one olefinically unsaturated monomer used in bulk by the process according to the invention.
  • suitable monomers which are suitable for the process according to the invention are acyclic and cyclic, optionally functionalized monooiefins and diolefins, vinylaromatic compounds, vinyl ethers, vinyl esters, vinyl amides, 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 monooiefins are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclobutene, cyclopentene, dicyclopentene and cyclohexene.
  • diolefins examples include butadiene, isoprene, cyclopentadiene and cyclohexadiene.
  • vinyl aromatic compounds examples include styrene, alpha-methyl styrene, 2-, 3- and 4-chloro, methyl, ethyl, propyl and butyl and tert-butyl styrene and alpha-methyl styrene.
  • An example of a suitable vinyl compound or a functionalized olefin is vinylcyclohexanediol.
  • Suitable vinyl ethers are methyl, ethyl, propyl, butyl and pentyl vinyl ether, allyl monopropoxylate and trimethylolpropane mono, di and triallyl ether.
  • 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-ethyl-hexyl, isodecyl, decyl and cyclohexyl , t-Butylcyclohexyl-, norbonyl-, isobomyl-, 2- and 3-hydroxypropyl-, 4-hydroxybutyl trimethylolpropane mono-, pentaerythritol mono- and glycidyl (meth) acrylate.
  • Trimethylolpropane and pentaerythritol into consideration. 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) acrylic acid amide and (meth) acrylic acid-N-methyl-, -N, N-dimethyl-, - N-ethyl-, -N-propyl-, -N-butyl-, -N -amyl-, -N-cyclopentyl- and -N-cyclohexylamide.
  • nitriles are acrylonitrile and methacrylonitrile.
  • suitable esters, amides, imides and anhydrides of maleic acid, fumaric acid and itaconic acid are maleic acid, fumaric acid and itaconic acid dimethyl, diethyl, dipropyl and dibutyl esters, maleic acid, fumaric acid and itaconic acid diamide, maleic acid and fumaric acid itaconic acid-N, N 'dimethyl, N, N, N', N etamethyl-, N, N 'diethyl, N, N' - dipropyl, N, N 'dibutyl, - N, N- ' diamyl-, -N, N ' -dicyclopentyl- and -N, N- 'dicyclohexyldiamide, maleic acid, fumaric acid and itaconic acid imide and maleic acid, fumaric acid and itaconic acid
  • the monomers described above can be polymerized radically, cationically or anionically. They are advantageously polymerized by free radicals.
  • 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, e.g. Di-tert-butyl peroxide, di-tert. -amyl peroxide and dicumyl peroxide; Hydroperoxides, e.g. Cumene hydroperoxide and tert-butyl hydroperoxide; Perester, e.g.
  • 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-diphenylbutane or hexane can be used.
  • styrene can also be used, which initiates polymerization thermally even without a radical initiator.
  • Dosed inlet area of the Taylor reactor according to the invention Preferably at least one of those described above Radical initiators or initiators are preferably metered in together with at least one monomer via a further side feed.
  • the monomer or monomers are polymerized in the annular reaction volume at least partially under the conditions of the Taylor flow.
  • the resulting liquid polymer is conveyed from the reaction volume in the form of an annular gap into the outlet area and from there into the product outlet and discharged via the pressure control valve.
  • the conditions for the Taylor flow are preferably fulfilled in part of the annular reaction volume or in the entire annular reaction volume, in particular in the entire annular reaction volume.
  • the temperature of the reaction medium can vary widely in the process according to the invention and depends in particular on the monomer with the lowest decomposition temperature, on the temperature at which the depolymerization is used and on the reactivity of the monomer or monomers and the initiators.
  • the polymerization is preferably carried out at temperatures from 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 offender reactor according to the invention.
  • the throughput time is preferably 15 minutes to 2 hours, in particular 20 minutes to 1 hour.
  • the conversion of the monomers is> 70 mol%.
  • conversions> 80, preferably> 90, particularly preferably> 95, very particularly preferably> 98 and in particular> 98.5 mol% can be achieved without problems.
  • the kinematic viscosity v can increase at least tenfold, in particular at least a hundredfold.
  • the molecular weight of the polymers prepared using the process according to the invention can vary widely and is essentially limited only by the maximum kinematic viscosity v at which the Taylor reactor according to the invention can maintain the conditions of the Taylor flow.
  • the number average molecular weights of the polymers prepared in the process according to the invention are preferably 800 to 50,000, preferably 1,000 to 25,000 and in particular 1,000 to 10,000 Daltons.
  • the non-uniformity of the molecular weight is preferably ⁇ 10, in particular ⁇ 8.
  • FIG. 1 shows a preferred embodiment of the Taylor reactor according to the invention in a schematic representation.
  • the process according to the invention is particularly economical because the subsequent separation of converted monomers and their recycling into the reaction medium can be dispensed with. This also eliminates all safety-related, procedural, toxicological and ecological problems and odor nuisances that are associated with a high monomer content.
  • the process according to the invention can be operated for a particularly long time without the formation of bubbles and / or addition of polymers. This results in particularly high yields of polymers.
  • the polymers produced in the procedure according to the invention have further particular advantages. They are ideal for all applications, such as those normally provided for polymers, such as the production of molded parts and films. Above all, however, they come into consideration as components of coating materials, adhesives and sealing compounds. They are used in particular as binders because the coating materials, adhesives and sealants which contain or consist of the binders produced in the process according to the invention have particularly excellent application properties.
  • these coating materials are physically drying or are cured thermally, with actinic light, in particular UV light, or by electron radiation. They are available as powder coatings, powder slurry coatings, coatings dissolved in organic media, aqueous coatings or as essentially or completely solvent and water-free, liquid coatings (100% systems). They can contain coloring and / or effect pigments. They are used as architectural paints for indoor and outdoor use, as paints for furniture, doors, windows, hollow glass bodies, coils, containers, white goods and other industrial applications, as automotive paints for original equipment (OEM) or as car refinish paints. When used in the automotive sector, they can be used as electrocoating paints, fillers, solid-color topcoats, basecoats and clearcoats.
  • OEM original equipment
  • the Taylor reactor (1) according to the invention from FIG. 1 was used to produce the copolymer.
  • the Taylor reactor was operated in a vertical position, the direction of flow being counter to gravity. All parts of the plant were heated by a double jacket. This was divided, the conical part of the outer reactor wall (3) having two heating zones and the other parts of the plant each having only one heating zone.
  • the temperature of the Taylor reactor (1) was carried out using two thermostats. The first thermostat was connected to the lower heating zone of the outer reactor wall (3) in the area of the annular reaction volume (2). The remaining heating zones were tempered using the second thermostat. The temperatures of the reaction medium or of the copolymer in the outlet area (9) were regulated by manually adjusting the thermostat temperatures. A temperature of 160 ° C. was set.
  • the Taylor reactor according to the invention had an annular gap-shaped reaction volume (2) of 1,666 ml.
  • the volume of the outlet area (9) was 287 ml.
  • the speed of the rotor (4) was 300 rpm.
  • the polymerization was carried out at 160 ° C. and 2 bar.
  • the residence time or throughput time was 35.3 minutes, the test duration was 4 hours.
  • the Taylor reactor (1) was completely filled with the organic solvent Shellsol ® in order to build up the pressure required for the polymerization and to set the polymerization temperature via the pressure maintaining valve (11).
  • the rotor (4) was put into operation before the feeds were metered in.
  • the organic solvent was then displaced through the monomer and initiator feeds. The flow of copolymer was discarded.
  • a monomer mixture consisting of 2,881.5 g styrene, 3,006.8 g methyl methacrylate and 4,510.2 g hydroxypropyl methacrylate with a mass flow of 43.33 g / min was mixed with a mixture consisting of 43.8 g di tert-butyl peroxide (DTBP), 20.3 g tert-butyl peroxyethyl hexanoate (TBPEH), 587.6 dicumyl peroxide (DCP) and 2,129.8 g tert-butylcyclohexyl acrylate, mixed with a mass flow of 12.02 g / min.
  • DTBP di tert-butyl peroxide
  • TPEH tert-butyl peroxyethyl hexanoate
  • DCP dicumyl peroxide
  • 2,129.8 g tert-butylcyclohexyl acrylate mixed with a mass flow of 12.
  • the resulting mixture was metered into the inlet area (8) with a mass flow of 55.35 g / min via a side inlet (8.1).
  • the mixing and metering took place via computer-controlled piston diaphragm pumps.
  • the pressure was regulated manually at the pressure maintaining valve (11).
  • the polymer resulting after the flow was continuously discharged via the pressure-maintaining valve (11) and via an isolated one Pipe passed into a collecting container.
  • the essential properties of the polymer were determined at regular intervals (1, 2 and 3 hours).
  • the polymer had a constant, constant profile of properties during the continuous bulk polymerization. Its number average molecular weight was 2,827 daltons and its mass average molecular weight was 16,089 daltons. The non-uniformity of the molecular weight was therefore 5.7.
  • the conversion, determined using gas chromatography, was 99.1 mol%.
  • the melt viscosity of the polymer at 160 ° C was 4.24 Pas and was thus about a factor of 2x10 3 higher than the viscosity of the reaction medium in the inlet area (8).
  • the polymer was outstandingly suitable for the production of coating materials, adhesives and sealants.

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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)
  • Polymerisation Methods In General (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

La présente invention concerne un réacteur de Taylor (1), représenté en figure 1, qui comprend 1. un espace de réaction (2) sous forme d'espace annulaire, qui s'élargit dans la direction d'écoulement et qui est défini par une paroi de réacteur externe (3), par un rotor (4), monté rotatif au fond du réacteur, à une extrémité (4.1), et libre à l'autre extrémité (4.2), et par un fond de réacteur (5) comprenant un joint d'étanchéité (6) pour l'arbre d'entraînement (7), 2. une zone d'entrée (8), située au-dessus du fond du réacteur (5) et comprenant au moins une conduite d'alimentation latérale (8.1) et/ou au moins une conduite d'alimentation (8.1) à travers le fond du réacteur (5), destinées aux éduits et/ou aux matières de processus, 3. une zone d'évacuation (9), située au-dessus de l'espace de réaction (2) sous forme d'espace annulaire, qui s'élargit sur l'espace de réaction (2) sous forme d'espace annulaire, dans la direction d'écoulement, puis qui s'amincit en direction d'une évacuation de produit (10), 4. une évacuation de produit (10), qui s'ouvre, au niveau de son diamètre supérieur, sur la zone d'évacuation (9) et qui s'amincit dans l'autre sens et 5. une soupape de maintien de pression (11). La présente invention concerne également l'utilisation de ce réacteur de Taylor pour une polymérisation continue en masse.
EP02777274A 2001-10-04 2002-10-02 Procede de polymerisation continue en masse et reacteur de taylor permettant de mettre en oeuvre ce procede Withdrawn EP1432509A1 (fr)

Applications Claiming Priority (3)

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DE10149015A DE10149015B4 (de) 2001-10-04 2001-10-04 Verfahren zur kontinuierlichen Polymerisation in Masse und Taylorreaktor für seine Durchführung
DE10149015 2001-10-04
PCT/EP2002/011033 WO2003031056A1 (fr) 2001-10-04 2002-10-02 Procede de polymerisation continue en masse et reacteur de taylor permettant de mettre en oeuvre ce procede

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DE102005026049A1 (de) * 2005-06-03 2006-12-07 Sca Schucker Gmbh & Co. Kg Verfahren zum Auftragen einer pastösen Masse
CN101130585B (zh) * 2006-08-25 2010-11-10 北京化工大学 一种丁基橡胶的制备方法
DE102007021012A1 (de) 2007-05-04 2008-11-06 Basf Coatings Ag Kontinuierliches Polymerisationsverfahren zur Erzeugung von Polymeren mit enger Molmassenverteilung und Taylor-Couette-Reaktor für seine Durchführung
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DE10149015A1 (de) 2003-04-24
US7651670B2 (en) 2010-01-26
DE10149015B4 (de) 2005-04-14
US20050159565A1 (en) 2005-07-21

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