WO2015101404A1 - Procédé de réalisation en continu d'une polymérisation - Google Patents

Procédé de réalisation en continu d'une polymérisation Download PDF

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Publication number
WO2015101404A1
WO2015101404A1 PCT/EP2014/001463 EP2014001463W WO2015101404A1 WO 2015101404 A1 WO2015101404 A1 WO 2015101404A1 EP 2014001463 W EP2014001463 W EP 2014001463W WO 2015101404 A1 WO2015101404 A1 WO 2015101404A1
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WO
WIPO (PCT)
Prior art keywords
monomer
polymerization
water
polymer
reactor
Prior art date
Application number
PCT/EP2014/001463
Other languages
German (de)
English (en)
Inventor
Roland Kunkel
Pierre-Alain Fleury
Original Assignee
List Holding Ag
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 List Holding Ag filed Critical List Holding Ag
Publication of WO2015101404A1 publication Critical patent/WO2015101404A1/fr

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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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/42—Nitriles
    • C08F20/44—Acrylonitrile

Definitions

  • the invention relates to a method for continuously carrying out a polymerization according to the preambles of claims 1 and 6.
  • Such methods are e.g. kneading in so-called mixing. They serve very diverse purposes.
  • evaporation with solvent recovery which is carried out batchwise or continuously and often under vacuum.
  • distillation residues and in particular toluene diisocyanates are treated, but also production residues with toxic or high-boiling solvents from chemistry and pharmaceutical production, washing solutions and paint sludge, polymer solutions, elastomer solutions from the solvent, adhesives and sealants.
  • CONFIRMATION COPY With the apparatuses is also a continuous or batchwise contact drying, water and / or solvent-moist products, often also under vacuum, performed.
  • the application is intended primarily for pigments, dyes, fine chemicals, additives such as salts, oxides, hydroxides, antioxidants, temperature-sensitive pharmaceutical and vitamin products, active ingredients, polymers, synthetic rubbers, polymer suspensions, latex, hydrogels, waxes, pesticides and residues from the chemical or pharmaceutical production, such as salts, catalysts, slags, waste liquors.
  • degassing and / or devolatilization may take place. This is applied to polymer melts, after condensation of polyester or polyamide melts, on spinning solutions for synthetic fibers and on polymer or elastomer granules or powder in the solid state.
  • a polycondensation reaction In a mixing kneader, a polycondensation reaction, usually continuous and usually in the melt, take place and is mainly used in the treatment of polyamides, polyesters, polyacetates, polyimides, thermoplastics, elastomers, silicones, urea resins, phenolic resins, detergents and fertilizers.
  • Ammonium polyphosphates sulfonates, pesticides and fertilizers.
  • reactions may take place solid / gaseous (e.g., carboxylation) or liquid / gaseous. This is used in the treatment of acetates, acids, Kolbe-Schmitt reactions, e.g. BON, Na salicylates, parahydroxibenzoates and pharmaceuticals.
  • Loosening and / or degassing in such mixing kneaders takes place in spinning solutions for synthetic fibers, polyamides, polyesters and celluloses.
  • Flushing takes place in the treatment or production of pigments.
  • a solid state postcondensation takes place in the production or treatment of polyesters and polyamides, a continuous mashing eg in the treatment of fibers, eg cellulose fibers with solvents, a crystallization from the melt or from solutions in the treatment of salts, fine chemicals, Polyols, alcoholates, compounding, mixing (continuous and / or batchwise) with polymer blends, silicone compositions, sealants, fly ash, coagulating (especially continuously) in the treatment of polymer suspensions.
  • a mixing kneader also multifunctional processes can be combined, for example heating, drying, melting, crystallizing, mixing, degassing, reacting - all this continuously or in batches. This produces and / or treats polymers, elastomers, inorganic products, residues, pharmaceutical products, food products, printing inks.
  • vacuum sublimation / desublimation may also occur, thereby reducing chemical precursors, e.g. Anthrachinon, metal chlorides, organometallic compounds, etc. are cleaned.
  • chemical precursors e.g. Anthrachinon, metal chlorides, organometallic compounds, etc.
  • pharmaceutical intermediates can be prepared.
  • Continuous carrier gas desublimation finds e.g. for organic intermediates, e.g. Anthraquinone and fine chemicals instead.
  • a single-shaft and two-shaft mixing kneader are distinguished.
  • a single-shaft mixing kneader is described for example in EP 91 405 497.1.
  • Multi-shaft mixing and kneading machines are described in CH-A 506 322, EP 0 517 068 B, DE 199 40 521 A1 or DE 101 60 535.
  • These mixing and kneading elements clean the disks and kneading bars of the first shaft.
  • the kneading bars on both shafts in turn clean the inside of the housing.
  • Object of the present invention is to provide a method which is more effective and in which in particular the monomer is better utilized.
  • the preparation of polyacrylonitrile by polymerization of its monomer is subject to a number of limitations which must be taken into account in the preparation process. This is especially true for the temperature control.
  • a heat input into the product or the starting material takes place in two ways. On the one hand there is contact heat, since usually a housing of the mixing kneader, the waves and / or the disc-shaped kneading and transport element are heated, on the other hand arises by kneading the product by means of the kneading elements, which interact with kneading counterparts in the rule , a significant shearing of the product, which generates heat in the product.
  • the monomer which contains corresponding initiators and / or catalysts, is introduced into the mixing kneader without the addition of solvent and can polymerize there in bulk.
  • a particular advantage of the present invention resides in the fact that functionalization of the polymer can already take place in the polymerization phase as a result of this bulk polymerization.
  • Functionalization means that property-modifying substances are added to the polymer or the forming polymer which influence the subsequent use of the polymer. For example, additional carboxyl groups or fluorine may be added, thereby improving the processing of the polyacrylonitrile into a carbon fiber. If, for example, metals are added, the conductivity of the polymer is thereby changed.
  • the functionalization can also be done by the addition of nanotubes.
  • the present invention relates specifically to the production of polyacrylonitrile
  • the claim is also made to the use of the process generally for the continuous performance of a polymerization. In this case, even a solution polymerization can be carried out.
  • Figure 1 is a schematic side view of a reactor for carrying out the inventive method for continuously carrying out a polymerization
  • Figure 2 are schematic representations of the inventive method in its individual stages in different embodiments.
  • a mixing kneader as reactor 1 is schematically indicated, in which a polymerization of acrylonitrile to polyacrylonitrile (PAN) takes place.
  • This reactor 1 has a diameter D and a length L.
  • at least one dome 2 is placed on it, through which in particular vaporized substances can pass and substances or condensates can enter the reactor.
  • An arrow represents an inlet 3 for the substance to be polymerized and an arrow the outlet 4 for the polymer.
  • the substance to be polymerized optionally passes through a liquid phase 5, a viscous phase 6 and a solid phase 7.
  • a liquid phase 5 In the interior of the reactor 1, the substance to be polymerized optionally passes through a liquid phase 5, a viscous phase 6 and a solid phase 7.
  • the latter is not necessarily given for the process according to the invention.
  • the reactor 1 is preferably a mixing kneader having an L / D ratio of 1 to 6. It may be a single or twin-screw kneader that is co-rotating or counter-rotating with the shafts at the same or different speeds as generally known in the art.
  • the process according to the invention proceeds according to FIG. 2 as follows: a) Addition of the substance to be polymerized
  • the substance to be polymerized (feed), in particular the monomer acrylonitrile (ACN) or a corresponding comonomer, is introduced into the reactor 1 at one or more feed sites.
  • Water in the case of precipitation polymerization or solvents in the case of solution polymerization, such as dimethyl sulfoxide (DMSO) or suitable monomers, e.g. Acrylic acid which releases water from carboxyl groups under thermal stress by anhydrogenation may also be introduced into the feed or together with the feed.
  • DMSO dimethyl sulfoxide
  • suitable monomers e.g.
  • Acrylic acid which releases water from carboxyl groups under thermal stress by anhydrogenation
  • Acrylonitrile, water or DMSO are used in the range of 50% to 100% and comonomers, such as itaconic acid or methacrylates or ethymethacrylates or styrene or vinyl acetates, or other monomers in the range 0% to 20%.
  • comonomers such as itaconic acid or methacrylates or ethymethacrylates or styrene or vinyl acetates, or other monomers in the range 0% to 20%.
  • Initiators are e.g. RAFT catalysts or sodium chlorates / sodium sulfide or hydrogen peroxide / thioglycerol or sodium bisulfite-potassium perulfate (more sodium bisulphite than potassium perulphate) or 2.2 azobis (2-methylpropionitrile, AIBN) or benzoyl peroxide (BPO) or other initiators added. This can be done in a pre-mixer 8 before dosing, together with the feed or later through the dome 2 directly into the kneader. c) cooling + evaporation
  • the cooling in the reactor 1 is preferably carried out by evaporation of water and / or evaporation of monomer M in the reactor.
  • the reaction conditions for the substance to be polymerized are 20 ° C to 150 ° C, preferably 60 ° C and 100mbar to 2000mbar, and a residence time of 1 to 300 minutes, preferably 30 minutes. d) condensation
  • the evaporated monomer or water can condense in the dome itself or in a heat exchanger on the reactor by reflux and be recycled.
  • the condensate in the feed zone which is provided in the range 0 to 0.5 of the process length of the reactor seen from the feed, returned again and there ideally mixed back.
  • An external condensation can also be effected by means of a spray condensation 9 with a monomer which optionally contains inhibitors and thus prevents the further reaction of the condensed monomer.
  • Oxygen may also be added to the condensed monomer to inhibit. e) discharge
  • the polymer may once accumulate as a solid and is then guided in the plugflow approximately at the end of the viscous zone 6.
  • the solid polymer is then discharged via an adjustable weir. If an overpressure prevails in the reactor, the resulting solid polymer is discharged with a rotary valve 11.
  • the PDI (polydispersity index) of the product is 1.0 to 2.0, preferably 1.1.
  • a degasser 12 is connected downstream.
  • water is preferably used as a stripping agent.
  • it may also be water from a monomer such as acrylic acid, which splits off from carboxyl groups under thermal stress by anhydration of water. The same is conceivable to enter water in several places in the degasser.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un procédé de production en continu de polyacrylonitrile (PAN) par polymérisation de son monomère acrylonitrile utilisé comme matériau de départ ou, en particulier, un procédé d'homopolymérisation et copolymérisation de diènes tels que des butadiènes, des isoprènes, des pipérylènes, pour obtenir des polymères. Le monomère est introduit par un orifice d'admission dans un mélangeur malaxeur, où il est transporté de l'orifice d'admission vers un orifice de sortie et polymérisé. Selon l'invention, on ajoute du monomère au matériau de départ, à un ou plusieurs endroits entre l'admission et la sortie, et on refroidit la matière en vaporisant le monomère. Le monomère vaporisé se condense et on le renvoie dans le mélangeur malaxeur.
PCT/EP2014/001463 2013-12-30 2014-05-30 Procédé de réalisation en continu d'une polymérisation WO2015101404A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013114965.0 2013-12-30
DE201310114965 DE102013114965A1 (de) 2012-12-28 2013-12-30 Verfahren zur kontinuierlichen Durchführung einer Polymerisation

Publications (1)

Publication Number Publication Date
WO2015101404A1 true WO2015101404A1 (fr) 2015-07-09

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PCT/EP2014/001463 WO2015101404A1 (fr) 2013-12-30 2014-05-30 Procédé de réalisation en continu d'une polymérisation

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DE (1) DE102013114965A1 (fr)
WO (1) WO2015101404A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH506322A (de) 1969-03-17 1971-04-30 List Heinz Mehrspindelige Misch- und Knetmaschine
EP0517068B1 (fr) 1991-06-07 1995-09-06 List Ag Pétrisseur de mélange
DE19940521A1 (de) 1999-08-26 2001-04-19 List Ag Arisdorf Mischkneter
DE10160535A1 (de) 2001-12-10 2003-06-18 List Ag Radial oder axial reinigende Mischbarren
DE102006015541A1 (de) * 2006-03-31 2007-10-04 List Holding Ag Verfahren und Vorrichtung zur Behandlung von zähviskosen Produkten

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH506322A (de) 1969-03-17 1971-04-30 List Heinz Mehrspindelige Misch- und Knetmaschine
EP0517068B1 (fr) 1991-06-07 1995-09-06 List Ag Pétrisseur de mélange
DE19940521A1 (de) 1999-08-26 2001-04-19 List Ag Arisdorf Mischkneter
DE10160535A1 (de) 2001-12-10 2003-06-18 List Ag Radial oder axial reinigende Mischbarren
DE102006015541A1 (de) * 2006-03-31 2007-10-04 List Holding Ag Verfahren und Vorrichtung zur Behandlung von zähviskosen Produkten

Also Published As

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DE102013114965A1 (de) 2014-07-03

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