WO2003016363A2 - Dispositif et procede pour realiser une polymerisation - Google Patents

Dispositif et procede pour realiser une polymerisation Download PDF

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Publication number
WO2003016363A2
WO2003016363A2 PCT/EP2002/008297 EP0208297W WO03016363A2 WO 2003016363 A2 WO2003016363 A2 WO 2003016363A2 EP 0208297 W EP0208297 W EP 0208297W WO 03016363 A2 WO03016363 A2 WO 03016363A2
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WO
WIPO (PCT)
Prior art keywords
polymerization
vinyl chloride
carried out
temperature
reaction
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/EP2002/008297
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German (de)
English (en)
Inventor
Heinz Klippert
Roland SCHÄFER
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.)
Westlake Vinnolit GmbH and Co KG
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Vinnolit GmbH and Co KG
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Filing date
Publication date
Application filed by Vinnolit GmbH and Co KG filed Critical Vinnolit GmbH and Co KG
Publication of WO2003016363A2 publication Critical patent/WO2003016363A2/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • 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
    • C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
    • C08F2/004—Scale prevention in a polymerisation reactor or its auxiliary parts by a prior coating on the reactor walls
    • 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
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00247—Fouling of the reactor or the process equipment
    • 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
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00254—Formation of unwanted polymer, such as "pop-corn"
    • 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
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0277—Metal based
    • B01J2219/0286—Steel
    • 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
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0277—Metal based
    • B01J2219/029—Non-ferrous metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation

Definitions

  • the invention relates to an apparatus and a method for polymerization, in particular a pressure vessel for the polymerization of vinyl chloride and / or of monomers copolymerizable with vinyl chloride.
  • anti-coating agents in particular based on phenothiazine oligomers, polyarylphenols, phenoxazine derivatives, phenol-formaldehyde condensation products and bisphenol-A condensation products, are used to suppress its formation, which are applied in different, generally known ways the inner wall of the container and the surfaces of the internals in the container are applied.
  • a deposit-preventing additive e.g. of an inorganic reducing agent (e.g. sodium nitrite) can be added to suppress its formation, which are applied in different, generally known ways the inner wall of the container and the surfaces of the internals in the container are applied.
  • an inorganic reducing agent e.g. sodium nitrite
  • the invention is therefore based on the object of creating a device and a method for polymerization which overcomes the disadvantages of the prior art by creating a permanently effective modification of the surface of the reaction vessel and / or the existing internals, as a result of which the Polymer deposits on the reaction vessel wall and / or the internals permanently prevented is changed and consequently the use of expensive anti-fouling agents and / or additives can be dispensed with.
  • the quasi-crystalline coating of a device for polymerization can be applied to a device that is used or to a device that is still new.
  • the coating is applied to e.g. Sandblasting, mechanical grinding, electropolishing according to prepared and cleaned inner wall made of e.g. Stainless steel and / or carbon steel by means of chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma coating and / or flame spraying, as known for example from EP 356287 or US Pat. No. 5,433,978.
  • a device for polymerization such as thermal sensors, baffles and / or stirrer blades
  • all surfaces of the internals and / or the inner walls of the device can be completely or partially coated with a quasi-crystalline surface.
  • the surfaces or inner walls completely coated with a quasi-crystalline surface.
  • aluminum transition metal alloy here comprises an alloy of at least two metals, in particular of more than two metals, such as a ternary, quaternary and / or higher alloy, as long as the stoichiometry involves the formation of a quasi-crystalline phase, as described, for example, by Stephens and Goldman in "The structure of Quasicrystals", Scientific American, April 1991.
  • Sensors such as temperature sensors, pressure sensors, stirrer blades and / or baffles or the like are referred to as internals of the pressure vessel.
  • all parts of the pressure vessel that come into contact with the reaction mixture can be coated with a quasi-crystalline alloy to avoid a deposit.
  • the coating will be carried out as completely as possible on the inner surface of the device and / or on its internals, so that the formation of a coating is suppressed and the homogeneity of the surface of the inner wall and / or the surface of the internals which come into contact with the reaction mixture (and thus Influence the course of the reaction and / or the quality of the product).
  • the device can e.g. a pressure vessel for the production of a plastic such as for the polymerization of monomers such as vinyl chloride and its copolymers such as vinyl esters, e.g. Vinyl acetate and vinyl propionate, such as (meth) acrylic acid and its
  • Esters and salts such as maleic acid, fumaric acid and their esters and anhydrides such as diene monomers such as butadiene, chloroprene and isoprene such as styrene and such as acrylonitrile. These monomers can be used alone or in combination of two or more monomers.
  • the containers coated according to the invention are particularly effective in the homopolymerization of vinyl chloride or the copolymerization of vinyl chloride with comonomers, which e.g. Vinyl esters such as vinyl acetate or vinyl propionate or (meth) acrylic acid esters such as methacrylate, butyl acrylate, 2-ethylhexyl acrylate or methyl methacrylate or olefins such as ethene and propene or acrylonitrile, styrene and vinylidene chloride can be.
  • vinyl esters such as vinyl acetate or vinyl propionate or (meth) acrylic acid esters such as methacrylate, butyl acrylate, 2-ethylhexyl acrylate or methyl methacrylate or olefins such as ethene and propene or acrylonitrile, styrene and vinylidene chloride
  • comonomers which e.g. Vinyl esters
  • the inner wall of a polymerisation device to be coated is made of steel, in particular of carbon steel and / or a stainless steel such as e.g. V2A or V4A.
  • the polymerization device is used, for example, for the production of plastics and can in particular be a pressure vessel.
  • the invention was made with regard to the polymerization of vinyl chloride, if appropriate in the presence of monomers copolymerizable with vinyl chloride, in the aqueous phase at a temperature between 35 and 90 ° C. under elevated pressure, in the presence of at least one free radical initiator and at least one suspending agent and / or an emulsifier is developed. This process can be carried out continuously or discontinuously because of the avoidance of the coating on the inner wall.
  • the temperature of the reaction mixture in particular of the water, can be above the polymerization temperature.
  • the temperature control in the pressure vessel or reactor takes place, for example, via external or internal heating and / or cooling circuits and / or units.
  • the reaction mixture in the container is brought to the polymerization temperature by charging part of the water of reaction as preheated water, the temperature of which is higher than the polymerization temperature, by the required amount of heat in whole or in part via the heating or cooling circuit or entirely or is introduced in part via additional heating and / or cooling units and / or in that the required amount of heat is introduced in whole or in part by the direct introduction of steam into the liquid reaction phase.
  • the aluminum transition metal alloy comprises at least two metals, aluminum (Al) and a transition metal (M 1 / M 2 ). It is advantageous to use a ternary, quaternary or higher alloy, the decisive factor in the choice being the temperature / pressure range in which the alloy forms the most stable quasi-crystalline phase.
  • the alloy comprises, for example, a compound of the general formula M0-M1-M 2 , where M ° is aluminum or aluminum / beryllium; M 1 is a transition metal selected from the group comprising copper (Cu), cobalt (Co), nickel (Ni), palladium (Pd) and / or platinum (Pt) and M 2 is a transition metal selected from the group comprising iron (Fe ), Ruthenium
  • the alloy has a composition in which the Al content is 55 to 90 atom%, the M 1 content is at least 5 atom% and the M 2 content is the rest. Alloys are mentioned as examples, whose Al content is 60 to 80 atom%, preferably 60 to 75 atom%, whose M x content 10 to 30 atom%, preferably 10 to 20 atom% and whose M 2 content 10 to 25 Atom%, preferably 10 to 20 atom%.
  • Cu and / or Ni and / or M 2 Fe and / or Co is preferably used as M 1 .
  • reaction vessels and the internals are coated with a continuous, quasi-crystalline surface in a manner known to the person skilled in the art from EP 356287 and US 5433978 by CVD, PVD, plasma coating, flame spraying or other suitable processes. Any subsequent surface refinement that may be required, such as grinding or polishing, is also carried out in a manner known to those skilled in the art.
  • Quasicrystalline compounds represent a new type of metal alloy, they have a well-ordered crystal structure, but the crystal lattice shows no periodicity. A number of quasicrystalline compounds have now been found, all of which are basically for the
  • Coating surfaces of reaction vessels and their internals are suitable. Two quasi-crystalline surfaces with different compositions were examined. These were i-Al-Cu-Fe and i-Al-Ni-Co alloys, which were applied to V4A and C steel.
  • a flat metal plate made of V4A steel was determined, half of which was made using the PVD method with an i-Al-Ni-Co metal alloy, the composition of which was Al 69 , 8 Nii 5 , ⁇ C ⁇ i 5 , ⁇ was coated and attached to the reactor wall.
  • the reactor was cleared by evacuation 0 2 - and 40 l of water, 42 g of a polyvinyl alcohol with a viscosity of the 4% strength aqueous solution of 5 mPas and a saponification number of 280, 42 g of a methylhydroxypropyl cellulose with a viscosity the 2% aqueous solution of 45 mPas, 150 g sorbitan monolearate, 80 g of a water-insoluble polyvinyl alcohol with a saponification number of 405.
  • VCM vinyl chloride
  • 410 kg of water were simultaneously charged into the reactor while stirring with a stirring energy of 1.6 kW / m 3 , the temperature of the water being chosen so that an internal temperature of 70 ° C. was reached.
  • the polymerization is started at this temperature by adding 306 g of Perkadox® 16W40 and 152 g of dilauroyl peroxide. It is stopped after 5 hours and a pressure drop of 4 bar. After emptying the reactor and rinsing the reactor surface with washing water, the sample plate was examined for PVC coating.
  • the coated part with the quasi-crystalline surface made of Al-Ni-Co was completely free of deposits, while the uncoated part of the test specimen was covered with a continuous layer of polyvinyl chloride.
  • Example 2 The procedure was as in Example 2. The reactor was made 0 2 - free by evacuation and 16 l of water, 56 g of methylhydroxypropyl cellulose with a viscosity of the 2% strength aqueous solution of 35 mPas, 28 g of a non-water-soluble polyvinyl alcohol were also added a saponification number of 405, 27 g of 30% hydrogen peroxide, 210 g of NaHC0 3 in the reactor. Thereafter, 140 kg of vinyl chloride and then 51 g of ethyl chloroformate were charged with stirring. By adding 164 liters of hot water, the polymerization temperature was set at 56 ° C.
  • the sleeve of the thermal sensor in an Im 3 reactor made of V4A steel was completely coated with an i-Al-Ni-Co metal alloy using the PVD method, the composition of which was determined as Al 6 9, 9 Nii5, ⁇ C ⁇ i5, o, coated and installed in the reactor. The procedure was then as in Example 1. After emptying the reactor and rinsing the reactor surface with wash water, the thermal sensor was examined for PVC coating.

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

Abstract

La présente invention concerne un dispositif et un procédé pour réaliser une polymérisation, notamment un réservoir sous pression permettant la polymérisation de chlorure de vinyle et/ou de monomères pouvant être copolymérisés avec du chlorure de vinyle. Le dispositif et le procédé selon cette invention permettent de mettre en oeuvre une réaction en continu puisqu'un revêtement quasi cristallin empêche la formation de dépôts sur les parois internes.
PCT/EP2002/008297 2001-07-25 2002-07-25 Dispositif et procede pour realiser une polymerisation Ceased WO2003016363A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10135402.9 2001-07-25
DE2001135402 DE10135402A1 (de) 2001-07-25 2001-07-25 Vorrichtung und Verfahren zur Polymerisation

Publications (1)

Publication Number Publication Date
WO2003016363A2 true WO2003016363A2 (fr) 2003-02-27

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PCT/EP2002/008297 Ceased WO2003016363A2 (fr) 2001-07-25 2002-07-25 Dispositif et procede pour realiser une polymerisation

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WO (1) WO2003016363A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10358813A1 (de) * 2003-12-16 2005-07-21 Alstom Technology Ltd Quasikristalline Legierungen und deren Verwendung als Beschichtung

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1837484A3 (fr) * 2006-03-23 2007-11-28 Siemens Aktiengesellschaft Revêtement quasi-crisytallin et son utilisation comme revêtement de barrière thermique
DE102014000933A1 (de) * 2013-12-16 2015-06-18 Epc Engineering Consulting Gmbh Reaktorgefäß oder Reaktorgefäßauskleidung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10358813A1 (de) * 2003-12-16 2005-07-21 Alstom Technology Ltd Quasikristalline Legierungen und deren Verwendung als Beschichtung

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Publication number Publication date
DE10135402A1 (de) 2003-02-13

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