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WO1997001585A1 - Procede de polymerisation anionique d'aromates vinyliques - Google Patents

Procede de polymerisation anionique d'aromates vinyliques Download PDF

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Publication number
WO1997001585A1
WO1997001585A1 PCT/EP1996/002738 EP9602738W WO9701585A1 WO 1997001585 A1 WO1997001585 A1 WO 1997001585A1 EP 9602738 W EP9602738 W EP 9602738W WO 9701585 A1 WO9701585 A1 WO 9701585A1
Authority
WO
WIPO (PCT)
Prior art keywords
reactor
styrene
polymerization
anionic polymerization
temperature
Prior art date
Application number
PCT/EP1996/002738
Other languages
German (de)
English (en)
Inventor
Wolfgang Loth
Konrad Knoll
Hermann Gausepohl
Original Assignee
Basf Aktiengesellschaft
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 Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO1997001585A1 publication Critical patent/WO1997001585A1/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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons

Definitions

  • the invention relates to a continuous process for the rapid, economical and safe production of vinylaromatic polymers such as polystyrene, which is thereby also obtained in improved quality, namely improved thermal stability.
  • the process uses anionic polymerization, the high space-time yield resulting in a small and safely controllable reactor.
  • the heat of reaction obtained is used in the non-isothermal process according to the invention to store energy for the subsequent removal of volatile constituents of the reaction mixture by heating the reaction medium to near the degassing temperature, which means a further advantage.
  • the mean residence time is more than
  • the process described can be operated with certain restrictions in a plant which is set up for radical polymerization, but because of the low possibility of increasing the space-time yield compared to the yield,
  • D5 describes the possibility of allowing the free-radical polymerization or copolymerization of styrene to take place under a partially adiabatic reaction regime and in this way to achieve higher conversions, i.e. to reaction mixtures with a lower content of residual monomers.
  • the object of the invention is to provide a process for the continuous, rapid, economical and safe production of vinylaromatic polymers such as polystyrene, which should also be obtained in improved quality, namely improved thermal stability .
  • the invention is based on the observation that the discontinuous, anionic polymerization of styrene in, for example, decalin as solvent leads to an unexpectedly narrow molar mass distribution even at a temperature of 170 to 270 ° C. if the reaction is carried out essentially without heat exchange with the Environment (ie adiabatically) is carried out and the residence time of the reaction mixture at the highest temperature occurring is limited to less than about 30 seconds. Here quantitative turnover can be achieved.
  • the red-colored, viscous solution obtained can be converted into a colorless liquid by protonation using customary means (alcohols, water), from which a colorless polymer can be isolated by dilution and precipitation.
  • Immediate subject matter of the invention is a preferably continuously (continuously) carried out process for the anionic, non-isothermal polymerization or copolymerization of vinyl aromatic compounds, in particular styrene, which is characterized in that the polymerization is solvent-free or with moderate dilution with an inert solvent a concentration of 40 to 100 percent by weight under non-isothermal conditions is carried out in such a way that the polymer solution leaving the reaction space has a temperature of at least 170 ° C.
  • the dwell time must be measured so that complete conversion is possible. At a temperature that can reach 170 to 270 ° C depending on the concentration of the monomer, a limitation to 300 to 30 seconds or less is recommended, the higher temperature requiring the shorter residence time.
  • the process according to the invention can be carried out in any pressure- and temperature-resistant reactor which permits a broad or narrow distribution of residence times.
  • stirred tank reactors and loop reactors as well as tubular reactors or tube bundle reactors with or without static or movable installations are suitable.
  • Tube or tube bundle reactors with or without static internals are preferred. The example below is based on the use of tubular reactors.
  • the reaction mixture to be polymerized generally consists of at least 40 percent by weight of monomer and correspondingly at most 60 percent by weight of solvent, a monomer concentration of, for example, 60 to 80 percent by weight being preferred, and the required amount of initiator, which, as is known, depends on the intended molecular weight of the polymer is selected and generally 0.001 to 0.1 part by weight per 100 parts of monomer.
  • Monomer is short compared to the total residence time in the reaction space, advantageously not more than about 10% of the residence time.
  • the flow rate should also be checked and kept in a range which ensures that the available reaction space is used on the one hand and on the other hand is sufficient for a practically complete conversion.
  • the absolute flow velocity is expediently in the range of over 0.05, preferably over 0.1 m / s; in a pipe without internals, this results in a shear rate (flow gradient) near the wall of at least 100, preferably at least 400 [1 / s].
  • the reactor to be used can advantageously be heated on the feed side, so that the reaction mixture can be brought to operating temperature as quickly as possible.
  • a first pipe section can be provided with a heating jacket, which quickly heats the solution to, for example, 80 to 100 ° C. Any small amounts of impurities present initially react here (possibly using a certain amount of initiator, which must be taken into account when determining the required amount of initiator) and the polymerization starts.
  • the polymerization proceeds almost spontaneously (generally in less than 20 seconds), the temperature depending rises to 170 to 270 ° C depending on the solvent content and insulation quality.
  • the converted polymer solution or melt leaves the reactor in a readily flowable state and is mixed with a polar protonating agent in a subsequent mixing section and thereby stabilized and decolorized and then by conventional means (vacuum degasifier, one or more stages, with / without addition) a stripping agent; extruder) processed into polymer granules.
  • the polymers obtained advantageously have a residual monomer content of less than 50, in favorable cases even less than 10 ppm.
  • Vinyl aromatic monomers for use in the process of the invention are primarily styrene, further e.g. p-methylstyrene, p-tert-butylstyrene, alpha-methylstyrene such as 1,1-diphenylethylene and also other monomers capable of anionic copolymerization, such as, in particular, the technically customary dienes.
  • the monomers can be used individually or as mixtures and must have a degree of purity suitable for anionic polymerization.
  • Suitable solvents are hydrocarbons which are inert under the reaction conditions and preferably contain 4 to 12 carbon atoms, such as cyclohexane, methylcyclohexane, isooctane, benzene, toluene, xylene, ethylbenzene or decalin. It is essential that the solvent used is free of proton-active impurities which would decompose the organometallic initiator. It is therefore distilled and dried thoroughly before use.
  • Mono- and bifunctional organometallic compounds can be used as initiators.
  • the easily manageable lithium alkyls n-butyl and sec-butyllithium are preferred.
  • the remaining tube section of 4000 mm is unheated and thermally insulated.
  • the temperature jacket is heated to 100 ° C. with an oil thermostat and the reactor is kept at 1000 ° C. per hour with three separate pumps, 1000 g styrene, 300 g ethylbenzene and 30 g 4% solution of s-butyl lithium in ethylbenzene fed continuously. A system pressure of approximately 22 bar is established.
  • the low-viscosity polymer solution leaving the reactor is continuously mixed under process pressure with an HPLC pump with 60 ml / h of a solution of 20 parts of methanol in 80 parts of ethylbenzene and homogenized in a static mixer.
  • the polymer solution obtained has a temperature of 235 ° C. It is decompressed into a container kept at 15 mbar via a dosing valve and the polymer melt is drawn off via a screw pump, pulled through a nozzle, cooled and granulated.
  • Crystal-clear, discoloration-free polystyrene with a residual monomer content of less than 5 ppm is obtained.
  • the GPC analysis gives a weight average molecular weight (M w ) of 115,000 g / mol and a number average molecular weight (M n ) of 96,000 g / mol, from which a distribution width (M w / M n ) of 1.20 is calculated.
  • M w weight average molecular weight
  • M n number average molecular weight
  • M n distribution width
  • the example shows that with the process according to the invention with a space-time yield of 1500 kg / l- * h- ⁇ a previously unattainable product quality can be generated.

Landscapes

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

Abstract

L'invention concerne un procédé de polymérisation ou de copolymérisation anionique de composés vinylaromatiques, tels que le styrène en solution avec une concentration initiale en monomères de 40 à 100 % en poids, dans des conditions non isothermes, de préférence dans un réacteur tubulaire ou à faisceau tubulaire qui est pourvu de moyens sur une section considérable. Ces moyens empêchent un transfert de chaleur avec l'environnement. On utilise, de préférence, comme solvant, du toluène, du méthylcyclohexane, de l'éthylbenzène ou du Dékalin, et la solution de polymère quittant la chambre de réaction est à une température d'au moins 170 °C. Un polymère styrène est produit avec une teneur en monomère inférieure à 50 ppm.
PCT/EP1996/002738 1995-06-29 1996-06-20 Procede de polymerisation anionique d'aromates vinyliques WO1997001585A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995123587 DE19523587A1 (de) 1995-06-29 1995-06-29 Verfahren zur anionischen Polymerisation von Vinylaromaten
DE19523587.8 1995-06-29

Publications (1)

Publication Number Publication Date
WO1997001585A1 true WO1997001585A1 (fr) 1997-01-16

Family

ID=7765516

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/002738 WO1997001585A1 (fr) 1995-06-29 1996-06-20 Procede de polymerisation anionique d'aromates vinyliques

Country Status (2)

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DE (1) DE19523587A1 (fr)
WO (1) WO1997001585A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6448353B1 (en) 2000-02-08 2002-09-10 3M Innovative Properties Company Continuous process for the production of controlled architecture materials
US6979717B2 (en) 2001-08-13 2005-12-27 Moore Eugene R Anionic process design for rapid polymerization of polystyrene without gel formation and product produced there from

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000019517A (ko) * 1998-09-12 2000-04-15 이정국 스티렌 다이머 및 스티렌 트리머의 용출이 되지 않는 식품포장재용 고순도 폴리스티렌 및 그의 제조방법

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2161178A1 (de) * 1970-12-10 1972-07-06 Int Synthetic Rubber Verfahren zur Polymerisation von vinylaromatischen Verbindungen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2161178A1 (de) * 1970-12-10 1972-07-06 Int Synthetic Rubber Verfahren zur Polymerisation von vinylaromatischen Verbindungen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6448353B1 (en) 2000-02-08 2002-09-10 3M Innovative Properties Company Continuous process for the production of controlled architecture materials
US6979717B2 (en) 2001-08-13 2005-12-27 Moore Eugene R Anionic process design for rapid polymerization of polystyrene without gel formation and product produced there from

Also Published As

Publication number Publication date
DE19523587A1 (de) 1997-01-02

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